WO2007025788A1 - Feuille protectrice autocollante exempte d'halogenes - Google Patents

Feuille protectrice autocollante exempte d'halogenes Download PDF

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Publication number
WO2007025788A1
WO2007025788A1 PCT/EP2006/063012 EP2006063012W WO2007025788A1 WO 2007025788 A1 WO2007025788 A1 WO 2007025788A1 EP 2006063012 W EP2006063012 W EP 2006063012W WO 2007025788 A1 WO2007025788 A1 WO 2007025788A1
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WO
WIPO (PCT)
Prior art keywords
protective film
self
adhesive
adhesive protective
film according
Prior art date
Application number
PCT/EP2006/063012
Other languages
German (de)
English (en)
Inventor
Nicolai Böhm
Michael Janning
Ingo Neubert
German Patino
Original Assignee
Tesa Ag
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Filing date
Publication date
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Publication of WO2007025788A1 publication Critical patent/WO2007025788A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/201—Adhesives in the form of films or foils characterised by their carriers characterised by the release coating composition on the carrier layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/006—Presence of polyolefin in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/10—Presence of homo or copolymers of propene
    • C09J2423/106—Presence of homo or copolymers of propene in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating

Definitions

  • the present invention relates to a halogen-free self-adhesive protective film which is suitable for covering, for example, graphics, prints, photos, reproductions, posters, brochures, pictures, plans, maps and books, and the use thereof on said substrates.
  • Digital printing is understood to mean graphics or images that are generated or processed by means of a computer and subsequently printed out by means of printers.
  • digital prints are used in advertising printing, shop window advertising, truck tarpaulins, advertising on building facades, trade fair construction, posters, posters, art prints and digital photography.
  • Conventional printing processes using printing stencils such as screen, gravure, flexographic and offset printing and printing processes without printing stencils such as electrography, laser, inkjet and thermal transfer printing are used as printing processes.
  • inkjet printing technology is the main method, since this printing process is the most flexible in terms of frequent pattern changes and small print jobs, and ensures excellent color and print quality.
  • ink jet printing technique different inks can be used.
  • water-based inks are used.
  • oil- or solvent-based printing inks are widespread. The reason for the widespread use of oil- and solvent-based Printing inks in these areas is due to the very good anchoring (adhesion) of these printing inks on the various printing media used here.
  • solvent-free printing inks are also being used to a greater extent in the industrial sector and in the advertising industry.
  • so-called UV printing inks solvent-free printing inks that crosslink or cure under UV irradiation, are becoming increasingly important in the future.
  • a wide variety of printing media such as paper, flexible PVC films, textiles, PET films for digital graphics use.
  • the print media often have to be provided with a special coating to ensure high print quality and anchoring of the printing ink.
  • Another possibility of protecting the digital prints results from a full-surface lamination of the same with a protective film, which is coated with a hot melt adhesive.
  • the print and the protective film must be laminated by means of a hot laminator at 60 to 150 0 C. This softens the hot melt adhesive and connects to the graphics.
  • a disadvantage of this method is that when paper is used as the printing medium, a dimensional change of the paper occurs due to drying out during the laminating process, with the consequence of later curling or wrinkling of the protected print. This method is also not suitable for printing media that soften like soft PVC at relatively low temperatures.
  • Another method for protecting digital prints results from a full-surface lamination with a self-adhesive protective film.
  • self-adhesive protective films does not show the previously mentioned disadvantages.
  • contact-transparent flexible PVC films are used as self-adhesive protective films, which are coated on one side with a pressure-sensitive adhesive.
  • a description of these surface protection films can be found in DE 44 05 568 A1 and DE 42 28 436 A1.
  • All self-adhesive protective films used today are laminated with a siliconized release paper or a siliconized release film which must be removed immediately prior to use.
