WO2021001448A1 - Silicone à surface modifiée, son utilisation dans des revêtements anti-adhésifs et matériau composite contenant ladite silicone - Google Patents

Silicone à surface modifiée, son utilisation dans des revêtements anti-adhésifs et matériau composite contenant ladite silicone Download PDF

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WO2021001448A1
WO2021001448A1 PCT/EP2020/068567 EP2020068567W WO2021001448A1 WO 2021001448 A1 WO2021001448 A1 WO 2021001448A1 EP 2020068567 W EP2020068567 W EP 2020068567W WO 2021001448 A1 WO2021001448 A1 WO 2021001448A1
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Prior art keywords
silicone
adhesive
range
modified surface
radiation
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PCT/EP2020/068567
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German (de)
English (en)
Inventor
Ralph Wilken
Laura SCHILINSKY
Christopher DÖLLE
Christoph SCHMÜSER
Martin WIESING
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Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein
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Priority to EP20737397.8A priority Critical patent/EP3994226A1/fr
Publication of WO2021001448A1 publication Critical patent/WO2021001448A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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 silicone with a modified surface, with this silicone with a modified surface particularly little carbon being exchanged for the unmodified silicone, a composite material comprising said silicone and a carrier material, as well as a method for producing said silicone with a modified surface .
  • the present invention also relates to the use of the said silicone with a modified surface in non-stick coatings and the use of the said composite material as a release film and / or as a release liner for substances with high surface adhesion.
  • Siliconization on foils and papers is used in a variety of ways, especially as release foils or release papers, for example to protect pressure sensitive adhesives and other substances with a high surface tack ("surface tack") such as highly viscous media, adhesives, varnishes or similar from unwanted sticking.
  • surface tack a high surface tack
  • Typical examples of such products are self-adhesive labels and self-adhesive semi-finished products such as mirror mountings, pressure-sensitive adhesives from or on screens of, for example, tablet computers or smartphones, and attachments in the vehicle exterior, such as trim strips or logos, or in the vehicle interior.
  • release films or release papers (often also referred to as “release liners”) are peeled off the pressure-sensitive adhesive and the adhesion is carried out by bringing it into contact with the substrate before the desired gluing.
  • the release force that is to say the force that has to be applied to peel the release liner from the pressure-sensitive adhesive
  • the double-sided adhesive tape in which one side of the release liner has to have higher release forces in order to ensure that the release line is always on one side, namely on the side of the pressure-sensitive adhesive that is to the center of the adhesive tape roll shows. This ensures that with a double-sided adhesive tape, the roll is always covered on the outside with the release liner and the pressure-sensitive adhesive is not exposed.
  • controlled release additives such as known "MQ resins”
  • Layer thicknesses of the silicone and the substrate can also influence the later release properties.
  • the document WO 2015/044247 relates to a plasma-polymer solid, in particular a plasma-polymer layer.
  • the document WO 01/32949 A1 specifies a method and a device for plasma coating of surfaces.
  • the document WO 2008/132230 A2 describes a method for producing thin layers and a corresponding layer.
  • WO 2015/075040 A1 describes a method for connecting silicone rubber to a substrate.
  • the document EP 0 550 510 B1 (equivalent to DE 692 24 370 T2) describes a composition of a modified polysiloxane and a rubber article coated therewith.
  • WO 2019/197492 A1 describes a surface-modified silicone, its use in non-stick coatings and a composite material containing this.
  • set-off is understood to mean the transfer of Si-containing components from one surface to another during or after the surfaces come into contact with one another.
  • a "small set-off” preferably denotes the transfer or removal from a modified silicone surface according to the invention with an Si content of ⁇ 1.5 at% after contact with another surface, in particular the surface of a pressure-sensitive adhesive tape, each measured with X-ray photoelectron spectroscopy (ESCA).
  • a further object of the present invention was to produce a method for producing said silicone with a modified surface or a composite material containing this.
  • Another specific object of the present invention was to provide a said silicone with a modified surface for use in non-stick coatings and to provide a said composite material containing said silicone with a modified surface for use as a release film or release liner liner for fabrics with high surface adhesion.
  • the primary object and further objects and / or sub-objects of the present invention are achieved by a silicone with a modified surface, preferably with a surface modified by UV radiation, the concentration of silanol groups on the modified surface versus the concentration of silanol groups in the unmodified silicone is increased by 0.0015 at% to 0.13 at%, preferably by 0.0015 at% to 0.08 at%, measured by ESCA after chemical gas phase derivatization and based on the total number of atoms detected by ESCA (X-ray photoelectron spectroscopy).
  • atomic percent is a percentage of the content of an atomic type (eg for silicon) in a mixture containing this atomic type, customary in the technical field. It is defined as the quotient of (i) the number (or amount of substance) all in one Mixture (usually in a solid) containing atoms of the type of atom under consideration (e.g. silicon) and (ii) the number (or amount of substance) of all atoms contained in the mixture (if these are accessible to the measuring method or measuring technology used):
  • the layer thickness range up to this depth (3 * t1) is considered modified.
  • the mean depth range 1 correlates with the mean penetration depth of the radiation.
  • the modification depth (3 * t1) therefore corresponds by definition in the present application to the penetration depth of the radiation.
  • the inventors have surprisingly found that, particularly in the area of very low increases in adhesive force, the control of the silanol groups in the sense of the present text is an extremely suitable variable in order to achieve the desired effects. This could not be foreseen from the state of the art known to date, and there were also hardly any detection methods with which the corresponding results of the respective modification could be checked.
  • a silicone according to the invention with a modified surface (or a silicone according to the invention with a modified surface which is specified as preferred in this text), preferably with a surface modified by UV radiation, with a surface of the modified surface or the surface modification having an opposite unmodified silicone has a carbon content reduced by ⁇ 0.1 atom%, measured by ESCA and based on the total number of atoms detected by ESCA.
  • a “modified surface” of a silicone comprises a structural change and / or a change in the material composition of the modified surface compared to the unmodified silicone, the modification preferably by means of radiation, preferably by means of UV radiation (for the preferred wavelength range see below), particularly preferably by means of VUV radiation, and very particularly preferably by means of longer-wave VUV radiation (> 150 nm - ⁇ 190 nm).
