DE102005056780A1 - Mixture for coating process, useful e.g. as active and passive corrosion protective coating, comprises a liquid, separating- or lubricating agent and sliding surface supporting substance e.g. antimicrobial active substance and fungicide - Google Patents

Abstract

Mixture for coating process, comprises a liquid comprising a substance or a plasma preparation with cross-linkable support and at least further functional components such as e.g. marking substance; separating- or lubricating agent; and sliding surface supporting substance e.g. antimicrobial active substance, fungicide, insecticide, hormone, protein, nutrient, pheromone, medically effective material, organoleptic active substance and magnetic substance. Mixture for coating process, comprises a liquid comprising a substance or a plasma preparation with cross-linkable support and at least further a functional components such as marking substance; separating- or lubricating agent; and sliding surface supporting substance such as antimicrobial active substance, fungicide, insecticide, acaricide, algicide, virucide, pesticide, (bio)-catalyst, enzyme, hormone, protein, nutrient, pheromone, medically effective material, organoleptic active substance (preferably odor- and aromatic substance), emulsifier, surfactant, growth substance, UV-absorber, photochrome and electrochrome substance, reflective substance, conductive substance, waxes, oil and lubricant, corrosion protective inhibitor, dye, luminescence dye, organic or inorganic dye pigment, magnetic substance, organic or inorganic solid particle with primary particle size of up to 5 mu m, preferably 1 mu m, preferably nano-filler, liquid crystal, organic solid substance, nano-filler with multitude of cross-linking point and carbon particle. Independent claims are included for: (1) a coating process comprising coating a liquid layer of the mixture on solid surface and cross-linking the liquid layer, such that solid layer is formed; and (2) a coated body, where the coating is obtained by the above process.

Description

The The invention relates to a product with a layer system of at least a cover layer and one between the cover layer and the product arranged plasma polymer molding layer, wherein the plasma polymers Impression layer containing a marking substance. It also concerns a procedure for marking a plasma polymer molding layer, a process for detecting a residue a plasma polymer molding layer on a molded product, the use of a mixture of precursor and marking substance for marking a plasma polymer impression layer, the use a marking substance for detecting a residue a plasma polymer molding layer on a molded product and a molding product comprising a labeled plasma polymer Impression layer on the surface.

The Molding of surfaces often takes place according to the prior art by pouring. It is it usually desired that the template or the original is as dimensionally as possible and Precision molded. additionally it is often desirable that the impression results (impression products) on their surface a Protection, for example by a protective layer obtained. To the pour off are predominantly low-viscosity polymers Used materials that harden on the surface to be molded. The casting material must be after curing easily removed from the molded product, this distance preferably residue should be done. Therefore, the casting weight should be compared to the surface of the product to be molded Have properties, allowing a separation of the casting material from the product or facilitate (dehäsive Properties). Thus, for the production of e.g. imitation leather used in many casts on the surface of Leather is applied, cured on this and then from the leather be separated so that the surface of the then cured casting material represents a negative of the molded (original) leather surface. Also in the field of microsystem technology (e.g., manufacturing mechanical Microteile) it is necessary to molds with finest structures very much to reproduce exactly to make flawless replicas.

The these requirements for the impression material limit the Number of well-usable materials known from the prior art very much one. Today's casts suffer u.a. many times under that they change shape can change a "flow" (e.g. under mechanical stress) that they are too soft (lack of mechanical Stability) or own a structure, so that the original Structure (possibly a nanostructure) of the original changed reproduced becomes. A problem is also the residue-free Separating the impression product from the surface to be molded, in particular during the molding of nano and microstructures. Other problems can be that the materials for some applications have insufficient temperature stability, are not sufficiently dimensionally stable and / or no suitable primer for subsequent coatings for example, to protect or stabilize the Negative (of the impression product) should serve.

