WO2001038450A1 - Complexe silicone reticulable par voie cationique/adhesif dont l'interface possede une force de decollement modulable - Google Patents
Complexe silicone reticulable par voie cationique/adhesif dont l'interface possede une force de decollement modulable Download PDFInfo
- Publication number
- WO2001038450A1 WO2001038450A1 PCT/FR2000/003293 FR0003293W WO0138450A1 WO 2001038450 A1 WO2001038450 A1 WO 2001038450A1 FR 0003293 W FR0003293 W FR 0003293W WO 0138450 A1 WO0138450 A1 WO 0138450A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silicone
- acrylate
- adhesive
- complex according
- additive
- Prior art date
Links
- 0 CCC(CC)(*(C)C)*(C)(C)CCC1CC2OC2CC1 Chemical compound CCC(CC)(*(C)C)*(C)(C)CCC1CC2OC2CC1 0.000 description 3
- HFHHWGFJWYRPCL-UHFFFAOYSA-N CCC(C)C1CC2OC2(C)CC1 Chemical compound CCC(C)C1CC2OC2(C)CC1 HFHHWGFJWYRPCL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C09D183/06—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
- 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
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/334—Applications of adhesives in processes or use of adhesives in the form of films or foils as a label
-
- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
- C09J2433/005—Presence of (meth)acrylic polymer in the release coating
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates generally to so-called "sticker” complexes composed in particular of a non-stick silicone coating and an adhesive coating.
- This type of complex is generally intended for a use in which the crosslinked or polymerized silicone matrix is affixed at the level of a support so as to make it non-stick vis-à-vis the adhesive.
- This type of complex finds applications in particular in the field of adhesive protective papers, labels, decorative papers and adhesive tapes.
- the silicone oils or resins proposed for obtaining this type of coating with non-stick properties generally derive from cationic photocrosslinkable systems. They are more particularly monomer (s), oligomer (s) and / or polymer (s) of polyorganosiloxane nature comprising functional and reactive radicals capable of forming intra- and inter-catenary bridging. These systems lead after polymerization under UV or electron beam and in the presence of a polymerization initiator, to non-stick coatings which form so-called "sticker" complexes with the adhesives which are applied to their surface after siliconization.
- this detachment force can be quantified. Although its values can vary significantly depending on the method measurement, we can generally characterize it as follows for a low release speed, that is to say of the order of 30 cm / m ⁇ and according to the FTM3 method:
- the object of the present invention is precisely to propose a silicone / adhesive complex, the release force of which can be adjusted on demand and preferably to a value included in the range stated above, namely between 15 g / cm and 200 g / cm. .
- the present invention relates to the field of adhesive / silicone complexes which can be polymerized and / or crosslinkable by the cationic route and whose detachment force of their silicone / adhesive interface is photochemically modular.
- Patent application DE 198 31 775 A already describes a silicone / adhesive complex with modular release force.
- the ability of this complex to manifest a modular release force is directly linked to the chemical nature of the silicone matrix. It is derived from acrylic polyorganosiloxanes and has acrylate crosslinking nodes. Depending on its degree of crosslinking, this silicone matrix manifests a more or less significant adhesion with respect to the adhesive film which is associated with it.
- the presence of a chromium salt in the silicone matrix is required for the manifestation of this property.
- the present invention aims to propose a silicone / adhesive complex whose ability to manifest a modular release force is linked to the presence of a specific additive within the silicone matrix.
- the present invention firstly relates to a silicone / adhesive complex comprising at least one silicone coating applied to a first support and an adhesive coating applied to a second support, and the release force of a silicone / adhesive interface is modular, characterized in that its silicone coating is derived from the polymerization and / or crosslinking by cationic means of monomers, oligomers and or polyorganosiioxane polymers carrying as reactive groups at least epoxy, oxetane, dioxolane and / or alkenyl ether functions and in that that said silicone coating also comprises at least one additive for regulating the release force of a silicone / adhesive interface and the activity of which is initiated and photochemically modular.