  • the use of siliconized release paper or release film is based on the one hand in the production process of these protective films and on the other hand ensures an easily removable protection of the PSA prior to use. From the use of these conventional self-adhesive protective films, however, there are some disadvantages.
  • the soft PVC film usually contains 20 to 30% of monomer plasticizer, which evaporate gradually from the film, resulting in a significant odor and health burden, in particular, the commonly used plasticizer DOP is questionable.
  • the plasticizers also tend to migrate into, for example, the adhesive, ink and printing medium. The migration of the plasticizers can adversely affect the prints, so that, for example, color change, bleeding of the color transitions (chromatography) or yellowing can not be excluded.
  • PVC films also contain a significant amount of halogen. Against the background of the discussion about the incineration of plastic waste, however, there is a trend towards the reduction of the halogen content and thus the dioxin formation or to avoid the use of halogen-containing plastics.
  • the object of the present invention is to provide a self-adhesive protective film for covering, for example, in particular digital graphics, prints, photos, reproductions, posters, brochures, pictures, plans, maps and books, which meet today's high environmental standards Avoiding halo-containing plastics and hazardous waste, as well as allowing easy application.
  • the invention relates to a self-adhesive protective film consisting of a halogen-free transparent or translucent carrier film which is coated on one side with a pressure-sensitive adhesive and on the other side with a silicone release-based release coating.
  • the protective film according to the invention is halogen-free in the sense that the halogen content is optionally present only in trace amounts (less than 1000 ppm), as might occur through impurities or as residues of catalysts (for example from the polymerization of polymers), and thus is disregarded.
  • the halogen-free self-adhesive protective film can be wound on itself and requires no additional release film or release paper.
  • Translucent bodies have light transmittances of less than 90% and are said to be contact-clear if the material alone appears cloudy, but not when in direct contact with a substrate such as a digital graphic.
  • a carrier film of a PVC replacement material is used in the protective film according to the invention.
  • Monolayer or multilayer films of homo- and copolymers of propylene or ethylene or of polyesters such as, for example, are particularly suitable as carrier film materials Polyethylene terephthalate (PET).
  • PET Polyethylene terephthalate
  • the production of the carrier film is carried out with a calender or by extrusion or coextrusion such as in the blow or casting process.
  • the carrier film may be monoaxially or biaxially stretched.
  • Particularly preferred carrier material is a non-stretched extrusion film consisting of a polypropylene copolymer or a biaxially hidden PET film coated on both sides with a polyethylene film.
  • the thickness of the carrier film is in the range of 30 to 180 .mu.m, preferably 50 to 150 .mu.m.
  • the surface of the carrier film can be structured or smooth.
  • the surface of the carrier film is preferably matt or slightly matt structured.
  • the matting can be achieved by using a filler with a sufficiently high particle size.
  • the filler is applied for example by means of a coating or by a coextruded outer layer on the carrier film.
  • the structuring of the film surface is achieved by a roller (for example embossing roller on the calender or matted chili roll or embossing roll in the extrusion process).
  • the carrier film contains the customary primary (for example sterically hindered phenols or C radical scavengers) and / or secondary (for example sulfur compounds, phosphites or sterically hindered amines) aging protection agents.
  • customary primary for example sterically hindered phenols or C radical scavengers
  • secondary for example sulfur compounds, phosphites or sterically hindered amines
  • the carrier film of the protective film according to the invention contains UV protectants and advantageously also UV absorbers as further additives.
  • UV protectants is highly recommended, especially in polypropylene or polyethylene backing films, if not absolutely necessary to protect the film from embrittlement and yellowing during use.
  • the graphics and prints adhered to the protective film of the invention are used for up to one year of intensive exposure to light from, for example, luminaires and headlamps in indoor applications or direct sunlight in outdoor applications. applications exposed.
  • the protective film undergoes considerable UV exposure to UV light (only long-wave UV-A radiation, 320 to 400 nm, a Rolle) it comes via a radical mechanism to a polymer degradation.