From the prior art, a Dehäsivbeschichtung prepared by means of low-pressure plasma polymerization is known: The DE 100 34 737 C2 discloses a plasma polymeric release liner having dehiscence properties so as to facilitate separation of the casting mass (after curing) from the forming master. This function is fulfilled by the fact that the plasma-polymer layer has an outstanding adhesion (adhesion) to the shaping surface, but has dehesive properties compared to the impression compound. This is achieved by the design of the plasma polymer layer, which is produced as a gradient layer with temporal variation of the deposition conditions. With such a coating, for example, metallic molds (negatives) are coated in plastics processing in order to be able to dispense with liquid release agents. The layer is characterized in particular by the fact that it allows a residue-free impression.

disadvantage The disclosed coating is that the original through the Coating changed irrevocably becomes. Such a change is e.g. For Artworks unacceptable. Here one pulls at present non-contact Procedure before. Further, the molded negative becomes the volume the coating (release layer) compared to the original reduced or - if first as a surface to be molded (Original) a negative was generated, which subsequently with the layer was coated - the after molding resulting positive model to the corresponding Volume reduced from the original. Ultimately, then leads the coating step means that the molded product of Original in addition differs. In addition, there is no possibility of the product of Impression (positive model or negative) during casting only with one, for example protective, To provide coating.

Disadvantage in the event that the original (the surface to be molded) classic with impression materials is molded, it is that the choice of materials is severely limited. It also follows that the smallest surface structures (nanostructures, ie structures in the size range of 10 nm-500 nm) and the resulting surface properties can not be imaged.

The DE 10353530 discloses a support system for a wafer comprising a cover layer and a release layer in which the release layer adheres more firmly to the cover layer than to the wafer. As a result, the entire carrier system is mechanically detachable from the wafer when needed. However, it is desirable when detaching the carrier layer that it can be determined whether the separating layer has actually been completely detached from the wafer. Residues of such a layer or of precursors thereof can severely disrupt the further processing of a wafer and make it unusable in the worst case. A disadvantage of the disclosed product (wafer) with a layer system is that it is not possible to ascertain in terms of quality assurance or only with great effort whether the impression layer has completely detached from the object to be shaped.

It For example, it is conceivable that a coating process is faulty carried out or the product to be molded was contaminated, so that the impression layer (possibly locally) changed adhesion properties or, if necessary, by incomplete wetting with a former liquid Precursor, an altered has internal strength or no good primer for the topcoat supplies. The usual liquid Precursors such as silicone oils (for the Case that a liquid Precursor used) are colorless and can be used for residues with a layer thickness less than 400-500 nm can be detected only with considerable technical effort. Often revealed But even from very low contamination of silicone oil considerable Problems, for example a subsequent one Gluing or coating the surface.

Therefore, it is desirable to determine if and to what extent the release layer has been completely released from the wafer. For this gives the DE 10353530 no indication.

task It was the object of the present invention to overcome the disadvantages of the prior art overcome the technique. Solved This task is performed by a product with layer system of at least a cover layer and one between the cover layer and an intermediate layer the cover layer and the product arranged Abformschicht, wherein the impression layer is a plasma polymer layer containing the contours of the product and adheres more firmly to the covering layer than on the product, and wherein the impression layer is a marking substance contains.

at a "product" is around any body with a solid surface, its surface (at least partially) to be molded.

• – Kunst- und Spaltleder
• – Optische Strukturen (Fresnel-Linsen, Beugungsgitter, Hologramme)
• – Gebrauchsgegenstände mit Nanostrukturierung
• – Formwerkzeuge für Gebrauchsgegenstände mit Nanostrukturierung
• – Formwerkzeuge für Gebrauchsgegenstände mit Wasser- oder schmutzabweisenden Oberflächenstrukturen
• – Mikroplättchen; Dies
• – Wafer mit elektronischen Bauelementen (ggf. mit Passivierungsschicht)

Products can be in particular:

• - Artificial and split leather
• - Optical structures (Fresnel lenses, diffraction gratings, holograms)
• - commodities with nanostructuring
• - Molds for commodities with nanostructuring
• - Molds for everyday objects with water- or dirt-repellent surface structures
• - microplates; This
• - wafers with electronic components (possibly with passivation layer)

The Cover layer serves to the impression layer after separation from the Product and, if necessary, to stabilize it. at the molding layer is according to the invention a plasma polymer layer, the method by which this impression layer was applied is not critical as long as the composition of the impression layer and the order method chosen is that the adhesion of the molding layer to the cover layer is higher as on the surface of the product. From DC to microwave excitation to Production of the plasma is all possible. Also the use of atmospheric pressure plasmas is executable.

