DE102006048339A1 - Protective film for reducing exposure to substance comprises flexible support to which layer having low permeability to substance, layer that reduces free substance content and another layer having low permeability to substance, are applied - Google Patents

Abstract

A protective film comprises a flexible support to which three layers are sequentially applied, where first layer has a low permeability to the substance (barrier layer (BL)), second layer reduces the content of free substance (absorber layer (AL)), and third layer has a low permeability to the substance (as another barrier layer (BL)). An independent claim is included for preparation (p1) of the protective film involving applying at least one layer by a continuous casting process.

Description

The The invention relates to a protective film against harmful substances, in particular against gaseous Substances to which an article or device is sensitive reacts, such as oxygen contained in the ambient atmosphere, Moisture or other gases; the manufacture and use of a such film; with such a film coated objects such as e.g. OLEDs or photochromic coated discs or glasses; such as Devices comprising articles coated with such a film, such as. lighting or displays based on OLED or windows coated with photochrome Slices.

To the Protection of food and other goods are used in the packaging industry Slides needed, the impermeable for harmful substances are. The main application is the protection against oxygen and water. Also other technical goods such as photochromic coated glasses or glasses, solar cells, flexible LCDs (liquid crystal displays) and OLEDs (organic light-emitting diodes) are et al sensitive to oxygen and water and therefore have to be shielded in a suitable manner against it.

Plastic films with barrier properties are known (eg EVOH, PVDC from Joachim Nentwig, plastic films, Carl Hanser Verlag Munich 1994) and have transmittances of barely less than 1 cm ³ / m ² · dbar. This is sufficient for many food applications, but not for the significantly higher demands of photochromic coated glass or glasses, solar cells or even OLEDs. For such applications, so-called ultra-barriers are under development, whose functional principle is based on the combination of an inorganic layer with organic hybrid polymers (eg ORMOCEREN). The inorganic layer is a priori very impermeable, but has inevitable breaks, which are closed by the hybrid polymers. In addition, there are interactions between the layers, which further reduce the permeability. With such combination layers, it is hoped to be able to bring the permeability itself to the value of 10 ^-6 cm ³ / m ² · dbar required for OLEDs. A disadvantage of such layer systems is that the inorganic layer can only be produced by vapor deposition or sputtering; both methods that are relatively expensive and less suitable for industrial mass production.

For packaging It is known that under the barrier an oxygen-consuming Layer puts the already contained in the packaged good oxygen should eat up. However, such layer combinations reduce the permeability not the barrier and have only a short-term and for critical Applications insufficient effect.

A The ideal barrier is glass, but this is because of flexible applications the risk of breakage little suitable.

aim The invention is a, for flexible applications suitable barrier against harmful substances ready to provide, which is inexpensive as a coating on films and other carriers can be realized. In the following, the invention is exemplified by oxygen as harmful However, it is a knowledgeable user with appropriately modified reagents on any other Fabrics, such as e.g. harmful Gases or moisture, transferable.

The permeability Q of a harmful substance layer depends inversely proportionally on the layer thickness and proportionally on the partial pressure difference of the harmful substance before and after the layer. It is therefore impossible to achieve a permeability lower by several orders of magnitude through a greater layer thickness, because the layer would then be impractically thick. Even a layer package reduces the total permeability only according to the formula Q ges -1 = Q 1 -1 + Q 2 -1 + ... + Q n -1 . usually the densest layer alone is hardly worse than the overall package.

The inventive idea This is a series of suitable layers one above the other to put that on at least one layer with good barrier effect for one harmful Substance the partial pressure difference for this substance as possible gets small. The total permeability for the harmful Cloth is drastically reduced and allowed by such an arrangement with it the prior art much lower layer thicknesses and use of barrier layers, even at very high layer thickness alone do not give adequate protection.

TR

flexibler Träger;

XS

schädlicher Stoff, gegen den die Folie schützt, z.B. Sauerstoff oder Feuchtigkeit;

BS

Schicht mit geringer Durchlässigkeit für den Stoff XS (Barriereschicht);

AS

Schicht, die den Gehalt des Stoffes XS in dieser Schicht herabsetzt (Absorberschicht);

FS

Funktionsschicht;

PS

photochrome Schicht; und

MA

gegen XS empfindliches, zu schützendes Material.

For the layer construction of a material according to the present invention will also be hereinafter the following abbreviations are used:

TR

flexible carrier;

XS

harmful substance against which the film protects, eg oxygen or moisture;

BS

Low permeability layer for fabric XS (barrier layer);

AS

Layer which reduces the content of substance XS in this layer (absorber layer);

FS

Functional layer;

PS

photochromic layer; and

MA

sensitive to XS material to be protected.

The local partial pressure of the harmful Stoffes XS can be made according to the present Invention preferably lower with absorber layers AS. As special Advantageously, it has been found, barrier layers BS and absorber layers AS alternately on top of each other on a flexible carrier TR, where as the medium with the substance XS facing (upper) layer, a barrier layer BS is particularly effective.

object The invention is therefore a protective film according to claim 1, whose preferred embodiment is described in the claims 2 to 7, a method for producing such films according to claims 8 to 10, the use thereof according to claim 11, with the film coated articles according to claims 12th to 13 and a device according to claim 14, with the Foil coated objects includes.

The minimal configuration of the protective film according to the invention is therefore:
TR-BS-AS-BS or
BS-AS-BS,
wherein in the latter case one of the BS or AS layers is the carrier. In the preferred embodiments of the present invention shown below, in which a carrier is explicitly described, it may instead be one of the other named layers.

In use, the protective film is applied as gas-tight as possible to the material to be protected MA, resulting in, for example, the following structure:
MA-TR-BS-AS-BS or
TR-BS-AS-BS-MA.

Of the The last-mentioned construction has the advantage that it is accessible through the outside carrier simultaneously mechanically protected is. The following protective films are suitable in use each for both material arrangements. In addition, the material MA ggfls. on be provided with more than one page with the protective film.

In an advantageous embodiment of the present invention, the following structure is used for the protective film:
TR-BS-AS-BS-AS-BS.