  • UV radiation for the preferred wavelength range see below
  • VUV radiation very particularly preferably by means of longer-wave VUV radiation (> 150 nm - ⁇ 190 nm).
  • silicone according to the invention with a modified surface only one surface can be modified (preferred) or two or optionally (if present) several surfaces can be modified.
  • unmodified silicone for the purpose of comparison with the silicone according to the invention with a modified surface, (i) an unmodified silicone from the same batch of manufacture, (ii) an unmodified part or area of the surface of the silicone according to the invention with a modified surface can be used or (iii) the unmodified silicone below the modified surface of the silicone with modified surface, preferably at a depth of> 1 pm, particularly preferably at a depth of> 3 pm, below the modified surface.
  • This is related to the usual penetration depth of the longer-wave VUV radiation, which is particularly preferably used to modify the surface of the silicone, with wavelengths in the range from> 150 nm to ⁇ 190 nm, which as a rule is the depth given above of 1 pm or 3 pm does not exceed.
  • the effects according to the invention of the surface modification of the silicone in a silicone with a modified surface can practically no longer be detected, but can be calculated in the manner described above.
  • the unmodified silicone below the modified surface (above alternative (iii)) is used.
  • silicone is understood to mean a poly (organo) siloxane in which silicon atoms are linked via oxygen atoms.
  • a silicone in the context of this invention can be present in uncrosslinked form (rubber), partially crosslinked or completely crosslinked. Partially crosslinked means that, preferably within the scope of a vulcanization reaction, further crosslinking up to complete crosslinking (fully crosslinked) can take place.
  • the molecular chains are preferably at least partially crosslinked.
  • the remaining free valence electrons of the silicon are saturated by hydrocarbon radicals, hydrogen or by functional groups that are or contain heteroatoms.
  • a silicone within the meaning of this text can include conventional additives such as additives or fillers and has a
  • SHORE> 1 Hardness of preferably SHORE> 1, more preferably> SHORE 3, classified according to the SHORE A test.
  • the SHORE A hardness is measured according to DIN ISO 7619-1: 2010.
  • silicones are preferably selected from the group consisting of silicone elastomer, silicone resin and silicone rubber, silicone elastomers being particularly preferred and silicone oils not being included.
  • Silicone elastomers have a SHORE A hardness of 1 to 90, preferably 3 to 80, and / or a modulus of elasticity at 100% elongation ⁇ 5 MPa and / or a tensile strength of ⁇ 11 MPa.
  • the SHORE A hardness is preferably measured according to DIN ISO 7619-1: 2010.
  • the tensile strength and the stress values in the tensile test are preferably measured in accordance with DIN 53504: 2009-10.
  • a silicone resin is not an elastomer, which preferably means that the elongation at break of the material of a silicone resin is ⁇ 100% according to the definition given above. Silicone resins typically do not contain fumed silica as a filler. In fully cross-linked form, “silicone resins” in the sense of this text preferably have a SHORE D “hardness” of 20-50 measured according to DIN ISO 7619-1: 2010.
  • Silicone rubbers are (as opposed to silicone oils) silicones that can be converted into a rubber-elastic state and have groups that are accessible for a crosslinking reaction, such as hydrogen atoms, hydroxyl groups, vinyl groups or acetate residues. In a special version (UV-crosslinking silicone rubber), uncrosslinked silicones can carry organic residues with an acrylate or epoxy function as functional groups. Silicone rubbers have a viscosity of 50 mPa * s to 700,000 mPa * s, preferably 1000 mPa * s up to 500,000 mPa * s, particularly preferably 5,000 mPa * s to 200,000 mPa * s. The viscosity is preferably measured according to EN ISO 3219.
  • the unmodified silicone is a silicone elastomer that resulted from an addition reaction, preferably a UV radiation-induced addition reaction, or more preferably a transition metal-catalyzed addition reaction, and very particularly preferably a Pt-catalyzed addition reaction is.
  • a silicone according to the invention with a modified surface or a silicone according to the invention with a modified surface which is specified above or below as preferred, the modified surface being a surface modified by UV radiation, preferably by VUV radiation.
  • UV radiation refers to electromagnetic radiation with a wavelength in the range from> 50 nm to ⁇ 380 nm.
  • VUV radiation vacuum ultraviolet radiation
  • longer-wave VUV radiation denotes VUV radiation with a wavelength in the range from 150 to 190 nm.
  • VUV radiation and longer-wave VUV radiation are accordingly preferred subregions of the UV radiation to be used according to the invention in the context of the present invention.
  • a silicone according to the invention with a modified surface or a silicone according to the invention with a modified surface that is specified above or below as preferred
  • the modified surface having a higher separation force compared with the unmodified silicone compared to the adhesive surface of a reference adhesive tape, the reference tape preferably being TESA 07475 and where the separation force increase is in the range> 10% to ⁇ 579%, preferably> 20% to ⁇ 299%, particularly preferably> 28% to ⁇ 299%, based on the separation force of the unmodified silicone.
  • the said modified surface preferably has a higher release force with respect to several or all of the reference adhesive tapes selected from the group consisting of Tesa®-Film 57386, Tesa®-Film 57370, Tesa®-Film 57405, Tesa ®-4651, Tesa ⁇ -07475, Tesa ⁇ -07475 PV2 and Tesa®- 07476 and Tesa®-4154.
  • the designations given above for the reference adhesive tapes preferably refer to those compositions of the reference adhesive tapes as they are or were commercially available on the filing date of the present invention.
  • a corresponding adhesive tape is preferably used which has an adhesive strength on steel in the range from 5 to 15 N / cm, preferably Range from 10 to 15 N / cm, preferably measured according to the method specified in document WO 2016/071387 A1, page 13, lines 12 to 22.
  • Particularly preferred as the corresponding reference adhesive tape to be used with preference according to the invention are the reference adhesive tape “Tesa®-07475” in the composition or with the properties as they existed or existed on the filing date of the present invention.