A marking substance in the context of this application is a chemical compound or substance which can be detected non-invasively, that is, which can be detected without being altered in its chemical structure. A marking substance can be detected more easily than silicone oil or as the respectively simultaneously used (unlabeled) precursor. Lighter means in this context that the proof with a lower expenditure on equipment (eg with a Light microscopy instead of XPS), or after separation of the impression layer of the product faster (within a shorter period) than in an equal volume of silicone oil or (unlabeled) Precursor, preferably because no further change (sample preparation) made at the Positv for a test must become. For the person skilled in the art, it is clear that for the implementation of the invention described in the context of this text, the marking substance must be selected so that it facilitates the detection of residues of the impression layer or of the precursor on the object compared to an unmarked impression layer or an unlabeled precursor or allows.

One Advantage of the product according to the invention with marked layer system is that after separation of the Layer system of the product by remaining on the top layer Impression layer e.g. a dimensionally true negative is present, which - as in many cases desired - at his surface a plasma polymer layer, for example, take over protective functions can. This layer may also be due to its dehäsiven properties but against the material of the surface of the molded product positive in the production of positive models of this product If a manufactured negative, e.g. for producing such Positive models can be used the dehasiven Properties of the layer with appropriate choice of the positive model material serve to support the separation of the positive model from the negative.

Of the particular advantage of the product according to the invention with labeled Layer system, however, is that after separation of the impression layer be checked on the product can, if and to what extent the impression layer actually-completely from Product was removed. This is especially rare (Works of art) or high-quality (wafers with electrical assemblies) to be molded Objects of high importance and is an essential help for deciding whether that Product processed as desired can be (for example in a further molding step), whether the product in certain circumstances has become unusable or another cleaning step necessary is.

Prefers is a product according to the invention with layer system, wherein the product is a wafer.

Prefers For example, a wafer includes electronic components or mechanical components (mechanical micro parts). Another preferred product is a mechanical microtext.

In the case, that the product is a wafer takes over the impression layer additionally the function of a release layer: In the preferred product according to the invention With layer system it comes to the wafer for certain processing steps to protect or manageable. At the same time, however, the surface of the Wafers molded from the molding layer, so that at the separation the impression layer (release layer) from the wafer, the release layer Negative represents the wafer surface covered by it. Accordingly has in the preferred product according to the invention, in which the Produce is a wafer, the impression layer simultaneously the function a separation layer. This dual function can also be used in other applications available. Accordingly, the use or the function Of course, the plasma polymer molding layer as a release layer with of the present invention.

Prefers is a product according to the invention with layer system, wherein the impression layer has a gradient layer and / or an adhesive zone adjacent to the cover layer and a dehesive zone adjacent to the product, and optionally a transition zone includes, wherein the adhesive and the dehesive zone are composed of different materials.

The Forming the impression layer as a gradient layer offers the advantage that the plasma polymer layer optimally in their adhesive properties adapted to the contacting layers (product, cover layer) be so that the desired Effect of the impression layer can be optimally realized.

Especially preferred is a product according to the invention, wherein the impression layer on the product side a formerly liquid precursor as an integral part.

• – Er sollte im Vakuum nicht zu wesentlichen Teilen verdampfen.
• – Er sollte eine trennaktive Substanz sein (z.B. ein Silikonöl wie AK5 bis AK50 der Firma Wacker Chemie).

A particularly good quality for the Dehäsiveigenschaften the impression layer can be achieved by the fact that the product to be coated is wetted before introduction into the vacuum chamber (the low-pressure plasma) thin with a liquid precursor to which the following requirements are made:

• - He should not evaporate to a significant extent in a vacuum.
• - It should be a separation active substance (eg a silicone oil such as AK5 to AK50 from Wacker Chemie).

Of the Professional becomes the liquid one Precursor preferably to the chemistry of the plasma polymer molding layer adjust, and the precursor should preferably applied as thin (e.g., 0.1 to 50 nm) that the precursor will be replaced by the subsequent plasma process Part of the plasma polymer coating is. Especially preferred is going to be that first liquid Precursor completely is integrated into the molding layer. The liquid precursor is placed on the Substrate (the product) preferably by dipping, spraying or spin coating applied.

Of the so applied liquid Precursor becomes the active ingredient in the first step of plasma polymerization of the plasma (electrons, photons, ions, etc.) exposed. Thereby usually takes place both crosslinking of the precursor molecules with one another (preferred to the polymer chain or to a three-dimensional polymer backbone) instead as well as one with the layer that is deposited from the gas phase. The first liquid Precursor is thus an integral part of the plasma polymer Abformschicht and can therefore also with this of the product be removed again.