For such Layer packages were found in the context of the present invention, that they are the material (volume) MA under the protective film against the Shield fabric XS much better than the barrier layers alone.

If, in a preferred embodiment of the invention, a functional layer FS is to be protected from the substance XS within the layer composite, layer sequences such as
TR-BS-AS-BS-FS-BS-AS-BS
advantageous. For the case described here of an integrated functional layer FS to be protected, the protective film according to the present invention may be the ready-to-use film itself having a function determined by FS. This film can either be used as such or applied to any material.

If the backing is impermeable to XS or is applied to a material that is impermeable to XS, the following layer construction may also be suitable:
TR-FS-BS-AS-BS.

If an FS sensitive to XS functional layer FS in the protective film of the invention inte It is advantageous to place them within the layer structure in such a way that they experience the least possible exposure through the substance XS.

These Arrangement can be made by those skilled in the art based on the present Description as well as by usual Find experiments easily.

The same generally applies to other than the layer construction variants explicitly listed here, to which the present invention is not limited.

in the In the context of the present invention, "impermeable to XS" means that the so-called material in FIG the desired Execution, especially in the desired Layer thickness, so little for XS permeable is that while the desired lifetime of MA no or at best an acceptable impairment from MA occurs through XS. As materials that are impervious to XS, are suitable e.g. Glass, metals, semiconductors, oxides, ceramics or Plastics with a correspondingly low permeability for XS. Such materials are common also as a flexible carrier available.

In the event that the wearer points to the side from which exposure to XS occurs (eg to the ambient air), the following construction is advantageous when the layer package with the side facing away from the wearer is applied to a material that is impermeable to XS is:
TR-BS-AS-BS-FS.

One example for an oxygen-sensitive functional layer FS is a photochromic Layer PS.

In an advantageous embodiment The present invention further encompasses the protective film more on top of each other arranged barrier layer / absorber layer pairs, which already clear Advantages with few couples, in particular with another 1 to 6 pairs are achieved, however even with a much higher one Number as 6 couples there are still improvements to be seen. An example of a preferred one Protective film according to the present invention Invention with a total of 3 such pairs (AS-BS) can thus the have the following structure: (TR-BS-AS-BS-AS-BS-AS-BS). The protective effect is characterized by the described splitting into more than one barrier layer / absorber layer pairs in Comparison to a couple with the same total layer thickness and the same ingredients significantly improved. The arrangement may be advantageous as described above also with function layers FS integrated in the protective film as well as be combined with any other layers.

The Protective film according to the present invention Invention may be referred to of the carrier be unilateral or bilateral, in both cases, the coating of the carrier may be different on the two sides. The protective film can e.g. only on one side of the carrier or on both sides each contain at least one functional layer. A two-sided Protective film could e.g. have the following structure: (BS-AS-BS-TR-BS-AS-BS). In spite of of the higher one Manufacturing effort could to offer such a structure, if required a very good flatness is because of the symmetrical structure, the tensile forces of Coating on the carrier be compensated. Here, too, can advantageously a functional layer be integrated into the protective film.

If the carrier a relatively high permeability for the harmful Fabric XS, it is preferred if he is on the back at least one barrier and / or Absorber layer contains.

in the Case of a vehicle with relatively high oxygen permeability and / or high Oxygen content after production, it has also been beneficial proved when the carrier coated on at least one side with an absorber layer is, e.g. according to the following Layer structures: (TR-AS-BS-AS-BS), (AS-R-BS-AS-BS) or (AS-TR-AS-BS-AS-BS). This has turned out to be preferred even if the page of the carrier otherwise for Oxygen is blocked, e.g. by sticking the carrier on a glass plate. Also for this if the mechanism is not known, it will be retrospectively believed that the harmful Infiltrate fabric XS laterally through free cut edges of the support and by the wearer can hike.

The inventive film enough Its barrier effect itself has high requirements and is e.g. when Oxygen protective film at least comparable to materials, at which an oxygen barrier layer was vapor-deposited consuming and is often more robust against mechanical stress.

A barrier layer according to the present invention can be used simultaneously with the barrier effect have an absorber effect as well as any other effects, and an absorber layer according to the present invention may simultaneously have a barrier effect as well as any other effects in addition to the absorber effect.

The individual layers of the film according to the invention can by conventional methods such as lamination or pouring method be applied. At least one layer with barrier and / or absorption effect not applied by a vapor deposition technique, none of the barrier and / or absorption layers is particularly preferred Applied vapor deposition and in particular does not become a layer applied with a vapor-deposition technique.

When casting or pouring method all known methods for the liquid coating of materials are suitable, ie e.g. also a doctor blade. It has been particularly preferred however, exposed as a carrier a flexible and for the casting process To use sufficiently stable film and this continuously baste, for what, in particular for more than one shift, a multiple-pour system, in particular a cascade or curtain caster is preferred, with which the multilayer material in particular is manufactured in a machine passage (Mehrfachbeguß). Surprised will the stability of the produced by continuous casting Material opposite the usual simple application methods such as knife-coating or brushing considerably improved. Another significant improvement is in multi-layered Materials by simultaneous application of several layers (Mehrfachbeguß) compared to several successive individual casts too observe. Without knowing the underlying mechanism, this could be the with such casting potential uniformity of the layers, so there are no weak spots in the barrier and / or absorber effect.

Speaks for it also that in the context of the present invention by the known activities to improve the quality of the casting, such as Optimization of the rheological properties of the casting solutions and / or their careful Degassing the stability the protective film could be further improved.

at The layers mentioned can each be individual layers or to act on multiple layers.