- Activation of the additive is preferably carried out by exposure, in the absence of the complex, of at least one silicone / adhesive interface to at least one photochemical irradiation preferably.
- the use of a polyorganosiloxane matrix in accordance with the invention for preparing the claimed complexes is particularly advantageous compared to a polyorganosiloxane matrix with acrylic functions insofar as its preparation does not require inerting. Unlike acrylates whose radical crosslinking can be stopped by the accidental presence of oxygen, the polyorganosiioxanes functionalized according to the invention are not sensitive to the ambient atmosphere. It is therefore not essential that their cationic crosslinking takes place in an inert atmosphere.
- the two supports are made up of two distinct entities, arranged so that the silicone coating of the first support is in contact with the adhesive coating of the second support.
- This embodiment is in particular illustrated by systems known as self-adhesive labels. In this particular case, the release force of the silicone / adhesive interface is exerted during the separation of the two supports.
- the two supports consist respectively of each of the two faces of the same entity.
- This second embodiment is in particular illustrated by the systems known as adhesive tapes.
- the non-stick coating that is to say based on the silicone matrix and the adhesive coating are brought into contact during the winding of the support on itself. In this case, the release force is exerted at the silicone / adhesive interface under the effect of the separation of a lower face with an upper face of the material.
- the additive for regulating the release force of a silicone / adhesive interface used in the context of the present invention is chosen from: - organic acrylics, alkenyl ethers, and acrylic silicones and / or with alkenyl ether functions.
- organic acrylics are the acrylate species and in particular epoxidized acrylates, acryloglyceropolyesters, multifunctional acrylates, acrylo-uretanes, acrylopolyethers, acrylopolyesters, unsaturated polyesters, and acrylo-acrylics. More particularly preferred are trimethylpentanediotriacrylate, trimethylol propane triacrylate, and tripropylene glycol diacrylate.
- alkenyl ethers can be chosen from cyclohexanedimethanoldivinyl ether, triethylenglycoldivinylether
- this additive is chosen from acrylic silicones and / or with alkenyl ether functions.
- acrylic or methacrylic silicone derivatives which are very particularly suitable for the invention, mention may more particularly be made of acrylic, methacrylic, ether and ester derivatives.
- polyorganosiioxanes with an acrylate and / or methacrylate function are especially suitable linked to the polysiloxane chain by an Si-C bond.
- acrylic derivatives are described in particular in patents EP 281 718 and FR 2 632 960.
- polyorganosiioxanes having an alkenyl ether function they generally derive from a hydrosilylation reaction between oils containing Si-H structural units and compounds carrying alkenyl ether functions such as allylvinyl ethers, allylvinyloxyethoxybenzene and the like. This type of compound is in particular referenced in US Pat. No. 5,340,898.
- This additive is contained in the silicone coating and is of course present in an amount sufficient to allow regulation of the release force of the adhesive / silicone interface. It can be present up to 50% by weight of the silicone coating expressed as dry matter.
- the additive is preferably used in an amount of approximately 0.1 to 20% of the weight of the total silicone mixture.
- the quantity in this additive is likely to vary significantly depending on whether it is of a similar nature or not.
- this additive is an organic acrylic derivative or an alkenyl ether
- its amount is generally between 0.1 and 10% approximately, preferably 0.5 and 5% approximately and more preferably 1 and 3 %.
- a silicone type additive is preferably used up to 20% by weight and preferably 15% by weight.
- the quantity of radiation generally expressed in doses of radiation preferably of the UV type is a useful parameter for modulating the activity of the additive defined above and therefore adjusting the level of the release force generated by this additive.
- the release force turns out to be variable depending on the number of passes under the UV lamps and therefore on the UV energy received.
- This UV energy can be provided by any suitable device, either under the effect of flash or strobe lighting.