Of the Professional becomes the kind of liquid Precursors and the coating thickness (on the substrate), as well the subsequent steps of the plasma polymer coating on each other agree that a broad integration, preferably a full integration of the first liquid Precursors takes place in the plasma polymer coating.

Especially preferred is a product according to the invention with layer system, wherein the impression layer on the product side a formerly liquid Includes precursor as an integral part and the marking Substance essentially only in the region of the impression layer which also contains the formerly liquid precursor.

At the Generating the impression layer for the said preferred product according to the invention with a layer system may be the same or directly before or be applied after the precursor, even before the plasma polymer Deposition process begins and as long as the precursor is still liquid. If the precursor and the marker are matched to each other, is it is easily possible in this way, the marker to the decisive point of the impression layer (or release layer) The main function of the marker is as described, the Proof of the degree of separation of the molding layer from the molded-off Product over To allow for the procedure of This is natural particularly important in the area of contact between the product and the product Shaping layer.

The Lastgeschilderte preferably inventive product also offers the Advantage that the marking substance reliably integrated into the impression layer and only for their function consumes necessary amount of marking substance becomes.

Especially preferred is a product according to the invention with layer system, the product side a formerly liquid precursor as an integral part, wherein the labeling substance at least when applying the liquid precursor to the product was bound to these.

Possibly the labeling substance can be made of a corresponding functional Group of precursor molecules consist. On the other hand, the marking substance forms one with the Precursor immiscible phase, for example when the marking Substance forms liquid droplets or it consists of pigments or other solids, then the Phases of the labeling substance in at least one direction Expansion of less than 1 μm, ideally only between 10 nm and 400 nm. marking Substances with an extent in at least one spatial direction less than 1 μm are also referred to below as nanomarkers.

Prefers is a product according to the invention with layer system, wherein the marking substance is a nanodimensional Owns size, d. H. she represents a nanomarker.

Prefers this nanomarker has one in at least one spatial direction Extension between 10 nm and 400 nm, more preferably between 10 nm and 200 nm.

Such a nanomarker is characterized in that it is smaller than or equal to the selected layer thickness of the liquid precursor. Furthermore, it must be designed so that it does not lose its marker function (eg, color, reflection behavior, luminescence, magnetic behavior, etc.) during the plasma polymerization process, or does not lose its crosslinking function. By means of such marking, it is possible in the quality assurance process to detect whether the impression layer is completely detached from the body to be shaped has been removed.

Especially preferred is a product according to the invention with layer system, wherein the marking substance is selected from the group consisting of (I) dyes, (II) chromophores or other detectable groups bindable to the precursor, (III) chromophores or other detectable groups that bind to im liquid Precursor soluble, dispersible or suspendable molecules are bindable, (IV) magnetizable Particles, (V) complexed nanoparticles, (VI) light-scattering Substances, (VII) dye pigments and (VIII) fluorescent pigments.

• 1. Farbstoffe (z.B. zur Überwachung mit Photodetektoren), beispielsweise natürliche Farbstoffe wie Alizarin oder Indigo oder synthetische Farbstoffe wie Azo-, Azin-, Anthrachinon-, Acridin-, Cyanin-, Oxazin-, Polymethin-, Thiazin- oder Triarylmethan-Farbstoffe.
• 2. flüssige Precursoren mit chromophoren Gruppen (z.B. Azo-, Azoxy-, Imino- und/oder Chinon-Gruppen), beispielsweise direkt gebunden an die Precursor-Moleküle oder an Moleküle, die im Precursor löslich sind.
• 3. flüssige Precursoren mit funktionellen Gruppen oder anderweitige funktionelle Einheiten beispielsweise direkt gebunden an die Precursor-Moleküle oder an Moleküle, die im Precursor löslich sind oder an Feststoffe, welche im Precusor suspendiert werden, oder an Molekülen in Flüssigkeiten, welche im Precusor dispergiert sind. Mögliche funktionelle Gruppen sind beispielsweise: – olefinischen Gruppen, Keto-, Imin- oder Aldehydgruppen, (z.B. für UV-Detektoren) – funktionellen Gruppen, die eine intensive und sehr charakteristische Adsorption von Infrarotlicht zeigen (z.B. mit Dreifachbindungen wie Nitrile oder Thiocyanate, mit kumulierten Doppelbindungen wie Isocyanate oder Carbonylen Carbonsäurederivate), (z.B. für IR-Detektoren) – funktionellen Einheiten, die lumineszente, insbesondere Photolumineszente Eigenschaften aufweisen (z.B. Bis(azomethin)), – funktionelle Gruppen oder Einheiten, die charakteristische Elemente enthalten, die eine klare Abgrenzung gegenüber dem Substratmaterial und der Umgebung darstellen und charakteristische Signale bei der optischen Emissions-Spektrographie zeigen (z.B. für optische Spektroskopie an einem laserinduzierten Mikroplasma (LIBS))
• 4. Magnetisierbare Nanopartikel
• 5. Komplexierte Nanopartikel, wie z.B. in „Polydimethylsiloxane-magnetite nanoparticle complexes and dispersions in polysiloxane carrier fluids"; K.S. Wilson, J.D.Goff, J.S. Riffle, L.A. Harris, T.G. St Pierre; Polym. Adv. Technol. 2005; 16: 200–211 beschrieben.
• 6. Dispersionen von Feststoffen oder Flüssigkeiten, die zu einer Lichtstreuung führen
• 7. Farbstoffpigmente
• 8. Leuchtstoffpigmente