For the purposes of the present invention, a barrier layer BS is preferably a layer which has a permeability coefficient P of less than 0.1, preferably less than 0.01, for the harmful substance. A definition of the permeability coefficient P and its values for the case where the harmful substance XS is oxygen can be found for numerous polymers in Polymer Handbook, 4th edition, J. Brandrup, EH Immergut and EA Grulke, John Wiley & Sons, Inc. New York, page VI / 543 et seq. , Suitable examples are listed in Table 1, the permeability coefficient mentioned therein has the unit
cm ³ (273.15 K, 1.013 x 10 ⁵ Pa) cm / (cm ² x s x Pa). Table 1 polymer abbreviation P (× 10 ¹³ ) at Low density polyethylene LDPE 2.2 25 ° C High density polyethylene HDPE 0.3 25 ° C polypropylene PP 1.7 30 ° C Polystyrene (biaxially oriented) PS 2.0 25 ° C polymethylmethacrylate PMMA 0.116 34 ° C polyacrylonitrile PAN 0.00015 25 ° C Polyacrylonitrile (BARER) PAN 0.04 25 ° C polymethacrylonitrile PMAN 0.0009 25 ° C polyvinyl acetate PVAc 0.367 30 ° C polyvinyl alcohol PVA 0.00665 25 ° C Polyvinyl chloride (without plasticizer) PVC 0.034 25 ° C polyvinylidene PVDC 0.00038 35 ° C polyvinylidene chloride copolymer Saran 0.0038 30 ° C polytetrafluoroethylene PTFE 3.2 25 ° C polybutadiene 14.3 25 ° C polydimethylbutadiene 1.58 25 ° C polyoxymethylene POM 0.057 23 ° C Polyester (Lexan) 1.05 25 ° C polymer abbreviation P (× 10 ¹³ ) at (Mylar A) 0.03 25 ° C (Hostaphan) 0,014 23 ° C polyethylene terephthalate PET 0.019 30 ° C polytetramethylene PC 0.105 35 ° C polydimethylsiloxane 695 35 ° C Polyamide (nylon 6) PA 0.0285 30 ° C cellulose acetate 0.58 30 ° C

The Barrier layers are preferably made from solution, in particular aqueous Solution, cast or presented in the form of dispersions. The barrier polymers can additions such as plasticizers, wetting agents and / or anti-aging agents. Suitable plasticizers are e.g. alone or in a mixture of tricresyl phosphate, Dibutyl phthalate, tributyl citrate or sebacic acid ester.

When Barrier polymers, such polyvinyl alcohols are particularly preferred which has an average molecular weight and a degree of hydrolysis of about 99%.

For the purposes of the present invention, an absorber or absorption layer AS is preferably a layer which is capable of permanently bonding a harmful substance XS, such as, for example, molecular oxygen, and thus of increasing the partial pressure of the substance XS in the layer to reduce. The substance XS which is located in the layer or which diffuses into the layer is thus trapped as completely as possible in the layer and the content of free substance in the layer is correspondingly reduced. The trapping of the substance XS can both physically, for example by adsorption, as well as chemically, for example by chemisorption or other chemical reactions such as reduction take place. In the context of the present invention, all agents with which the harmful substance XS is captured are also referred to below as pollutant scavengers and in the case of oxygen as substance XS oxygen scavengers.

When Absorber AS are especially for oxygen matrix materials like PVOH or gelatin suitable in the absorbing substances are embedded. Examples of this are L-ascorbic acid, isoascorbic acid, L-ascorbates, isoascorbates, ascorbyl palmitate and stearate, tocopherols (Alpha, gamma, delta tocopherol), gallates (propyl, octyl, dodecyl), Butylhydroxyanisole (BHA), butylhydroxytoluene (BHT). Due to the castable Matrices can also such layers on a large scale be applied. Alternatively, oxygen-consuming copolymers applicable, e.g. in the form of one- or two-component paints to let. Should others be harmful Substances are absorbed as oxygen, e.g. Moisture (water vapor), the person skilled in the art can easily find suitable materials and according to the present invention.

at Use of insoluble in the respective casting solution pollutant scavengers these are introduced in the form of dispersions. For the production of Dispersions become the pollutant with a dispersing device in an aqueous polymer solution Use of wetting agents or dispersants in known Dispersed way. This method is particularly advantageous around watery Casting solutions too enable, the for all with a casting process applied layers according to the present Invention are preferred because they burden the environment less than organic solutions and no explosion protection measures require.

at Use of organic soluble pollutant scavengers For example, in a high boiler (oil former, remaining solvent) solved and the solution emulsified into an aqueous polymer solution using an emulsifier. It is useful to use emulsifying aids such as emulsifiers or low-boiling water-insoluble solvents, which are evaporated during the emulsification process. Examples of water-soluble polymers are polyvinyl alcohol, gelatin, polyacrylamides, polyvinylpyrrolidone, Polyvinylimidazole, hydroxyethyl cellulose, cellulose, polyoxazolinones, Polyallylamine, polyacrylic acids or copolymers or mixtures of these polymers. Examples of high boilers are tricresyl phosphate, tritoloyl phosphate, dibutyl phthalate, N, N-diethyl dodecanamide, N, N-dibutyldodecanamide, tris (2-ethylhexyl) phosphate, Acetyltributyl citrate, 2,4-di-tert-pentylphenol, 2- (2-butoxyethoxy) ethyl acetate and 1,4-cyclohexyldimethylene-bis (2-ethylhexanoate). As auxiliary solvent can Ethyl acetate or diethyl carbonate may be exemplified.

Another possibility of introduction when using water-soluble polymers is to use the water-insoluble pollutant scavenger together with a polymer dispersion or a polymer latex in finely divided form. This technique is known as the loading of latices and is described in eg DE 25 41 274 . US 4,199,363 . DE 25 41 230 . US 4,247,625 and EP 049 399 described.

at Use of water-soluble pollutant scavengers they are dissolved in water, together with an aqueous binder solution or binder dispersion mixed and then to a layer potted and dried. For example, PVA, gelatin, Polyvinylimidazole, polyvinylpyrrolidone substituted celluloses, Polyacrlsäuren, Polyacrylamide and mixtures thereof are used.

In front the Beguss can the dispersions, emulsions or solutions obtained in this way in known With watering agents, biocides, thickeners or other additives be added to improve the quality and stability of the casting.