  • UV light only long-wave UV-A radiation, 320 to 400 nm, a Rolle
  • the result is embrittlement, brittleness and discoloration of the carrier film.
  • Particularly vulnerable to UV radiation are films made of polyethylene and polypropylene.
  • the polymer degradation and thus the embrittlement of the carrier film can be stopped by the use of UV protection agents.
  • UV protectants preference is given to using hindered amines (HALS).
  • the self-adhesive protective film according to the invention likewise protects the graphics or prints from the damaging effect of UV radiation.
  • Particularly at risk here are the printing inks, which can fade under the influence of UV radiation.
  • the UV protectants just mentioned in the protective film do not offer effective protection since they only interfere with the polymer degradation process of the film.
  • the use of UV absorbers which absorb or filter out the UV radiation is particularly advantageous.
  • the UV absorbers used are usually benzophenones and benzotriazoles.
  • Ultraviolet absorbers which have good compatibility with the base polymer are particularly preferably used, since the UV absorbers tend to have a high tendency to chalk, which is also known to the person skilled in the art as blooming.
  • UV absorber based on benzotriazole having long-chain side chains are, for example, Tinuvin ® 1577 from Ciba, and Cyasorb UV-1164 ® from Cytec. To avoid Auskreidungen also a combination of different UV absorbers is helpful.
  • the UV absorbers are used in a concentration of 0.2 to 0.6 wt .-% based on the carrier film.
  • the concentration of the UV absorbers in the protective film according to the invention should be selected such that the transmission of light having a wavelength of less than 360 nm (UV light) is less than 40% and preferably less than 30%.
  • UV protectants and UV absorbers are described in "Plastics Additives Handbook", chapter “Light Stabilizers", Carl Hansa Verlag, 5th edition.
  • the self-adhesive protective film according to the invention is coated on one side with a translucent or transparent PSA.
  • the adhesive application is 10 to 40 g / m 2, preferably 18 to 28 g / m 2 (this is the amount after any necessary removal of water or solvent, the numerical values also correspond approximately to the thickness in ⁇ m).
  • the coating is preferably applied over the entire surface of the carrier film.
  • Suitable pressure-sensitive adhesives are all common types. Such pressure-sensitive adhesives may be, for example, homopolymers or copolymers of isobutylene, of 1-butene, of vinyl acetate, of ethylene, of acrylic acid esters, of butadiene or of isoprene.
  • pressure-sensitive adhesive special attention must be paid to aging resistance and compatibility with printing inks and printing media.
  • formulations based on polymers and copolymers based on acrylic esters or vinyl acetate are especially suitable.
  • the self-adhesive composition used can be mixed with one or more additives, such as tackifiers (resins), plasticizers, fillers, flame retardants, pigments, UV absorbers, light stabilizers, aging inhibitors, photoinitiators, crosslinking agents or crosslinking promoters.
  • additives such as tackifiers (resins), plasticizers, fillers, flame retardants, pigments, UV absorbers, light stabilizers, aging inhibitors, photoinitiators, crosslinking agents or crosslinking promoters.
  • Tackifiers are, for example, hydrocarbon resins (for example polymers based on unsaturated C 5 or C 9 monomers), terpene-phenolic resins, polyterpene resins from raw materials such as ⁇ - or ⁇ -pinene, aromatic resins such as cumarone-indene resins or Resins based on styrene or ⁇ -methylstyrene, such as rosin and its derivatives, for example disproportionated, dimerized or esterified resins, for example reaction products with glycol, glycerol or pentaerythritol, to name but a few, and also other resins (such as listed in detail) in Ullmann's Encyclopedia of Industrial Chemistry, Volume 12, pages 525 to 555 (4th edition), Weinheim).
  • hydrocarbon resins for example polymers based on unsaturated C 5 or C 9 monomers
  • terpene-phenolic resins polyterpene resins from raw materials such as ⁇ - or ⁇ -pinene
  • Suitable fillers which do not affect the transparency of the adhesive are nano-scale fillers, for example based on titanium dioxide, calcium carbonate, zinc carbonate, silicates or silicic acid.