For the selection of the marking substance, the detector system required for the quality control is decisive. As markers can be used:

• 1. Dyes (eg for monitoring with photodetectors), for example natural dyes such as alizarin or indigo or synthetic dyes such as azo, azine, anthraquinone, acridine, cyanine, oxazine, polymethine, thiazine or triarylmethane dyes.
• 2. liquid precursors with chromophoric groups (eg azo, azoxy, imino and / or quinone groups), for example directly bonded to the precursor molecules or to molecules which are soluble in the precursor.
• 3. liquid precursors having functional groups or other functional units, for example directly bonded to the precursor molecules or to molecules which are soluble in the precursor or to solids which are suspended in the precursor or to molecules in liquids which are dispersed in the precursor. Possible functional groups are, for example: - olefinic groups, keto, imine or aldehyde groups (eg for UV detectors) - functional groups which show an intense and very characteristic adsorption of infrared light (eg with triple bonds such as nitriles or thiocyanates, with cumulative Double bonds such as isocyanates or carbonyl carboxylic acid derivatives), (eg for IR detectors) - functional units which have luminescent, in particular photoluminescent properties (eg bis (azomethine)), - functional groups or units which contain characteristic elements which are clearly differentiated represent the substrate material and the environment and show characteristic signals in optical emission spectrography (eg for optical spectroscopy on a laser-induced microplasma (LIBS))
• 4. Magnetizable nanoparticles
• 5. Complex nanoparticles, such as in "polydimethylsiloxane-magnetite nanoparticle complexes and dispersions in polysiloxanes carrier fluids", KS Wilson, JDGoff, JS Riffle, LA Harris, TG St Pierre, Polym Adv. Technol. 2005; 16: 200-211 described.
• 6. Dispersions of solids or liquids that cause light scattering
• 7. Dye pigments
• 8. Phosphorus pigments

Of the The person skilled in the art will mark the liquid precursor (mixture or chemical compound of the labeling substance with the liquid precursor) preferably make so that the density of marking substance or on nanomarkers, or on the detectable functional groups in the case of a homogeneous (precursor) liquid, for easy identification is sufficient and on the other hand, the curing of the liquid precursor is not disturbed. Care must also be taken when selecting the marking substance be that the application method (dipping, spraying, spin coating, etc.) is easily possible. For example, where appropriate by appropriate measures, prevents agglomeration of the particles of the labeling substance become. This is most easily possible because the marking Substance, e.g. as in "polydimethylsiloxane-magnetite nanoparticle complexes and dispersions in polysiloxanes carrier fluids ", K.S. Wilson, J.D. J.S. Riffle, L.A. Harris, T.G. St Pierre; Polym. Adv. Technol. 2005; 16: 200-211 described to the liquid Precursor is bound.

Of the so applied liquid and labeled precursor is in the first step of the plasma active components of the plasma (electrons, protons, ions, etc.) exposed. This usually takes place both crosslinking of the precursor molecules with one another (preferred to polymer chains or to a three-dimensional polymer backbone) instead as well as one with the layer deposited from the gas phase becomes. The first liquid Thus, precursor becomes an integral part of the plasma polymer molding layer and can therefore be subsequently be removed with this from the product again. An inspection the product surface will show in the case of success that no or almost no nanomarker on the surface remained.