  • the 180 ° peel test based on test method FINAT FTM 10 is preferably used as the peel test for the purposes of the present invention, as described in the FINAT Technical Handbook, 9th edition 2014, with a FINAT test roller (pressure roller) 5kg roll is used, preferably as described in measurement example 3 of the present text.
  • the peel test to determine the release force of the modified surface of a silicone according to the invention with a modified surface is preferably carried out with a composite material according to the invention (see below), which comprises a silicone according to the invention with a modified surface and preferably on one of the surfaces of its carrier material with a carrier material according to the invention Silicone is coated with a modified surface, the modified surface of the silicone facing away from the carrier material and is thus available for the peel test.
  • a silicone according to the invention with a modified surface is preferred (or a silicone according to the invention with a modified surface specified above or below as preferred), the separation force measured with a peel test against the adhesive surface of a reference adhesive tape, the reference tape preferably being TESA 07475, in the range of 0.018 N / cm to 1.2 N / cm, preferably from 0.02 N / cm to 0.75 N / cm, particularly preferably 0.031 N / cm to 0.38 N / cm.
  • the modified surface and / or the unmodified silicone preferably comprises at least partially crosslinked silicone elastomer.
  • the at least partially crosslinked silicone elastomer preferably comprises units of dimethylsiloxane, phenylmethylsiloxane, copolymers of dimethylsiloxane, copolymers of phenylmethylsiloxane and mixtures thereof.
  • a silicone according to the invention with a modified surface or a silicone according to the invention with a modified surface which is specified above or below as preferred, the unmodified silicone being based on a dimethylsiloxane, a phenylmethylsiloxane and / or diphenylsiloxane and their copolymers.
  • uncrosslinked silicone can also be used as the unmodified silicone whose surface is modified.
  • uncrosslinked, UV-crosslinking silicone rubbers which usually crosslink by UV light with wavelengths> 220 nm, also crosslink by irradiation with VUV radiation with wavelengths in the range from> 150 nm to ⁇ 190 nm and then in one practically not to be separated step can also be modified by the irradiation.
  • silicone which comprises MQ resin preferably with a mass fraction of MQ resin in the range from> 3% by weight to ⁇ 50% by weight, particularly preferably in, can also be used as the unmodified silicone whose surface is modified Range from> 20% by weight to 35% by weight, based on the total mass of the unmodified silicone comprising MQ resin.
  • unmodified silicone comprising MQ resins is not preferred for the purposes of the present invention, since it is often not possible to achieve satisfactory selectivity in the range of low release forces.
  • the level of the respective release force of a pressure-sensitive adhesive of a conventional silicone-based release liner is usually set by means of silicone resins and in particular by means of so-called MQ resins.
  • MQ resins A good overview of silicone resins and especially MQ resins is provided by D. Satas, Handbook of Pressure Sensitive Adhesive Technology, 3rd Edition, p. 664.
  • the different separation forces of the individual release layers compared to a pressure sensitive adhesive are then the result of different MQ resin proportions in the respective release composition.
  • the MQ resins offer the option of setting the release forces, e.g. of a release liner, and in particular the release forces of the release liner on the sides of a double-sided adhesive tape (and separately from one another), a specific silicone composition must be selected for each desired release force which is then coated on a carrier and cured. This makes it necessary to use several release liners with different MQ resin contents and to stock them if there is a need for different release properties. Because of the great variety of different pressure-sensitive adhesive compositions, such a storage is hardly feasible. Furthermore, the use of many different pressure-sensitive adhesive compositions can lead to increased waste material, since the individual pressure-sensitive adhesive compositions cannot be stored permanently. Instead, for example, the respective pressure-sensitive adhesive composition must be produced directly before application.
  • a silicone according to the invention with a modified surface is therefore preferred (or a silicone according to the invention with a modified surface which is specified above or below as preferred), wherein the modified surface and / or the unmodified silicone (from which the silicone with modified surface is or was preferably produced) comprises at least partially crosslinked silicone elastomer, the at least partially crosslinked silicone elastomer preferably comprising dimethylsiloxane units, and / or in the unmodified silicone (from which the silicone with modified surface is or was preferably produced) the proportion of oxygen, based on the total number of atoms present in the silicone with the exception of hydrogen atoms, ⁇ 33 at%, preferably ⁇ 30 at% and particularly preferably ⁇ 27 at%, preferably measured by means of elemental analysis.
  • the silicone according to the invention with a modified surface thus preferably comprises silicone which only comprises a small proportion of MQ resin or resins, particularly preferably which does not contain any MQ resin or resins.
  • silicone according to the invention with a modified surface it is particularly well possible to selectively set different separation forces even in the range of relatively low separation forces.
  • a silicone according to the invention is particularly preferred, the unmodified silicone containing no controlled release additives, in particular no MQ resins and no pyrogenic silicas.
  • a silicone according to the invention with a modified surface (or a silicone according to the invention with a modified surface that is specified above or below as preferred), the modified surface having a layer thickness in the range from> 100 to ⁇ 6000 nm, preferably in the range from> 300 to ⁇ 3000 nm, and / or the modified surface with a higher separation force compared to the adhesive surface of a reference adhesive tape, in comparison with the unmodified silicone, has two or more surface areas which have differently increased separation forces compared to the unmodified silicone.
  • the modified surface with a higher separation force compared to the adhesive surface of a reference adhesive tape, compared with the unmodified silicone has two or more surface areas which have differently increased separation forces compared to the unmodified silicone, it is possible to provide modified surfaces with areas of specifically adjusted, different separation forces. This is particularly advantageous when surfaces with areas of different adhesive properties are desired, for example areas in which a strongly adhesive surface sticks relatively less, so that in these areas the surface can be touched and handled without problems ("handles") without it comes to an undesirable adhesive contact.