When pollutant trap All compounds that are capable of producing a substance are suitable (XS), e.g. molecular oxygen, to bind or convert, in particular adsorbents, oxidants (not in the case of oxygen) and reducing agents. The pollutants can be directly in their reactive Mold are introduced, but particularly preferred are activatable Pollutant scavengers. By activating it can be avoided that the pollutant catcher in the Production process of the material according to the invention already partially is consumed. Suitable activation reactions may be e.g. through light, heat or chemical additives triggered become. It is for that all reactions applicable to the release of acting as a pollutant compound suitable are, in particular the splitting of masked pollutant catcher.

Suitable oxygen scavengers are, for example, those in US 5,350,622 . US 5 211 875 . US 6,287,481 . WO 94/12590 and in particular the in US Pat. No. 6,942,821 , Columns 7 to 10 listed compounds.

Examples of oxygen scavengers according to the present invention are alone or in mixture organic oxygen scavengers, for example unsaturated hydrocarbons, both high and low molecular weight, in combination with transition metal compounds, ascorbic acid, ascorbates, isoascorbic acid, isoascorbates, ascorbyl palmitate, gallic acid and its salts, tocopherol, hydroquinone, catechol , Resorcinols, dibutylhydroxytoluene, dibutylhydroxyanisole, pyrogallol, Rongalit, sorbose, glucose, lignins, sulfites, tannin, ascorbates in combination with transition metal catalysts, thiosulfite, mercaptopropionic acid, thiosulfate, bisulfite, hydrogensulfite, dithionate, dithionite, hyposulfite, sulfide, tin compounds, hydroxylamine, hydrazine , Phosphine compounds, iron-based oxygen scavengers such as iron powder, activated iron, iron oxide or iron salts, polymeric oxygen scavengers such as oxidation-reduction resins and polymeric metal complexes, oxygen adsorbers such as zeolites and activated carbon, or mixtures of g called oxygen scavenger. Preferred phosphine compounds include triphenylphosphine, tri-p-tolylphosphine, diphenylmethylphosphine, diphenylethylphosphine, diphenylpropylphosphine, dimethylphenylphosphine, diethylphenylphosphine, dipropylphenylphosphine, divinylphenylphosphine, divinyl-p-methoxyphenylphosphine, divibyl-p-bromophenylphosphine, divinyl-p-tolylphosphine, diallylphenylphosphine, diallyl-p methoxyphenylphosphine, diallyl-p-bromo-phenylphosphine and diallyl-p-tolylphosphine. Particularly preferred is triphenylphosphine. Preferred ascorbates and phenolic oxygen scavengers are, for example, in US 5,977,212 , Column 5, lines 15-67.

In a preferred embodiment of the present invention the material of the invention Oxygen quenchers and in particular singlet oxygen quenchers. The quencher mentioned can in any layer of material and also in several layers be included.

Suitable singlet oxygen quenchers are for example JP-A Nos. 58-175693 . 59-81194 . 60-18387 . 60-19586 . 60-19587 . 60-35054 . 60-36190 . 60-36191 . 60-44554 . 60-44555 . 60-44389 . 60-44390 . 60-54892 . 60-47069 . 63-209995 and 4-25492 . JP-B Nos. 1-38680 and 6-26028 . DE.350 399 and Journal of the Chemical Society of Japan, October 1992, p. 1141 known. NQ-13 by Hayashibara Biochemical Laboratory, Inc. is an example of a commercially available singlet oxygen quencher.

In a preferred embodiment of the present invention conjugated as singlet oxygen quenchers, transition metal complexes, amines including hindered amines (HALS compounds), aminium salts, iminium salts and / or in EP 0 486 216 B1 listed oxygen quenchers, in particular the compounds of the formula II-a-2 and R mentioned there substances used.

In an advantageous embodiment In the present invention, the protective film comprises further layers such as intermediate layers, functional and protective layers, with which the material of the desired application can be adjusted.

If the film should also provide protection against light, or against substances which are formed under the influence of light, such as singlet oxygen, it has proven to be advantageous if the material contains at least one UV absorber. Although the UV absorber in any layer, so for example, the functional layer, the barrier and / or the absorber layer and in the carrier to stability advantages, the effect is more pronounced, the closer it is to the side of the material exposed directly to the light is particularly pronounced if it is contained in a separate layer of US, which is exposed as the uppermost layer of the protective film directly to the light. Such a structure is for example:
TR-BS-AS-BS-US,
when the protective film is applied on the carrier side to the material to be protected and
US-TR-BS-AS-BS,
when the protective film is applied on the BS side to the material to be protected.

As UV absorbers, any substances that absorb UV radiation can be used alone or in a mixture. Suitable UV absorbers and their amount used can be found by a person skilled in the art by conventional tests. Preference is given to organic substances such as triazines (eg loud EP 531 258 ), Hydroxyphenylbenzothiazoles (eg EP451813 . EP190003 and EP577122 ), polymeric UV absorbers (eg loud DE 195 00 441 ) and inorganic compounds such as ZnO nanoparticles (eg DE 198 32 937 and US 6,015,655 ), as well as in DE 197 46 513 described substance classes.

• a) Benzotriazol-Derivate:
  
  wobei R, X gleich oder verschieden H oder Alkyl oder Alkylaryl sind;
• b) Dimere Benzotriazol-Derivate:
  
  worin R¹, R² gleich oder verschieden sind und H, Halogen, C₁- bis C₁₀-Alkyl, C₅- bis C₁₀-Cycloalkyl, C₇- bis C₁₃-Aralkyl, C₆- bis C₁₄-Aryl, -OR⁵ oder -(CO)-OR⁵ bedeuten, R³, R⁴ gleich oder verschieden sind und H, C₁- bis C₄-Alkyl, C₅- bis C₆-Cycloalkyl, Benzyl oder C₆- bis C₁₄-Aryl bedeuten, R⁵ H oder C₁ bis C₄-Alkyl bedeuted, m 1, 2 oder 3 ist und n 1, 2, 3 oder 4 ist;
  