The person skilled in the art will appreciate the nature of the liquid labeled precursor and the coating thickness (on the Substrate), as well as the subsequent steps of the plasma polymer coating coordinated so that a high degree of integration, preferably complete integration of the initially liquid and labeled precursor takes place in the plasma polymer coating.

at The nanomarker can be very different substances (if necessary in addition to the above) namely for example, soluble Dyes, pigments below one micron in size (organic or inorganic), metal or metal oxide particles, Metal clusters, semiconductor particles, photochromic or electrochromic Substances, luminescent substances, salts, graphite, organic solids. Important criterion for their selection is that a simple (quantifiable) proof possible is, so that it can be seen whether the impression layer completely from the surface solved has been.

• – Markierende Substanz: ZnS-Nanopartikel → Nachweis über Lumineszen
• – Markierende Substanz: Farbstoffnanopartikel → Nachweis über Lichtmikroskop (vergleiche weiter unten)
• – Markierende Substanz Ag – Nanopartikel → Nachweis über Graufärbung

Examples of labeling substances / detection systems:

• - Labeling substance: ZnS nanoparticles → detection by luminescence
• - Marking substance: Dye nanoparticles → detection by light microscope (see below)
• - Labeling substance Ag - nanoparticles → detection by gray staining

part The invention is also to select the marking substance so that If necessary, it fulfills another function, namely the improvement of Networking of the liquid Precursors, and thus improved chemical and mechanical Properties of the impression layer causes. Also, a crosslinking invention Nanomarker can therefore over have functional groups, so that he while the curing process of the liquid Precursors can build chemical bonds to this.

Prefers is a product according to the invention with layer system containing a formerly liquid precursor as integral Component, wherein the marking substance or another Substance that is coated with the precursor, more than one Compound valence to the precursor has. This way you can the marking substance or the further substance as a crosslinking node act and the properties of the deposited plasma polymers Impression layer in desired Influence way.

A such stabilization of the impression layer is particularly interesting if this is used for the molding of negatives, then for a embossing process Find application. This allows the mechanical and chemical stability of the plasma polymer Impression layer increased become. For example, the liquid precursor may be a UV-curing liquid Precursor attached be to the degree of crosslinking during increase the plasma process.

there in the context of this text, is to be understood as meaning "coated with the precursor" the substance in question simultaneously with, before or after the precursor is applied so that it comes into contact with this before a plasma polymer deposition on the precursor (or the mixture with the precursor).

Prefers is a product according to the invention with layer system, wherein the impression layer on the product side a formerly liquid Includes precursor as an integral part, wherein the marking substance or another substance that is applied with the precursor, can act as a crosslinking initiator. Also in this preferred product according to the invention be by the appropriate choice of the marker or the further substance the properties of the plasma polymer molding layer in a desired manner affected.

alternative can also different marking substances as well as further connections be mixed with the precursor, so that the desired Properties, such as color marking and initiating the cross-linking can be made parallel to each other.

Prefers is a product according to the invention with layer system, wherein the impression layer substantially residue from the product lets and most preferably the impression layer and the product are mechanically entnehmbar.

• (a) Bereitstellen eines abzuformenden Erzeugnisses,
• (b) Auftragen einer markierenden Substanz auf das abzuformende Erzeugnis und
• (c) Abscheiden einer plasmapolymeren Abformschicht unter Bedingungen, so dass die markierende Substanz integraler Bestandteil der Abformschicht wird.

Part of the invention is also a method for marking a plasma polymer molding layer comprising the steps:

• (a) providing a product to be molded,
• (b) applying a marking substance to the product to be molded, and
• (c) depositing a plasma polymer impression layer under conditions such that the marking substance becomes an integral part of the impression layer.

Especially it is preferred to apply a liquid precursor to the substance to be removed before step (c) To apply the product.

Also preferred is a method according to the invention wherein the marking substance or another substance with the precursor is applied, more than one binding valency has the precursor and / or can act as a crosslinking initiator. It is also preferred that the marking substance and / or the precursor be networked. Preferably, this crosslinking begins before the Start of the deposition process of the plasma polymer molding layer.

The described processes are part of the manufacturing process the products according to the invention with layer system.