  • Suitable miscible plasticizers are, for example, aliphatic, cycloaliphatic and aromatic mineral oils, di- or polyesters of phthalic acid, trimellitic acid or adipic acid, liquid rubbers (for example low molecular weight nitrile or Polyisoprenkautschuke), liquid polymers of butene and / or isobutene, acrylic acid esters, polyvinyl ethers, liquid and soft resins based on the raw materials of tackifier resins, wool wax and other waxes or liquid silicones.
  • Crosslinking agents are, for example, isocyanates, phenolic resins or metal chelates, such as aluminum and titanium chelate.
  • Suitable crosslinking promoters are, for example, maleimides, allyl esters, such as triallyl cyanurate, polyfunctional esters of acrylic and methacrylic acid.
  • Anti-aging agents include, for example, hindered phenols, known, for example, under the trade name Irganox TM.
  • the bond strength of the self-adhesive protective film according to the invention to steel is at least 2.0 N / cm.
  • the preferred embodiment of the invention has on one side a pressure-sensitive adhesive based on homopolymers or copolymers of acrylic acid esters, which has been achieved by solvent-containing or particularly preferably by dispersion coating of polyacrylic acid esters.
  • This preferred embodiment of the protective film according to the invention is characterized in particular by its very good aging stability and compatibility with the printing inks and printing media, for example, from flexible PVC films. Even in outdoor applications of up to one year, where the protective film may be exposed to intense sunlight, no change in transparency or occurrence of yellowing of the PSA is observed. Furthermore, there is a very good compatibility with the different printing inks, that is, no chromatography of the various constituents of the printing inks is observed.
  • an adhesion promoter a so-called primer layer
  • the known dispersion and solvent systems can be used, for example, based on isoprene- or butadiene-containing rubber, acrylate rubber, polyvinyl, polyvinylidene and / or cyclic rubber. Isocyanates or epoxy resins as additives improve the adhesion and in part also increase the shear strength of the pressure-sensitive adhesive.
  • the adhesion promoter can likewise be applied to the carrier by means of a coextrusion layer. be applied foil. For example, flame treatment, corona or plasma or coextrusion layers are suitable as physical surface treatments.
  • the back side of the carrier film is coated with a release agent or release agent of preferably polysiloxane.
  • This silicone release coating allows a very easy and uniform unrolling of the protective film according to the invention in the application. This results in the case of the protective film according to the invention over the prior art, the advantage that can be dispensed with the use of a release paper or a release film.
  • release coatings such as stearyl compounds, however, too high separation forces are observed to PSA, so that a slight unrolling in the application is not possible. The result of this is that so-called trigger or chatter marks form at each start of the unwinding after a stop, which lead to disturbing horizontal stripes at these points on the graph laminated with the protective film.
  • Suitable coatings are the customary polysiloxane release coating, for example from Wacker, Rhodia or Dow Corning. Suitable coatings are solvent-based, emulsion-based or 100% systems. These polysiloxane coatings are usually crosslinked by an addition reaction or by a condensation reaction.
  • a very easily separating polysiloxane system is used for the coating, in which the release forces with the test tape tesa ® 7475 (substrate white PVC film, adhesive acrylate) is less than 30 cN / cm and the unwinding force, the invention wound on itself Protective film, smaller than 0.8 N / cm are.
  • the carrier film is preferably pretreated before the coating by means of corona or likewise coated with a bonding agent.
  • UV silicones contain epoxy rings that are incorporated in the polysiloxane chains. UV radiation liberates a cation which causes a cationic ring opening followed by a crosslinking reaction via the epoxy rings in the individual polysiloxane chains.
  • This crosslinking method seems to have a stabilizing effect on the aging and UV resistance of the polysiloxane.