  worin L¹ die Brücke -(CHR³)_p-C(=O)-O-(Y-O)_q-C-(CHR⁴)_p- bedeutet, p eine ganze Zahl von 0 bis 3 ist, q eine ganze Zahl von 1 bis 10 ist, Y -CH₂-CH₂-, -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅-, -(CH₂)₆-, oder CH(CH₃)-CH₂- bedeuted und R¹, R², R³, R⁴, m und n die für Formel (UV-III) genannte Bedeutung haben;
• c) Triazin-Derivate
  
  worin R¹, R², R³, R⁴ unabhängig voneinander H, Alkyl, CN oder Halogen bedeuten und X Alkyl bedeuted;
• d) Triazin-Derivate wie in EP1033243 beschrieben;
• e) Dimere Triazin-Derivate
  
  wobei R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ unabhängig voneinander H, Alkyl, CN oder Halogen bedeuten und X Alkyl oder -(CH₂CH₂-O-)n-C(=O)- bedeuted;
• i) Diarylcyanoacrylate
  
  worin R C₂-Alkyl bis C₁₀-Alkyl oder Aryl bedeuted, und wovon Uvinul 3035 mit R gleich -C₂H₅ und Uvinul 3039 mit R gleich -CH₂CH(C₂H₅)C₄H₉ bevorzugt sind;
• h) Hydroxybenzophenon-Derivate
  
  worin A H oder OH und R H, Alkyl, Acyl, -(CH₂)_n-O-(CH₂)_n-CH₃, -(CH₂)_n-O-C(=O)-(CH₂)_n-CH₃ bedeuten und n eine ganze Zahl von 1 bis 20 ist;
• i) Resorcin- Derivate
  
  wobei Ar Phenyl, Naphthyl, Alkylphenyl oder Alkoxyphenyl und R H, Alkyl, Isoalkyl, Cycloalkyl, Acyl, -(CH₂)_n-O-(CH₂)_n-CH₃, -(CH₂)_n-O-C(=O)-(CH₂)_n-CH₃, -C(=O)-(CH₂)_n-CH₃ oder -C(=O)-Ar bedeuted und n eine ganze Zahl von 1 bis 20 ist;

The following UV absorbers are preferred:

• a) Benzotriazole derivatives:
  
  wherein R, X are the same or different and are H or alkyl or alkylaryl;
• b) Dimer benzotriazole derivatives:
  
  wherein R ¹ , R ^{2 are the} same or different and H, halogen, C ₁ - to C ₁₀ alkyl, C ₅ - to C ₁₀ cycloalkyl, C ₇ - to C ₁₃ aralkyl, C ₆ - to C ₁₄ aryl , -OR ⁵ or - (CO) -OR ⁵ , R ³ , R ^{4 are} identical or different and are H, C ₁ - to C ₄ -alkyl, C ₅ - to C ₆ -cycloalkyl, benzyl or C ₆ - to C _{14 is} aryl, R ^{5 is} H or C ₁ to C ₄ alkyl, m is 1, 2 or 3 and n is 1, 2, 3 or 4;
  
  where L ^{1 is} the bridge - (CHR ³ ) _p -C (= O) -O- (YO) _q -C- (CHR ⁴ ) _p -, p is an integer from 0 to 3, q is an integer of 1 to 10, Y is -CH ₂ -CH ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, or CH (CH ₃ ) _{2 3} ) -CH ₂ - and R ¹ , R ² , R ³ , R ⁴ , m and n have the meaning given for formula (UV-III);
• c) triazine derivatives
  
  wherein R ¹ , R ² , R ³ , R ^{4 are} independently H, alkyl, CN or halogen and X is alkyl;
• d) triazine derivatives as in EP1033243 described;
• e) Dimer triazine derivatives
  
  where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ independently of one another are H, alkyl, CN or halogen and X is alkyl or - (CH ₂ CH ₂ -O-) nC ( = O) - meaning;
• i) diaryl cyanoacrylates
  
  wherein R ₂ signifies alkyl to C ₁₀ alkyl or aryl, and of which Uvinul 3035 with R equal -C ₂ H ₅ and Uvinul 3039 with R equal to -CH ₂ CH (C ₂ H ₅ ) C ₄ H _{9 are} preferred;
• h) hydroxybenzophenone derivatives
  
  wherein A is H or OH and R is H, alkyl, acyl, - (CH ₂ ) _n -O- (CH ₂ ) _n -CH ₃ , - (CH ₂ ) _n -OC (= O) - (CH ₂ ) _n -CH ₃ and n is an integer from 1 to 20;
• i) resorcinol derivatives
  
  where Ar is phenyl, naphthyl, alkylphenyl or alkoxyphenyl and R is H, alkyl, isoalkyl, cycloalkyl, acyl, - (CH ₂ ) _n -O- (CH ₂ ) _n -CH ₃ , - (CH ₂ ) _n -OC (= O) - (CH ₂ ) _n -CH ₃ , -C (= O) - (CH ₂ ) _n -CH ₃ or -C (= O) -Ar and n is an integer from 1 to 20;

Especially suitable UV absorbers from the abovementioned substance classes are e.g. Tinuvin 234, Tinuvin 360, Tinuvin 1577, Uvinul 3030, Chinaassorb 81, Tinuvin 329, Tinuvin 350, Uvinul 3035 and Uvinul 3039.

Surprised it is in the material according to the present Invention also possible to apply an anti-scratch coating without the protective effect of the film to worsen. Rather, through this coating, the preferred as an outer layer applied, the effect can even be improved. An anti-scratch coating In particular, has also been considered favorable in terms of the weather resistance of the protective film and proved. As an anti-scratch coating are e.g. UV-curable Acrylic varnishes suitable, i.a. from Bayer and Cytec and preferably nanoparticles e.g. from Clariant or Byk included.