  • the present invention also relates to a method for producing a silicone with a modified surface, preferably a preferred silicone according to the invention with a modified surface specified above, comprising the steps:
  • (V1) providing silicone, preferably at least partially crosslinked silicone elastomer, and (V2) irradiating at least part of the surface of the silicone from step (V1) with UV radiation of at least one wavelength in the range from> 50 nm to ⁇ 380 nm, preferably in the range from> 150 nm to ⁇ 200 nm, more preferably in Range from> 150 to ⁇ 190 nm, in an atmosphere with an oxygen content in the range from> 0 to ⁇ 22% by volume, preferably in the range from> 10 to ⁇ 21% by volume, so that a silicone according to the invention with modified surface results.
  • the irradiation in step (V2) preferably takes place by means of an excimer lamp or a low-pressure mercury lamp as the radiation source, since these lamps have proven to be particularly suitable and easy to handle for the method according to the invention.
  • low-pressure mercury lamps have a radiation band at 254 nm.
  • This radiation band can generally have an advantageous effect on the silicone elastomer activation in step (V2).
  • ozone is broken down by the 254 nm radiation and partially converted into atomic, reactive oxygen. The latter can be used advantageously for activation.
  • the radiation dose (as for the entire text) only radiation with a wavelength ⁇ 250 nm is taken into account. This means that the dose introduced due to the 254 nm band is not included in the calculation of the dose to be used according to the invention.
  • lasers preferably excimer lasers, they are preferably selected so that their pulse energies are below the ablation threshold of the silicones to be irradiated. Continuous lasers are preferred.
  • the silicone elastomer can be treated with a plasma, which also emits radiation in the above-mentioned wavelength range.
  • Plasmas consisting of a hydrogen / oxygen mixture are preferred. Hydrogen-containing plasmas are particularly preferred here.
  • one radiation source (as described above) or several radiation sources can be used, for example as a battery of several radiation sources (as described above), which can be the same or different (different types of radiation).
  • Achieving the desired effect of the method according to the invention ie the production of a silicone with a modified surface which has an (defined above) proportion of silanol groups on the surface of the modified surface compared to the unmodified silicone, can be based on the following parameters in more detail below The following can be influenced: - The wavelength of the UV radiation, with shorter wavelengths resulting in a lower penetration depth and thus a lower modification depth due to the higher absorption cross-section, but at the same time leading to a more modified surface (closer to the surface, stronger crosslinking of the silicone) and thus to a stronger one Increase in the separation force of the modified surface, preferably compared to the adhesive surface of a reference adhesive tape.
  • a wavelength of the UV radiation used in the range from> 50 nm to ⁇ 380 nm preferably in the range from> 150 nm to ⁇ 200 nm, more preferably in the range from> 150 to ⁇ 190 nm.
  • a distance between the radiation source and the surface of the silicone to be irradiated is preferred in the range from 0.5 to 50 mm, preferably in the range from 0.5 to 10 mm, particularly preferably in the range from 1 to 5 mm.
  • the irradiation power of the radiation source or radiation sources used with higher irradiation powers preferably leading to a higher radiation dose and thus to a greater increase in the separating force of the modified surface (closer to the surface, stronger cross-linking of the silicone), preferably compared to the adhesive surface of a reference adhesive tape.
  • the duration of the irradiation is often determined by the relative movement between the surface of the silicone to be modified and the VUV radiation source. In the case of industrially particularly relevant web material, the duration is defined by the web speed. Web speeds in the range from 1 to 1000 m / min, preferably in the range from 50 to 500 m / min, particularly preferably in the range from 60 to 400 m / min, are preferred according to the invention.
  • maximum radiation intensities on the irradiated silicone surface in the range from 0.01 to 1000 mW / cm 2 , preferably in the range from 0.03 to 200 mW / cm 2 , particularly preferably in the range from 0.1 to 100 mW / cm 2 and very particularly preferably in the range from 1.0 to 40 mW / cm 2 .
  • the oxygen partial pressure in the working atmosphere or the volume fraction of oxygen in the working atmosphere is preferred in which the working atmosphere has an oxygen content in the range from> 0 to ⁇ 22% by volume, preferably in the range from> 10 to ⁇ 22% by volume, particularly preferably in the range from> 15 to ⁇ 21 , 0% by volume and very particularly preferably in the range from> 20 to ⁇ 21 vol .-%, the rest of the working atmosphere to 100 vol .-% preferably being occupied by an inert gas, preferably selected from the group consisting of noble gases, nitrogen, carbon dioxide and mixtures thereof.
  • the working atmosphere contains only air from the ambient atmosphere and / or is provided from a compressed air tank or generator.
  • a method according to the invention for producing a silicone with a modified surface is preferred, the irradiation at an average radiation dose in the range from> 0.01 to ⁇ 10 mJ / cm 2 , preferably in the range from> 0.02 to ⁇ 9 mJ / cm 2 , particularly preferably in the range from> 0.03 to ⁇ 8 mJ / cm 2 , more preferably in the range from> 0.035 to ⁇ 2.2 mJ / cm 2 and very particularly preferably in the range from> 0.035 to ⁇ 0.99 mJ / cm 2 is carried out.
  • the absorption behavior of silicones for UV radiation depends on the wavelength of the incident light. For a rough orientation, the absorption spectrum B from Fig.
  • Degree of absorption 1 - io A (A) * d
  • the degree of absorption indicates how high the proportion of absorbed photons is in relation to the radiated photons. In the case of 185 nm radiation, the proportion calculated using the above information is 1.1%. In contrast, in the case of 172 nm radiation, a 7 times higher value of 7.7% is calculated.
  • 172 nm radiation from xenon excimer lamps is not monochromatic, but the emission occurs spectrally with a half width of 14 nm, so that on the one hand there is a spectrally different absorption of the radiation by oxygen and on the other hand a spectrally different absorption of the radiation by the silicone.
  • the degree of absorption of a silicone layer is reduced if the absorption is considered spectrally (and thus more realistic). The rule that 185 nm photons are less strongly absorbed than radiation emitted from xenon excimer lamps is always true.
  • the radiation dose is an indication of the desired effects, but does not only allow statements about the effect achieved.
  • the type of radiation plays a major role (see also above), so the same dose irradiated by a xenon excimer leads to a stronger modification of the surface of a silicone than the same dose, provided that it causes longer-wave radiation from a wave has been.