• (a) Herstellen eines erfindungsgemäßen Erzeugnisses
• (b) Lösen der plasmapolymeren Abformschicht und
• (c) Detektieren von gegebenenfalls an dem Erzeugnis verbliebener markierender Substanz.

Part of the invention is also a method for detecting a residue of a plasma polymer molding layer on a molded product or for detecting a residue-free dissolution of a plasma polymer molding layer from a molded product, comprising the steps:

• (a) producing a product according to the invention
• (b) dissolving the plasma polymer molding layer and
• (c) detecting any marking substance remaining on the product.

With This method provides the advantages of the present invention particularly exploited, because so a quality control of demolding or the separation of the impression layer from the object to be shaped possible is.

part The invention also relates to the use of a mixture of precursor and marking substance for marking a plasma polymer molding layer and the use of a marking substance for detection a residue a plasma polymer molding layer on a molded product or to prove a residue-free solving a plasma polymer molding layer of a molded product.

part The invention is also an impression product comprising a labeled Plasma polymer impression layer on the surface. Such a molded product not only has the advantage that through the plasma polymer molding layer desired Properties on its surface exist such as increased protection or improved water repellency properties as well as a detail molded (negative) surface of the object to be molded. It can also by the mark its surface layer (the impression layer) also produce particular effects, e.g. luminescence, Refraction and the like, what aesthetic or technical reasons he wishes can be.

It ze igen

1a ) a product (with surface to be molded) ( 11 ), with a layer system of a plasma polymer molding layer ( 13 ) and a cover layer ( 15 ), wherein the impression layer ( 13 ) on the top layer ( 15 ) is more firmly attached than to the product ( 11 ). On the product side, the impression layer comprises substance ( 17 ). This puts the 1a ) is a preferred product according to the invention with a layer system;

1b ) the layer system from the impression layer ( 13 ) and the cover layer ( 15 ) after separation from the product ( 11 ). The layer system of impression layer ( 13 ) and cover layer ( 15 ) forms the negative impression of the product ( 11 ). At its surface or near the surface comprises the resulting negative-marking substance ( 17 );

2 a three-dimensional elevation image in gray cast of the product to be molded (positive);

3 a height profile of the product to be molded (positive);

4 an inverse three-dimensional height image representation in gray values of the impression product (negative):

5 a height profile of the impression product (negative).

Example:

For this example, a matt metallised plastic surface was used ( 2 ). An associated height profile is in 3 shown. The considered surface area is characterized by a circular defect.

These surface was with solvents cleaned and then by means of a dipping process with a 60 nm thick liquid precursor layer (AK 50 from the company Wacker Chemie) provided. In this liquid precursor were red dye particles (Clariant 5BO2) with a maximum Particle diameter of 200 nm introduced. Then took place a further processing in the low-pressure plasma with the specified in Tab Parameters. An examination with an optical microscope (500-fold Enlargement) clearly shows the dye particles.

Tabelle 1: Parameter des Niederdruckplasmaprozesses

Table 1: Parameters of the low pressure plasma process

Subsequently was a 2K polyurethane adhesive is used as impression compound (DELO-PUR 9694). This adhesive is also suitable for thicker hairbrushes and therefore also in a layer thickness of about 2-3 mm can be applied. Furthermore, the material has a sufficient flexibility for the Detachment.

After curing, the adhesive could be easily and residue-free removed. The color play of the molded surface initially made it possible to optically recognize that the release layer had been transferred. 4 (inverse representation) and 5 depict this surface. Due to the material shrinkage of the adhesive, a slight decrease in surface roughness can be seen; but otherwise a perfect replica of the topography.

To the detachment were on the metallized plastic surface (positive) no dye particles found more (optical examination with a microscope). Instead the dye particles were recognizable on the polyurethane negative. You could use a solvent soaked Rags can not be removed.

The Marker substance is completely in this example with the formerly liquid precursor transferred to the negative Service. The proof could be done easily with an optical Microscope guided become. Individual residues would be on the positive had been well visible if no complete transfer occurred would have.