These it is the material according to the contemplated Invention to a one-sided coated film, the other Body, such as. a window area or a semiconductor is to be applied, so can in favorable make already the adhesion between body and slide sufficient to allow adhesion. For a safer application however, it is generally preferred to place the film on the desired one Side with an adhesive layer (KS) to provide, advantageously in turn has a cover sheet. Adhesive layer and film are preferably applied in one step after the casting of the material according to the invention and in particular laminated but also directly on an already with the adhesive layer and the Cover foil provided with film. It is also possible the provided with the adhesive layer cover itself as a carrier according to the present invention Invention to use and to water when the thus obtained Including stratification the adhesive layer has sufficient mechanical strength, to remove it from the cover.

in the Case of a window film has a suitable material after peeling the cover sheet and applying to the glass pane, e.g. the following Construction in the order given: Glass-glass adhesive FS-BS-AS-BS-TR anti-scratch coating air. The functional layer may in this case be e.g. one more below described photochromic layer PS act.

Should the film according to the present Invention against heat protect, can it be done this way that they have light in the infrared and especially in the near infrared, so with Wavelengths greater than 700 nm, preferably between 700 nm and 2000 nm and in particular between 700 nm and 1500 nm absorbed and / or reflected. This absorption and / or reflection can also increase with increasing radiation (thermochromism) or be permanent. The absorption or reflection can by corresponding dyes in the carrier material or a layer of the film (IR or NIR filter) can be achieved, but also e.g. by interference or refraction effects, such as multiple thin layers the appropriate layer thickness and refractive index.

All previously mentioned layers not just one-sided on the carrier be applied, but alone or in combination also on the other side of the wearer, e.g. to obtain a particularly high protective effect.

Suitable supports are, in particular, thin films and films having a thickness of from 10 μm to 300 μm, in particular from 50 μm to 150 μm. An overview of carrier materials and auxiliary layers applied to their front and back is in Research Disclosure 37254, Part 1 (1995), p. 285 and in Research Disclosure 38957, Part XV (1996), p. 627 shown. Carrier materials which are particularly suitable for the present invention are cellulose triacetate, polycarbonate, polystyrene, polyvinyl chloride and polyesters such as polyethylene terephthalate (PET) or polyesters of ethylene glycol and naphthalenedicarboxylic acid (PEN).

Of the carrier and / or at least one layer applied thereto may preferably electrically conductive be, depending on the degree of conductivity an antistatic Effect or effect as an electrode e.g. for semiconductor elements such as solar cells or OLEDs is obtained. Suitable additives increasing the conductivity of layers such as e.g. Polythiophenes are known to those skilled in the art.

Information about suitable binders for the layers according to the present invention can be found in Research Disclosure 37254, Part 2 (1995), p. 286 and in Research Disclosure 38957, Part II.A (1996), p. 598 ,

hydrophobic Constituents of the layers, e.g. UV absorbers, stabilizers, oxygen scavengers etc. as described above, e.g. For oxygen scavengers described, preferably in high-boiling organic solvents solved, dispersed or incorporated using loadable latexes.

The protective film of the present invention may further contain filter dyes, plasticizers (latices), biocides, yellowing reduction additives, and others. Suitable compounds are found, for example, in Research Disclosure 37254, Part 8 (1995), p. 292 , in Research Disclosure 37038, parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 et seq and in Research Disclosure 38957, Parts VI, VIII, IX and X (1996), pp. 607 and 610 et seq ,

The Layers of the protective film according to the invention can hardened are, i. the binder used, for example gelatin or PVA, is crosslinked by suitable chemical methods.

Suitable hardener substances are found, for example, in Research Disclosure 37254, Part 9 (1995), p. 294 , in Research Disclosure 37038, Part XII (1995), page 86 and in Research Disclosure 38957, Part II.B (1996), p. 599 ,

When a possible embodiment the present invention describes a photochromic material which is e.g. suitable as a window film. In this application, the Photochromic layer otherwise unprotected from the weather and thereby especially exposed to atmospheric oxygen and humidity and thereby rapidly destroying the sensitive photochromic dye. By the protective film of the invention is met very effectively.

Under a photochromic layer is within the scope of the present invention a layer that at least one photochromic reacting Contains pigment or a photochromic dye. Prefers it is an organic photochromic dye, in The following also briefly called photochromic dye, or a mixture of two, three, four or more different photochromic dyes. Photochromic dyes are in particular due to their absorption spectrum characterized in the switched state and in the ground state, wherein it for the present invention is preferred when the photochromic dye in the ground state only slightly or not at all in the visible light range absorbed, but in the switched state as strong as possible in the visible Absorbed light area. The switching, so the excitation in the (stronger) colored Condition happens preferably with short-wave radiation such blue or ultraviolet light, e.g. with light from 200 to 500 nm, preferably with light of 250 to 450 nm, more preferably with Light of 300 to 420 nm and in particular of 350 to 420 nm. Preferred are the photochromic dyes according to the present invention not in inorganic-organic hybrid polymers, so-called ORMOCERE introduced and are preferably also not surrounded by a supramolecular protective sheath.

In a preferred embodiment of the present invention, the coloring by the photochromic dye or the dye mixture is largely neutral gray. The criterion for this is the subjective color perception of a statistically relevant group of persons who judge a colored film with the desired color in the switched state, which covers only half of the window area of a room. The better the color neutrality of the film is evaluated, the better the dye or dye mixture contained therein is suitable for the present invention. Only half of the window area is covered to prevent color adaptation by the human eye, which corresponds, for example, to the condition with partially opened windows. Particular preference is given to selecting those photochromic dyes which already ensure an acceptable neutrality as a single dye in the test. Sol dyes show greater long-term stability of gray neutrality, whereas gray-neutral dye blends frequently show discoloration over time.

The photochromic compounds usable for the present invention are not specifically limited. Preferably, they may be selected from the class of benzopyrans, spirobenzopyrans, spirobenzoxazines and higher annulated ring systems derived therefrom, such as in particular naphthopyrans, spironaphthopyrans, spironaphthoxazines or fluorenopyrans, as well as fulgides and fulgimides. Thus, for example, in the 2,2-position aromatic or heteroaromatic substituted [2H] -naphtho (1,2-b) -pyrane, but also in the 3,3-position appropriately substituted [3H] -naphtho (2,1-b ) -pyrane, such as those in PCT-DE 98/02820 described naphthopyrans and in PCT / EP 99/05258 described indeno [2,1-f] naphtho [1,2-b] pyrane derivatives and / or spiro-9-fluoreno [1,2-b] pyrene derivatives.