  • the method according to the invention for producing a silicone with a modified surface is preferably carried out at atmospheric pressure or at (compared to normal pressure) reduced pressure (low pressure).
  • the method according to the invention for producing a silicone with a modified surface is carried out at a defined relative humidity, preferably at a relative humidity in the range from 20 to 80%, more preferably in the range from 40 to 60%.
  • the process according to the invention for producing a silicone with a modified surface can be carried out at room temperature, preferably at a temperature in the range from 15 to 25 ° C, more preferably at a temperature in the range from 18 to 22 ° C.
  • sample temperature the samples comprising the silicone used in the method according to the invention
  • this is ⁇ 70 ° C, more preferably ⁇ 50 ° C and particularly preferably ⁇ 40 ° C.
  • the preferred process parameters listed above and below can be selected depending on the process requirements, combinations of the preferred process parameters with one another being possible. This makes it possible to ideally adapt the method to desired or particularly preferred manufacturing requirements.
  • the UV irradiation according to the invention thus in most cases modifies a significant part of such a silicon material, ie the modified surface of such a material Then silicone makes you a considerable proportion of the total silicone forming such a siliconization (ie silicone coating).
  • the determination or measurement of the (maximum) irradiance or the average radiation dose to be used in the method according to the invention is not trivial due to the complexity of the measurement (apparatus) in the radiation measurement and the relatively low average radiation dose to be used in the present case:
  • a method according to the invention for producing a silicone with a modified surface (or a method according to the invention, indicated above or below as preferred, for producing a silicone with a modified surface) whereby different surface areas of the silicone are irradiated with different radiation doses from the radiation dose range specified (for the method according to the invention), and / or the silicone in step (V1) comprises a carrier material and is preferably applied to a carrier material (preferably the modified surface of the silicone facing away from the carrier material).
  • the radiation sources can therefore be positioned parallel to one another or in any desired orientation.
  • the distances between the respective radiation sources and the surface or surfaces to be irradiated can be the same for all radiation sources or different for individual, multiple or all radiation sources. If individual, several or all radiation sources are arranged at different distances from the surface or surfaces to be irradiated, local areas of the surfaces to be irradiated can be treated with different radiation doses, whereby, for example, surface areas with different adhesive properties can be generated. Different distances between the radiation sources and the surface or surfaces can also be useful for combining different radiation wavelengths. Using suitable technical measures to set the radiation dose (e.g.
  • selected areas of flat siliconization can be made different treat (irradiate) and thus provide any separating force.
  • the present invention also relates to a silicone with a modified surface, preferably with a surface modified by UV radiation, produced or producible by a method according to the invention for producing a silicone with a modified surface (or according to a production method according to the invention specified above or below as preferred a silicone with a modified surface).
  • the silicone comprises a carrier material in step (V1) and is preferably applied to a carrier material
  • a composite material according to the invention can preferably be produced in this way (see below).
  • the carrier materials described in more detail below, which can be part of the composite material according to the invention, can preferably be used as carrier material.
  • the present invention therefore also relates to a method for producing a composite material, comprising the steps
  • V1A providing silicone, preferably at least partially crosslinked silicone elastomer, comprising a carrier material (the silicone preferably being present as a coating on at least one surface of the carrier material),
  • step (V2) irradiating at least part of the surface of the silicone from step (V1) with UV radiation of at least one wavelength in the range from> 50 nm to ⁇ 380 nm, preferably in the range from> 150 nm to ⁇ 220 nm, in an atmosphere with an oxygen content in the range from> 0 to ⁇ 22% by volume, preferably in the range from> 10 to ⁇ 21% by volume, so that a composite material comprising silicone according to the invention with a modified surface results.
  • the silicone provided in step (V1A) comprising a carrier material can be produced in a manner known per se, in particular by applying the silicone or a silicone known per se to a suitable carrier material, preferably to a carrier material defined in more detail below. This process is also known as "siliconizing". In this way, according to the method according to the invention, a permanent composite material can be produced which is suitable, among other things, for carrying out a pull-off test (for more details, see above).
  • the present invention also relates to a composite material, produced or producible by a method according to the invention for producing a composite material (or according to a method according to the invention for producing a composite material specified above or below as preferred).
  • a method according to the invention for producing a composite material or according to a method according to the invention for producing a composite material specified above or below as preferred.
  • the following apply to the silicone according to the invention with a modified surface, to the method according to the invention for producing a silicone with a modified surface and to the method according to the invention for producing a composite material the explanations given above accordingly (if necessary, analogously), and vice versa.
  • Step (V2A) of the above-specified method for producing a composite material is preferably followed by one or more further steps, preferably rolling the produced composite material into a roll and / or coating the produced composite material with one or more pressure-sensitive adhesives.
  • the carrier material is coated with one or more pressure-sensitive adhesives and / or the modified surface of the silicone is coated with one or more pressure-sensitive adhesives.
  • the present invention also relates to a composite material comprising silicone with a modified surface, preferably with a surface modified by UV radiation (or a silicone according to the invention with a modified surface specified above or below as preferred), and a carrier material, wherein the carrier material is preferably selected from the group consisting of
  • Polyester preferably polyethylene terephthalate, particularly preferably biaxially oriented polyethylene terephthalate;
  • Polyethylene preferably high density polyethylene and low density polyethylene; - Polypropylene, preferably monoaxially stretched polypropylene, biaxially stretched
  • Paper preferably glassine paper, clay coated paper, kraft paper, machine smooth paper and polyolefin coated paper;
  • Metal preferably aluminum; such as
  • a composite material according to the invention (or a composite material according to the invention specified above or below as preferred) is preferred, comprising a silicone according to the invention with a modified surface, preferably with a surface modified by UV radiation, in the form of a web or a film, preferably a thickness in the range from> 0.5 to ⁇ 200 ⁇ m, which on at least one of its surfaces to an area proportion of> 50%, preferably> 75%, particularly preferably completely, with the silicone according to the invention with a modified surface, preferably with UV radiation modified surface, is coated, wherein the layer comprising the silicone with surface modified by UV radiation preferably has a layer thickness in the range from> 0.1 to ⁇ 20 ⁇ m on the composite material.