  • Syl-Off UV® UV silicone systems from Dow Corning.
  • a structured carrier foil can be used as already described.
  • matting of the protective film according to the invention is also possible by adding suitable finely divided fillers into the polysiloxane release coating system. The amount added, the grain size and the quality of the filler must be selected such that, on the one hand, the release values and, on the other hand, the transparency or the transmission of the polysiloxane release coating are not impaired.
  • the polysiloxane 0.5 to 30 wt .-%, preferably 2 to 10 wt .-% (each based on the amount of release coating) of a filler having a particle size of 1 to 15 microns, preferably 3 to 8 ⁇ m added (see also "Plastics Additives Handbook", chapter “Anti-Block Additives", Carl Hansa Verlag, 5th edition).
  • Suitable fillers are, for example, calcium carbonate, Zeo- lite, natural and / or particularly preferred synthetic silica such as Syloid ® by the company Grace (micronized silica).
  • the surface of the self-adhesive protective film according to the invention preferably has a matted surface to avoid light reflection.
  • the measurement of the gloss level reflects this effect.
  • the degree of gloss, measured at 60 °, in the case of the protective film according to the invention is less than 40 and particularly preferably less than 30.
  • the protective film can be used particularly advantageously as protection for graphics, prints, photos, reproductions, posters, brochures, pictures, plans, maps and books and similar printing units.
  • the peel strength (bond strength) was tested on the basis of PSTC-1.
  • a 20 mm wide strip of the protective film is glued on a ground steel plate as a test surface by five times double rolling over with a 5 kg roll.
  • the plate is clamped, and the self-adhesive strip is peeled over its free end on a tensile tester at a peel angle of 180 ° at a speed of 0.3 m / min, and determines the force required for this.
  • the measurement results are given in N / cm and averaged over three measurements. All measurements are carried out in an air-conditioned room at 23 ° C and 50% relative humidity.
  • the release properties of release coatings are compared to the standard test tapes tesa ® 7475 and tesa ® 7476 determined.
  • 20 mm wide strips of test tapes tesa ® 7475 and tesa ® are glued on the tested release varnish coating 7476th
  • a 24-hour storage takes place under a weight block of 20 kg at 70 ° C (tesa ® 7475) or at 40 ° C (tesa ® 7476).
  • the force that is required to subtract the test tape at an angle of 180 ° from the tested release coating is carried out in accordance with PSTC-4B.
  • the release forces are preferably determined at higher take-off speeds of 10 and 50 m / min.
  • the adhesive tape is glued in a width of 50 mm on the release coating.
  • the adhesive tape is then peeled off from the release lacquer coating at an angle of 180 ° at 10 or 50 m / min, thereby measuring the required force. Again, between bonding and measurement storage at elevated temperatures is possible. The measurements are carried out.
  • the unwind force 50 mm wide rolls are unrolled at different speeds (10, 20 and 30 m / min). The force needed to unroll the test roll is determined. The unwind force is measured by deflecting the adhesive tape web via a load cell. The measurement is carried out according to PSTC-8.
  • the self-adhesive protective films are bonded to a test print.
  • the test print consists of different shades. Ideally, at the same time test prints are tested with loose ittel containing and water-based colors. For comparison, a narrow opaque strip of, for example, paper over the graphic placed and fixed (to create a color reference).
  • the test print coated with the protective film is now stored for 36 d under UV irradiation (Sanolux HRC 300-280 Radium Lampenwerk GmbH), the samples being examined every 5 days. Subsequently, the color quality and color intensity in relation to the color reference (covered area) as well as the properties (brittleness, discoloration, etc.) of the protective film are evaluated.
  • This protective film is characterized by a very good contact transparency and a very easy unrollability without chatter marks. Furthermore, this protective film has excellent aging and UV stability, but it should mainly be used only for indoor applications because it does not protect the print or graphics from UV radiation due to the absence of UV absorbers.