Furthermore, the in US 5,753,146 and EP-A-0 562 915 described pyrans, as well as photochromic dyes of other classes, such as oxazines, such as those in US 5,753,146 described oxazines, or fulgides are used.

Farbstoff der Formel (PF-IV) R¹ R² R³ R⁴ R⁵ FS-1 Phenyl H OCH₃ OCH₃ H FS-2 Phenyl H OCH₃ N(Phenyl)₂ H FS-3 H H H OCH₃ OCH₃ FS-4 H CH₃ CH₃ OCH₃ OCH₃ FS-5 H H OCH₃ H OCH₃ FS-6 H Phenyl OCH₃ H OCH₃ FS-7 C₂H₅ H OCH₃ H OCH₃ FS-8 1-Naphthyl H OCH₃ H OCH₃ FS-9 Phenyl H OCH₃ H OCH₃ FS-10 o-Toloyl H OCH₃ H OCH₃ FS-11 2-p-Xylyl H OCH₃ H OCH₃ FS-12 3-Methyl-2-thienyl H OCH₃ H OCH₃

Farbstoff der Formel (PF-V) R¹ R² R³ FS-13 H OCH₃ OCH₃ FS-14 OCH₃ OCH₃ OCH₃ FS-15 H N-Morpholinyl H FS-16 OCH₃ N-Morpholinyl H FS-17 OCH₃ H H FS-18 OCH₃ OCH₃ H FS-19 OCH₃ N-Morpholinyl H FS-20 OCH₃ N(Phenyl)₂ H FS-21 OCH₃ N(CH₃)₂ H FS-22 OCH₃ OCH₃ H FS-23 OCH₃ OCH₃ OCH₃ Examples of photochromic dyes which are particularly advantageous in the context of the present invention are the following dyes of the formula (PF-IV) and in particular the following dyes of the formula (PF-V):

Dye of the formula (PF-IV) R ¹ R ² R ³ R ⁴ R ⁵ FS-1 phenyl H OCH ₃ OCH ₃ H FS-2 phenyl H OCH ₃ N (phenyl) ₂ H FS-3 H H H OCH ₃ OCH ₃ FS-4 H CH ₃ CH ₃ OCH ₃ OCH ₃ FS-5 H H OCH ₃ H OCH ₃ FS-6 H phenyl OCH ₃ H OCH ₃ FS-7 C ₂ H ₅ H OCH ₃ H OCH ₃ FS-8 1-naphthyl H OCH ₃ H OCH ₃ FS-9 phenyl H OCH ₃ H OCH ₃ FS-10 o-tolyl H OCH ₃ H OCH ₃ FS-11 2-p-xylyl H OCH ₃ H OCH ₃ FS-12 3-methyl-2-thienyl H OCH ₃ H OCH ₃

Dye of the formula (PF-V) R ¹ R ² R ³ FS-13 H OCH ₃ OCH ₃ FS-14 OCH ₃ OCH ₃ OCH ₃ FS-15 H N-morpholinyl H FS-16 OCH ₃ N-morpholinyl H FS-17 OCH ₃ H H FS-18 OCH ₃ OCH ₃ H FS-19 OCH ₃ N-morpholinyl H FS-20 OCH ₃ N (phenyl) ₂ H FS-21 OCH ₃ N (CH ₃ ) ₂ H FS-22 OCH ₃ OCH ₃ H FS-23 OCH ₃ OCH ₃ OCH ₃

The photochromic dyes can be incorporated into layers that are made of organic soluble or water-soluble (Co) polymers.

at in organic solvents soluble Polymers become the photochromic dye together with the polymer in an organic solvent solved, potted and dried. As organic solvents, e.g. Acetone, ethanol, ethyl acetate, tetrahydrofuran, methylene chloride, Methanol, dioxane, butyl acetate, isopropanol, toluene or mixtures such solvents be used.

When (Co) polymers can for example, polymethyl methacrylate, co-poly (butyl acrylate-styrene 45:55), polycarbonate, Cellulose triacetate, polybutylmethacrylate, polyester, polyurethane, Polyamides, copolymers of vinylidene chloride and acrylic esters and acrylonitrile copolymers are used.

In a particular embodiment, it is also possible to use mixtures of (meth) acryl-modified polymers with reactive solvents, such as hexanediol diacrylate or trimethylolpropane triacrylate. These solutions are coated and then cured thermally or by means of UV light or electron beams. Depending on the type of curing these solutions contain thermally activatable curing agent such as peroxides or azo compounds or UV-activatable hardener such as Darocur ^® or Irgacure ^® compounds. Hardening with electron beams requires no hardening.

to Improvement of stability of the photochromic dyes included in the polymer matrix can be the Reactive monomers, other monomers may be added, e.g. acrylamides, Vinylpyridine or vinylimidazole.

at water-soluble Copolymers become the water-insoluble ones photochromic dyes in the form of dispersions, emulsions or loaded polymer latices introduced.

to Preparation of the invention used Dispersions of particles containing the photochromic dyes (Dye latexes) is allowed to water in a solution the water-insoluble photochromic dyes and the ionomeric product in one with Water-miscible low-boiling solvent or solvent / water mixture with stirring incorporated.

Out the resulting dispersion becomes the solvent by distillation or by other suitable separation techniques, such as dialysis or ultrafiltration separated.

To another embodiment can the solution the water-insoluble photochromic dyes in a water-miscible low-boiling solvent with the solution a urethane prepolymer, that still NCO groups contains after which the polyaddition in the presence of the dyes leads to an end. This embodiment can be used with particular advantage when the dyes contain no isocyanate-reactive groups.

When water-miscible organic solvents are for the preparation the dispersion suitable for use with both the ionomeric products as well as the photochromic dyes are able to solve. Examples of such solvent are acetone, tetrahydrofuran, dioxane, isopropanol, methanol, ethanol, Methyl ethyl ketone, acetonitrile.