  • a composite material according to the invention (or a composite material according to the invention specified above or below as preferred) is also preferred, in addition comprising an adhesive in contact with the modified surface of the silicone and / or an adhesive layer in contact with the modified surface of the silicone.
  • the carrier material of the composite material according to the invention can be coated on one of its surfaces or on two or more of its surfaces (if present) with the silicone with a modified surface, for example on the front and back of a web or film. If the carrier material is coated on two or more of its surfaces with silicone with a modified surface, the modified surfaces of the silicone can have the same or different separation forces. In this way, for example, a release film or a release liner can be made available which has different release forces on its upper and lower side.
  • the present invention also relates to the use of a silicone according to the invention with a modified surface (or a silicone according to the invention with a modified surface specified above or below as preferred) in non-stick coatings, preferably as an adhesive force regulator, preferably in non-stick coatings selected from the group consisting of:
  • Non-stick coatings for self-adhesive products preferably selected from the group consisting of self-adhesive labels, adhesive tapes, self-adhesive decorative films, self-adhesive protective films, plasters and hygiene products, and
  • Non-stick coatings for idler papers, rubber or plastic production, tire molds and baking paper are examples of non-stick coatings for idler papers, rubber or plastic production, tire molds and baking paper.
  • the present invention also relates to the use of a composite material according to the invention or a composite material produced or produced by a process according to the invention (or a corresponding composite material according to the invention specified above or below as preferred) as a release film and / or release liner for substances with a high surface area Adhesiveness, preferably selected from the group consisting of
  • Self-adhesive products preferably selected from the group consisting of self-adhesive labels, adhesive tapes, self-adhesive decorative films, self-adhesive protective films, plasters and hygiene products; preferably adhesive tapes, particularly preferably double-sided adhesive tapes;
  • Substances with high surface adhesion preferably selected from the group consisting of unreacted resins and prepregs, highly viscous media, preferably selected from the group consisting of adhesives, paints and printing inks, and self-adhesive semi-finished products, preferably selected from the group consisting of attachments in the exterior of motor vehicles , preferably trim strips and logos, and attachments in the interior of motor vehicles.
  • the following apply to the silicone according to the invention with a modified surface, for the method according to the invention for producing a silicone with a modified surface, for the method according to the invention for producing a composite material, for the according to a Composite material produced or producible according to the method according to the invention, for the composite material according to the invention and for the use according to the invention of a silicone with a modified surface, corresponding to the explanations given above (if appropriate, analogously) and vice versa.
  • prepregs is understood - in accordance with the usual understanding in the specialist world - to be understood as meaning pre-impregnated textile fiber matrix semi-finished products that are used to manufacture Position of components are cured under temperature and pressure.
  • the reaction resins consist of a mostly highly viscous, but not yet polymerized, thermosetting plastic matrix, which is mainly used in lightweight construction.
  • the fibers contained can be present as a pure unidirectional layer, as a fabric or scrim. Prepreg, for example, is supplied in web form, wound on rolls.
  • prepreg includes not only unidirectionally reinforced or flat semi-finished products, but also other preforms of basically any shape that, in the broadest sense, consist of an uncured thermoset matrix filled with fibers.
  • the matrix is in the partially networked, so-called B-stage, and is pasty to solid, but can be liquefied again by heating.
  • Silicone S Unless otherwise stated, the Easy Release silicone treatment Separacon 9160-60 on glassine paper (160 g / m 2 ) from MariaSoell (Nidda-Eichelsdorf) was used. This is a silicone system that does not cross-link UV during production, but rather a platinum-catalyzed (thermally activated) cross-linking silicone system. The application weight was 3 g / m 2 .
  • Irradiation example 1 vacuum-UV modification of siliconizations
  • the siliconizations are irradiated by means of a low-pressure mercury lamp (UVX 120 4C S 19/670 Co, Hönle) with an irradiation power: 0.176 W / cm (10 W at 568 mm light length, manufacturer information) using the following parameter sets (partly a selection from them):
  • Parameter set P2 (according to the invention): (working atmosphere with N2 proportion: 79 vol .-%, O2 proportion 21 vol .-%, distance 10 mm, travel speed 1.01 m / min) or Parameter set P3 (according to the invention): (working atmosphere with ISfe content: 79 vol .-%, O2 fraction 21 vol .-%, distance 10 mm, travel speed 1, 68 m / min) or
  • Parameter set P6 (according to the invention): (working atmosphere with ISfe content: 79% by volume, O2 content 21% by volume, distance 30 mm, travel speed 6.8 m / min) irradiated.
  • This siliconization was also carried out using a xenon excimer lamp (XERADEX L40 / 375 / DB-AZ48 / 90, Osram) with a 375 mm light length, an irradiation power:
  • Parameter set P1 (not according to the invention): (working atmosphere with ISfe content: 95% by volume, O2 content 5% by volume, distance 50 mm, travel speed 3 m / min) irradiated.
  • the silicone S1 -PET from the application with the German official file number DE 10 2018 108 881 .7 was reworked here. The production took place as described in the application mentioned.
  • Parameter set P7 (according to the invention): (working atmosphere with ISfe content: 79% by volume, O2 content 21% by volume, distance 30 mm, travel speed 19.2 m / min) irradiated. Values for the mean radiation dose, the maximum and the mean radiation power, are determined with the help of the ray tracing software as described in the German patent application with the official file number DE 10 2018 108 881 .7. In case of doubt, a translation distance of 20 cm symmetrical and orthogonal to the lamp axis is taken into account for the simulation of the mean radiant power. The values listed in Table 1 result for the parameter sets. Also included is the reference (“Ref), which corresponds to a sample that was irradiated with a radiation dose of 0 mJ / cm 2 . Table 1: Simulation result for mean radiation doses and mean radiation powers of the parameter sets P1-P7
  • Derivatization example 1 For this chemical gas phase derivatization, the sample was placed in a Petri dish with a volume of 75 cm 3 and a diameter of 100 mm and gaseous chlorodimethyl (3,3,3-trifluoropropyl) silane (97%, chemical formula: CI- ( CH3) 2 Si- (CH 2 ) 2 CF3, FZ: 3, CAS 1481 -41 -0, but GmbH) exposed.