  • a transparent PP film is produced using the Cast process, whereby a matted Chill-RoII is used to matt the film.
  • the film containing 0.1 wt .-% Chimasorb ® 944 (Ciba) and 0.3 wt .-% of the UV absorber Tinuvin ® 1577 (Ciba).
  • the foil is coated on one side (on the etched side) to corona treatment with the solvent-silicone release coating system Syl-off ® 7020 (Dow Corning).
  • a second step after renewed corona treatment, the coating of the other side of the film in the Meyer-Barr process with a mixture of the 40 wt .-% Acronal ® DS 3502 (aqueous acrylate dispersion, solids content 55 wt .-%; pH 6.5 to 8.5, T 9 4 0 C from BASF) and 60 wt .-% Acronal ® V 212 (aqueous acrylic dispersion, solids content 69 wt .-%; pH 3.5 to 6.0 , BASF T 9 -40 0 C) in a coating width of 2000 mm.
  • an adhesive application of 23 g / m 2 is obtained .
  • this protective film In addition to the very good contact transparency, UV stability, very easy unwindability, this protective film also has good UV absorption, so that the protected graphics are very well protected against fading of the colors in outdoor applications.
  • a transparent PP film is produced using the cast process.
  • the film containing 0.1 wt .-% Chimasorb ® 944 (Ciba) and 0.3 wt .-% of the UV absorber Cyasorb UV-1164 ® (Cytec).
  • the foil is coated on one side by corona treatment with the solvent-silicone release coating system Syl-Off UV ® (Dow Corning) containing 3 wt .-% for matting Sylobloc ® 44 (Grace Davison).
  • This protective film shows good contact transparency, UV stability, very easy unwindability and good UV absorption.
  • a 23 ⁇ m thick PET film is coated on both sides with 20 g / m 2 with a PE layer, wherein the surface of a PE layer is matted by an embossing roller. Subsequently, the matte side is coated after Corona treatment with the silicone release coating system Syl-Off ® 7400 (Dow Corning). The other side of the film is coated analogously to Example 2 with adhesive.
  • This protective film shows a very good contact transparency, UV stability, very easy unwindability and good UV absorption.
  • the standard product Filmolux ® satin (Neschen AG) consists of a 75 micron satin soft PVC support film (containing about 26% monomeric plasticizer) that on one side with 35 g / m 2 acrylate Dispersionsklebmasse is coated with a 65 g / m 2 Release paper is covered.
  • the use of a release paper is urgently necessary because otherwise the unwinding of the protective film bales is no longer possible.
  • Other problems arise from the high halogen and plasticizer content that commonly occurs with the use of PVC materials.
  • the product Filmolux PP® satin (Neschen AG) consists of a 80 ⁇ m silk-matt UV-protected PP carrier film which is coated on one side with 28 g / m 2 of an acrylate dispersion adhesive which is covered with a 80 g / m 2 release paper. Again, it is not possible to use the product without release paper, otherwise the unrolling of the bale is no longer possible.
  • An 80 ⁇ m PP cast film (without UV protection agent) is coated on the one side with 1.5 g / m 2 of Release Coat KB (Clariant AG) from toluene solution and on the other side with an acrylate dispersion adhesive analogous to Example 1 coated and wound up after drying at 110 0 C without release paper.
  • This protective film can be developed only with relatively high unwinding forces. When unwinding, clear chatter marks are visible, which significantly degrade the optical quality of the protected graphics and prints. In UV storage tests, a clear embrittlement appears after only 5 days and, after 9 days, the appearance of break lines in the protective film. The inks under the protective film bleach very much in the UV test.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Feuille protectrice autocollante destinée à couvrir en particulier des graphiques, impressions, photos, reproductions, affiches, prospectus, images, plans, cartes topographiques et livres obtenus de manière numérique, qui est constituée d'une feuille de support exempte d'halogènes, transparente ou translucide, couverte sur une face d'une masse adhésive et sur l'autre face d'un vernis de séparation de préférence à base de polysiloxane.