The for the Preparation of the dispersion applied amount of photochromic dye is in general 2 to 200 wt .-%, based on ionically modified Polymer. Preference is given to weight ratios of dye to polymer from 1: 200 to 1:10.

These Procedure allows dispersions of dyes with a Particle size of less than 150 nm to produce. Preferably, the average particle size (diameter) is in the range of 10-100 nm. In contrast, the particles of dispersions, those using common oil formers produced, significantly larger.

In addition, the Latices in addition to the dye even with suitable light stabilizers and / or Antioxidants are loaded, indicating the stability of the photochromic Dye increases.

The Dye latices can continue with surface active Connections are offset.

Prefers contain the photochromic layers according to the present invention still dye stabilizers. For this purpose, particularly suitable dye stabilizers are listed below.

Of the Dye stabilizer ST-10 is under the trade name Lowinox 22CP46 for sale available.

In addition, thiomorpholine dioxide stabilizers (singlet oxygen quenchers), such as those in US 5,491,054 and US 5,484,696 and silicon-bridged bisphenols as described, for example, in US Pat EP 1 191 398 described in the context of the present invention proved to be advantageous. Furthermore, the known antioxidants are preferred as dye stabilizers.

Examples

Layer structure 101 (construction: TR-PS)

The photochromic material 101 was prepared as an example of an oxygen-sensitive layer by first applying to a triacetate film of 120 μm thickness (TR) a layer having the following composition by means of a continuously running casting machine: Layer 1 (photochromic layer, PS), dry coating 10 microns 99.97% by weight Acrylatlack (30 wt .-% solids) with a solvent mixture of ethyl and butyl acetate of 1: 1 and 0.03% by weight Dye according to Table 1.

Of the Dye was added in toluene in a concentration of each 30 g / 1 dissolved. The weight data refer to this and the following Layers each on the dry matter of the specified additives, ie without the substances which are volatile during drying, such as e.g. volatile solvents.

Subsequently was the material is dried in air at room temperature.

Layer structure 201 (Structure: TR-PS-BS)

The photochromic material 201 was first prepared as described for 101 and then another layer of the following composition was applied: layer 2 (barrier layer BS), dry coverage 10 μm 100.0% by weight Polyvinyl alcohol Elvanol T-66 from Dupont (10% by weight), aqueous solution

The The material obtained was again air-dried at room temperature.

Layer structure 301 (construction: TR-PS-BS-AS-BS)

The photochromic material 301 was first prepared as described for 201 and then the following further layers were applied in the order given: Layer 3 (absorber layer AS), dry application 10 μm 100.0% by weight Ascorbic acid (5% by weight), polyvinyl alcohol Elvanol T-66 from Dupont (10% by weight), aqueous solution Layer 4 (barrier layer BS), dry application 10 μm 100.0% by weight Polyvinyl alcohol Elvanol T-66 from Dupont (10% by weight), aqueous solution

The The material obtained was again air-dried at room temperature.

The photochromic materials were irradiated with the light of a daylight normalized 100 kL x xenon lamp and the percentage density decrease of the dye in the switched state was measured. Low percentage density decreases correlate with high stability of the dye in the photochromic layer. A sample was used as the 100% sample, which was exposed only until the maximum absorption was reached. As a measure of the life, the irradiation time was determined, after which the optical density in the switched state has decreased to 1 / 10th of the initial value. Relative life values are given as percentages in Table 1, with the value for layer 101 being arbitrarily set at 100%. Table 1 layer structure dye Relative life 101 FS-19 100 comparison 201 FS-19 500 comparison 301 FS-19 5000 invention

As can be seen from the table is through a barrier layer Alone the lifetime of the photochromic layer clearly improved, that's enough for However, critical applications are not enough. Only through the barrier layer package according to the present Invention, a qualitative stability improvement is achieved, the also for such critical cases provides adequate protection.

Claims (14)

Protective film to reduce exposure with a fabric XS that has a flexible backing and applied thereto Layers in the order given include: a) a layer, the low permeability for the Substance XS has (barrier layer BS), b) a layer that reduces the content of free substance XS in this layer (absorber layer AS) and c) another layer, which has a low permeability for the Substance XS has (barrier layer BS), taking the protective film under over and between the layers mentioned arbitrarily arranged further layers It may contain one of the barrier or absorber layers around the carrier can act and the barrier levels BS equal or different can be constructed. A protective film according to claim 1, comprising in the specified Order a carrier, Barrier layer, absorber layer and barrier layer (TR-BS-AS-BS). Protective film according to one of claims 1 or 2, comprising in the specified order a carrier, barrier layer, absorber layer, Barrier layer, absorber layer and barrier layer (TR-BS-AS-BS-AS-BS). A protective film according to any one of claims 1 to 3, additionally comprising 1 to 6 couples from absorber and barrier layer. Protective film according to one of the preceding claims, characterized characterized in that the barrier layer has a permeability coefficient for the harmful Substance XS of less than 0.1. Protective film according to one of the preceding claims, characterized characterized in that the substance XS is oxygen. Protective film according to one of the preceding claims, characterized characterized in that it comprises a functional layer FS. Process for producing a protective film according to one of the preceding claims, characterized in that at least one layer having a continuous Begussverfahren is applied. Method according to claim 8, characterized in that that it is the one with a continuous casting process applied layer around the most distant from the carrier barrier layer is. Method according to one of claims 8 or 9, characterized that at least two layers with a continuous casting process Applied in a machine passage by means of a Mehrfachgießers become. Use of a protective film according to one of claims 1 to 7 or one produced according to one of claims 8 to 10 Protective film as a protective film for OLEDs, solar cells or photochromic layers. Subject, with a protective film after a the claims 1 to 7 or one produced according to one of claims 8 to 10 Protective film is coated. Article according to claim 12, characterized that it is an OLED, a solar cell or a windowpane is. Device containing an article after a the claims 12 or 13.