  • a small aluminum dish with 0.15 enr 3 of the silane was placed in the Petri dish and the arrangement was heated in a gas-tight convection chamber oven (KU15 / 06 / A, Thermconcept Dr. Fischer GmbH & Co. KG). The oven was heated from 20 to 105 ° C. within 40 minutes and the temperature was kept constant at 105 ° C. for 6 hours. The cooling to 30 ° C. was uncontrolled. The sample was then analyzed using ESCA. Derivatization example 2:
  • Measurement example 1 Determination of the element composition, determination of the fluorine concentration - calculation of the silanol concentration
  • ESCA analysis The surfaces were examined analytically with regard to their element concentration (based on all atoms of the surface layer except hydrogen and helium).
  • the high detection sensitivity of the method is element-specific and dependent on the measurement parameters and is around 1000 ppm for silicon and carbon and around 250 ppm for fluorine.
  • the information depth is approx. 10 nm.
  • the ESCA examinations were carried out with a Kratos-Axis-Ultra system.
  • the silanol concentration in at% based on the atoms recorded by ESCA is calculated (in fact, we only consider the 0 atom here).
  • the C, O and Si atoms of the derivatization reagent additionally incorporated by the derivatization can be rounded up the low silanol group concentrations up to 0.135 at% are neglected in the evaluation.
  • the increased fluorine or silanol concentration for irradiated samples compared to the unpunished reference is calculated from the difference between these values for the irradiated less the non-irradiated sample.
  • the reduction in the C concentration for irradiated samples compared to the unpunished reference is calculated from the difference in the value for the C concentration for the unirradiated sample minus the value for the C concentration for the irradiated sample.
  • the ESCA experiments to determine the reduced C concentration were each determined (for the samples irradiated using parameters P1-P7 and the non-irradiated reference) without prior derivatization of the samples.
  • ESCA experiments after derivatisation were carried out using the same samples, which were irradiated using identical parameters P1-P7, and other identical, non-irradiated reference samples. In other words, after an ESCA experiment, the samples were not subjected to further experiments, instead samples were freshly prepared.
  • Measurement example 2 Determination and analysis of the depth profile of silanol groups
  • the siliconization is on the back of a rigid, low-temperature stable carrier, z. B. an aluminum block, glued. This specimen is clamped in an ultramicrotome and carefully aligned with the cutting plane. While cooling with liquid nitrogen, a maximum of 30 microtome sections with a thickness of 100 nm are prepared and collected and numbered in sequence (starting with 1).
  • the constant t1 corresponds to the mean depth range of the modification.
  • the layer thickness of the modified area as above defined is calculated according to
  • Measurement example 3 Separation force measurement
  • samples modified according to irradiation example 1 were initially stored at room temperature for 1 day.
  • the adhesive tapes were each pressed 10 times with the pressure roller at an unwinding speed of approx. 1 cm / s and the glued samples were then stored at 40 ° C. for a further 20 hours.
  • the bonded samples were loaded between two flat metal plates with a pressure of approx. 70 g / cm 2 .
  • the samples were stored again for approx. 4 h without stress at room temperature.
  • the material according to the invention (or the unirradiated silicone elastomer on paper as a reference) and the pressure-sensitive adhesive tape were then separated and each in a 180 ° peel test based on the FINAT test method FTM 10 (see FINAT Technical Handbook, 9th edition 2014) the necessary separation force was measured over a travel distance of 175 mm at a test speed of 500 mm / min, whereby the first 25 mm and the last 10 mm were not evaluated.
  • the Tesa® adhesive tape 7475 (acrylate-based pressure-sensitive adhesive) was used, an adhesive tape intended according to FINAT FMT for the characterization of siliconizations.
  • the separation force increase factor is calculated as the quotient of the measured separation value and the reference separation value (non-irradiated sample).
  • Example table 1 to example table 5 show the results for material example 1 and derivatization example 1 and 2 with the name of silicone, irradiation parameter set and measurement specification.
  • Example table 1 Results for silicone S1 from German patent application with the official file number DE 10 2018 108 881 .7 after irradiation using process P1
  • Example table 2 Results for silicone S after irradiation using process P2-P7
  • Example table 3 Results for silicone S after irradiation using process P2-P5
  • Example table 4 Results for silicone S after irradiation using process P6-P7
  • Example table 5 Results for silicone S after irradiation using process P2-P7 and the non-irradiated reference silicone S "Ref"
  • Example depth profile determination of the fluorine concentration as a function of the depth
  • the siliconization “S” is irradiated according to parameter set P4 from irradiation example 1 (according to the invention). Following measurement example 2, a total of 32 microtome sections with a thickness of 100 nm are prepared and the fluorine depth profile is analyzed according to the instructions in measurement example 2.
  • the mean depth range (constant t1 according to the analysis according to measurement example 2) is 833 nm.

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Abstract

L'invention concerne une silicone à surface modifiée, dont la quantité de carbone qui a été remplacée est particulièrement faible par rapport à la silicone non modifiée, un matériau composite comprenant ladite silicone et un matériau support, ainsi qu'un procédé de fabrication de ladite silicone à surface modifiée. L'invention concerne en outre l'utilisation de ladite silicone à surface modifiée dans des revêtements anti-adhésifs et l'utilisation dudit matériau composite comme feuille de séparation et/ou pellicule anti-adhésive pour des matières à haut pouvoir adhésif de surface.