PCT/EP2006/063012 2005-06-24 2006-06-08 Feuille protectrice autocollante exempte d'halogenes WO2007025788A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005029722A DE102005029722A1 (de) 2005-06-24 2005-06-24 Halogenfreie selbstklebende Schutzfolie
DE102005029722.6 2005-06-24

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WO2007025788A1 true WO2007025788A1 (fr) 2007-03-08

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WO (1) WO2007025788A1 (fr)

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US9752022B2 (en) 2008-07-10 2017-09-05 Avery Dennison Corporation Composition, film and related methods
DE102009006936A1 (de) * 2009-01-30 2010-08-05 Tesa Se Trennmittel insbesondere für ein Klebeband
BR112012022175A2 (pt) 2010-03-04 2016-10-25 Avery Dennison Corp película não de pvc e laminado não de pvc
EP2802454A1 (fr) * 2012-01-11 2014-11-19 Avery Dennison Corporation Films de stratification de protection
MX2016007964A (es) 2013-12-30 2016-09-09 Avery Dennison Corp Pelicula protectora de poliuretano.
DE102018116748A1 (de) 2018-07-11 2020-01-16 Infiana Germany Gmbh & Co. Kg Lokal deaktivierte Releasebeschichtung

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DE4121599A1 (de) * 1991-06-29 1993-01-07 Alkor Gmbh Kunststoffolienbahn
WO2001098425A1 (fr) * 2000-06-21 2001-12-27 Tesa Ag Bande adhesive de securite destinee a deceler l'ouverture non autorisee d'un emballage
WO2005037906A1 (fr) * 2003-10-14 2005-04-28 Tesa Ag Pellicule de gainage souple exempte d'halogenes composee d'hydroxyde de magnesium contenant une polyolefine

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DE2629535C3 (de) * 1976-07-01 1979-10-11 Beiersdorf Ag, 2000 Hamburg Verfahren zur Herstellung von blatt- oder bahnförmigen Materialien, die mindestens auf einer Seite eine beschriftbare klebstoffabweisende Beschichtung tragen
DE4405568C2 (de) * 1994-02-14 1998-04-16 Hans Neschen Gmbh Verwendung eines Haftklebers auf Basis von wäßrigen Dispersionen zur Herstellung von Klebefolien
WO1997008260A1 (fr) * 1995-08-22 1997-03-06 Minnesota Mining And Manufacturing Company Film adhesif autocollant, antistatique et optiquement transparent
DE19532220A1 (de) * 1995-09-01 1997-03-06 Beiersdorf Ag Selbstklebende Schutzfolie
DE19707786A1 (de) * 1997-02-27 1998-09-03 Ppg Industries Inc Kunststoffolie, ihre Verwendung in Verfahren zur Herstellung von Verpackungsbehältern, die so hergestellten Verpackungsbehälter sowie die Verwendung von Lacken zur Applikation über Druckfarbe
DE19923780A1 (de) * 1999-05-22 2000-11-23 Beiersdorf Ag Unverstreckte Oberflächenschutzfolie aus Polypropylenblockcopolymer
DE10318151A1 (de) * 2003-04-17 2004-10-28 Tesa Ag Selbstklebende Schutzfolie zum temporären Schutz von Fahrzeuglacken

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Publication number Priority date Publication date Assignee Title
DE4121599A1 (de) * 1991-06-29 1993-01-07 Alkor Gmbh Kunststoffolienbahn
WO2001098425A1 (fr) * 2000-06-21 2001-12-27 Tesa Ag Bande adhesive de securite destinee a deceler l'ouverture non autorisee d'un emballage
WO2005037906A1 (fr) * 2003-10-14 2005-04-28 Tesa Ag Pellicule de gainage souple exempte d'halogenes composee d'hydroxyde de magnesium contenant une polyolefine

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