Claims (22)

Product ( 11 ) with layer system ( 13 ; 15 ) of at least one cover layer ( 15 ) and one between the cover layer ( 15 ) and the product ( 11 ) arranged impression layer ( 13 ), wherein the impression layer ( 13 ) is a plasma polymer layer, which the contours of the product ( 11 ) and on the top layer ( 15 ) is more firmly attached than to the product ( 11 ), characterized in that the impression layer is a marking substance ( 17 ) contains. Product ( 11 ) with layer system ( 13 ; 15 ) according to claim 1, wherein the product is a wafer or a component of microsystem technology. Product ( 11 ) with layer system ( 13 ; 15 ) according to claim 1 or 2, wherein the impression layer ( 13 ) is a gradient layer and / or one of the cover layer ( 15 ) Adjacent adhesive zone and one to the product ( 11 ) adjacent Dehäsivzone and optionally comprises a transition zone, wherein the adhesive and Dehäsivzone are composed of different material. Product ( 11 ) with layer system ( 13 ; 15 ) according to one of the preceding claims, wherein the impression layer ( 13 ) comprises on the product side a formerly liquid precursor as an integral constituent. Product ( 11 ) with layer system ( 13 ; 15 ) according to claim 4, wherein the marking substance ( 17 ) essentially only in the region of the impression layer ( 13 ), which also contains the formerly liquid precursor. Product ( 11 ) with layer system ( 13 ; 15 ) according to claim 4 or 5, wherein the marking substance ( 17 ) at least when the liquid precursor is applied to the product ( 11 ) was bound to these. Product ( 11 ) with layer system ( 13 ; 15 ) according to any one of the preceding claims, wherein the marking substance ( 17 ) has a nanodimensional size. Product ( 11 ) with layer system ( 13 ; 15 ) according to any one of the preceding claims, wherein the marking substance ( 17 ) is selected from the group consisting of (I) dyes, (II) chromophores or other detectable precursor-bindable groups, (III) chromophores or other detectable groups that are bindable to liquid precursor-soluble, dispersible or suspendible molecules, ( IV) magnetizable particles, (V) complexed nanoparticles, (VI) light-scattering substances, (VII) dye pigments and (VIII) fluorescent pigments. Product ( 11 ) with layer system ( 13 ; 15 ) according to one of claims 4 to 8, wherein the marking substance ( 17 ) is selected so as to improve the crosslinking of the precursor in the molding layer. Product ( 11 ) with layer system ( 13 ; 15 ) according to one of claims 4 to 9, wherein the marking substance ( 17 ) or another substance applied with the precursor has more than one binding valency to the precursor. Product ( 11 ) with layer system ( 13 ; 15 ) according to any one of claims 4 to 10, wherein the marking substance ( 17 ) or another substance which is applied with the precursor, can act as a crosslinking initiator. Product ( 11 ) with layer system ( 13 ; 15 ) according to one of the preceding claims, wherein the impression layer ( 13 ) essentially free from residues of the product ( 11 ). Product ( 11 ) with layer system ( 13 ; 15 ) according to one of the preceding claims, wherein the impression layer ( 13 ) and the product ( 11 ) are mechanically entnehmbar. Method for marking a plasma polymer molding layer ( 13 ), comprising the steps of: (a) providing a product to be molded ( 11 ), (b) applying a marking substance to the product to be molded ( 11 ) and (c) depositing a plasma polymer impression layer ( 13 ) under conditions such that the labeling substance ( 17 ) integral part of the impression layer ( 13 ) becomes. A method according to claim 14, wherein before step (c) a liquid precursor to the product to be molded ( 11 ) is applied. A method according to claim 14 or 15, wherein the labeling substance ( 17 ) or another substance applied with the precursor has more than one binding valency to the precursor. Method according to one of claims 14 to 16, wherein the marking substance ( 17 ) or another substance which is applied with the precursor, can act as a crosslinking initiator. Method according to one of claims 14 to 17, wherein the marking Substance and / or the liquid precursor be networked. Method for detecting a residue of a plasma polymer molding layer ( 13 ) on a molded product ( 11 ) or for detecting a residue-free dissolution of a plasma polymer molding layer ( 13 ) of a molded product ( 11 comprising the steps of: (a) producing a product according to any one of claims 1 to 13, (b) dissolving the plasma polymer molding layer and (c) detecting any marking substance remaining on the article. Use of a mixture of precursor and marking Substance for marking a plasma polymer impression layer. Use of a marking substance for detecting a residue of a plasma polymer molding layer ( 13 ) on a molded product ( 11b ) or for detecting a residue-free dissolution of a plasma polymer molding layer ( 13 ) of a molded product ( 11 ). Impression product ( 13 . 15 ) comprising a labeled plasma polymer molding layer ( 13 ) on the surface.