PCT/EP2020/068567 2019-07-04 2020-07-01 Silicone à surface modifiée, son utilisation dans des revêtements anti-adhésifs et matériau composite contenant ladite silicone WO2021001448A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0165059A2 (fr) 1984-06-14 1985-12-18 Minnesota Mining And Manufacturing Company Matériau à faible énergie de surface
EP0550510B1 (fr) 1990-09-21 1994-12-21 ANTON STEINECKER ENTWICKLUNGS GmbH & Co. Buse d'aeration de liquides contenant des substances organiques
DE69224370T2 (de) 1992-01-23 1998-05-28 Daikyo Gomu Seiko Kk Zusammensetzung eines modifizierten Polysiloxans und damit beschichteter sanitärer Kautschukartikel
WO2001032949A1 (fr) 1999-10-30 2001-05-10 Agrodyn Hochspannungstechnik Gmbh Procede et dispositif servant au revetement par plasma de surfaces
WO2008132230A2 (fr) 2007-04-30 2008-11-06 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procédé de fabrication de couches minces et couche mince obtenue par ce procédé
WO2015044247A1 (fr) 2013-09-25 2015-04-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Corps solide de polymère de plasma (en particulier couche de polymère de plasma)
WO2015075040A1 (fr) 2013-11-19 2015-05-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procédé de liaison de caoutchouc silicone à un substrat
WO2016030183A1 (fr) 2014-08-26 2016-03-03 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Silicone modifié en surface, et procédé pour sa production
WO2016071387A1 (fr) 2014-11-06 2016-05-12 Tesa Se Traitement électrostatique de couches anti-adhérentes
WO2019197492A1 (fr) 2018-04-13 2019-10-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Silicone à surface modifiée, son utilisation dans des revêtements antiadhésifs et matériau composite la comprenant

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0165059A2 (fr) 1984-06-14 1985-12-18 Minnesota Mining And Manufacturing Company Matériau à faible énergie de surface
EP0550510B1 (fr) 1990-09-21 1994-12-21 ANTON STEINECKER ENTWICKLUNGS GmbH & Co. Buse d'aeration de liquides contenant des substances organiques
DE69224370T2 (de) 1992-01-23 1998-05-28 Daikyo Gomu Seiko Kk Zusammensetzung eines modifizierten Polysiloxans und damit beschichteter sanitärer Kautschukartikel
WO2001032949A1 (fr) 1999-10-30 2001-05-10 Agrodyn Hochspannungstechnik Gmbh Procede et dispositif servant au revetement par plasma de surfaces
WO2008132230A2 (fr) 2007-04-30 2008-11-06 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procédé de fabrication de couches minces et couche mince obtenue par ce procédé
WO2015044247A1 (fr) 2013-09-25 2015-04-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Corps solide de polymère de plasma (en particulier couche de polymère de plasma)
WO2015075040A1 (fr) 2013-11-19 2015-05-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procédé de liaison de caoutchouc silicone à un substrat
WO2016030183A1 (fr) 2014-08-26 2016-03-03 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Silicone modifié en surface, et procédé pour sa production
DE102014217000A1 (de) 2014-08-26 2016-03-03 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Oberflächenmodifiziertes Silikon und Verfahren zu dessen Herstellung
WO2016071387A1 (fr) 2014-11-06 2016-05-12 Tesa Se Traitement électrostatique de couches anti-adhérentes
WO2019197492A1 (fr) 2018-04-13 2019-10-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Silicone à surface modifiée, son utilisation dans des revêtements antiadhésifs et matériau composite la comprenant
DE102018108881A1 (de) 2018-04-13 2019-10-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Oberflächenmodifiziertes Silikon, dessen Verwendung in Antihaftbeschichtungen sowie dieses enthaltendes Verbundmaterial

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
ALEXANDER G. SHARD: "Detection limits in XPS for more than 6000 binary systems using Al and Mg K[alpha] X-rays : XPS detection limits", SURFACE AND INTERFACE ANALYSIS., vol. 46, no. 3, 3 February 2014 (2014-02-03), GB, pages 175 - 185, XP055727751, ISSN: 0142-2421, DOI: 10.1002/sia.5406 *
BERNHARD SCHNYDER ET AL: "UV-irradiation induced modification of PDMS films investigated by XPS and spectroscopic ellipsometry", SURFACE SCIENCE, vol. 532-535, 1 June 2003 (2003-06-01), AMSTERDAM, NL, pages 1067 - 1071, XP055727838, ISSN: 0039-6028, DOI: 10.1016/S0039-6028(03)00148-1 *
CEFALAS ET AL.: "Absorbance and outgasing of photoresist polymeric materials for UV lithography below 193 nm including 157 nm lithography", MICROELECTRON. ENG., vol. 53, no. 1-4, 2000, pages 123 - 126, XP004237735, DOI: 10.1016/S0167-9317(00)00278-1
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 102488-47-1
DEVER ET AL.: "Effects of vacuum ultraviolet radiation on DC93-500 silicone", JOURNAL OF SPACECRAFT AND ROCKETS, 2006, pages 386 - 392, XP055509145, DOI: 10.2514/1.15226
JOYCE A. DEVER ET AL: "Effects of Vacuum Ultraviolet Radiation on DC93-500 Silicone", JOURNAL OF SPACECRAFT AND ROCKETS., vol. 43, no. 2, 1 March 2006 (2006-03-01), US, pages 386 - 392, XP055727828, ISSN: 0022-4650, DOI: 10.2514/1.15226 *
MUNIEF, HEIB, F.HEMPEL, FLU, X.SCHWARTZ, M.PACHAURI, V.HEMPELMANN, R.SCHMITT, M.INGEBRANDT. S., LANGMUIR, vol. 34, no. 35, 2018, pages 10217 - 10229
SKURATDOROFEEV: "The transformation of organic polymers during the illumination by 147.0 and 123.6 nm light", ANGEW. MAKROMOL. CHEMIE, vol. 216, no. 1, 1994, pages 205 - 224
V.M. GRAUBNER ET AL., MACROMOLECULES, vol. 37, 2004, pages 5936 - 5943
VERA-MARIA GRAUBNER ET AL: "Photochemical Modification of Cross-Linked Poly(dimethylsiloxane) by Irradiation at 172 nm", MACROMOLECULES, vol. 37, no. 16, 1 August 2004 (2004-08-01), WASHINGTON, DC, UNITED STATES, pages 5936 - 5943, XP055728207, ISSN: 0024-9297, DOI: 10.1021/ma049747q *

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