- sources of UV rays which can be used to activate the additive, mention may in particular be made of UV systems such as microwave lamps or arc lamps.
- the concentration of additive dispersed within the silicon matrix appears as a parameter for modulating this release force. This impact of the additive concentration on the release force is in particular illustrated by the results appearing in the examples below.
- the invention has the advantage of proposing a silicone / adhesive complex, the strength of which proves to be possible. detachment at its silicone / adhesive interface as a function, on the one hand, of the quantity of incorporated additive and, on the other hand, of the quantity of radiation applied at this interface.
- silicone coating it can be derived from the polymerization and / or crosslinking of polyorganosiioxanes consisting of units of formula (II) and terminated by units of formula (I) or cyclic consisting of units of formula (II) shown here. below:
- a linear or branched alkyl radical containing 1 to 8 carbon atoms optionally substituted with at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,
- an aralkyl part having an alkyl part containing between 5 and 14 carbon atoms, and an aryl moiety containing from 6 to 12 carbon atoms, optionally substituted on the aryl part with halogens, alkyls and / or alkoxyls containing 1 to 3 carbon atoms,
- the polyorganosiioxanes used comprise from 1 to 10 organofunctional groups per macromolecular chain.
- an epoxyfunctional group this corresponds to epoxide levels varying from 20 to 2000 meq. molar / 100 g of polyorganosiloxane.
- the nodes of the silicone matrix obtained are of the polyether type.
- the linear polyorganosiioxanes can be oils of dynamic viscosity at 25 ° C, of the order of 10 to 10,000 mPa.s at 25 ° C, generally of the order of 20 to 5,000 mPa.s at 25 ° C and , more preferably still, from 20 to 600 mPa.s at 25 ° C., or gums having a molecular mass of the order of 1,000,000.
- cyclic polyorganosiioxanes these consist of units (II) which can be, for example, of the type dialkylsiloxy or alkylarylsiloxy. These cyclic polyorganosiioxanes have a viscosity of the order of 1 to 5000 mPa.s.
- divalent radicals linking an organofunctional group of the epoxy and / or oxetane type mention may be made of those included in the following formulas:
- n 0 or 1 and n" an integer between 1 and 5 • R 3 represents:
- R 4 represents a linear or branched CC 6 alkyl radical.
- the linear polyorganosiioxanes can be oils of dynamic viscosity at 25 ° C, of the order of 10 to 10,000 mPa.s at 25 ° C, generally of the order of 20 to 5,000 mPa.s at 25 ° C and , more preferably still, from 20 to 600 mPa.s at 25 ° C., or gums having a molecular mass of the order of 1,000,000.
- cyclic polyorganosiioxanes When cyclic polyorganosiioxanes are involved, these consist of units which can be, for example, of the dialkylsiloxy or alkylarylsiloxy type. These cyclic polyorganosiioxanes have a viscosity of the order of 1 to 5000 mPa.s.
- the epoxy or vinyloxyfunctional polyorganosiioxanes are generally in the form of fluids having a viscosity at 25 ° C of 10 to 10,000 mm 2 / s and preferably from 100 to 600 m ⁇ rVs.
- the dynamic viscosity at 25 ° C. of all the silicones considered in the present description can be measured using a BROOKFIELD viscometer, according to the AFNOR NFT 76 102 standard of February 1972.
- the vinyloxyfunctional polyorganosiioxanes can be prepared by hydrosilylation reaction between oils with Si-H units and vinyloxyfunctional compounds such as allylvinylether, allyl-vinyl oxyethoxybenzene ...
- the functional epoxy polyorganosiioxanes can be prepared by hydrosilylation reaction between oils with Si-H units and epoxyfunctional compounds such as vinyl-4 cyclohexeneoxide, allylglycidylether ...
- the functional oxetane polyorganosiioxanes can be prepared by hydrosilylation of unsaturated oxetanes or condensation of oxetanes containing a hydroxy function.
- the functional dioxolane polyorganosiioxanes can be prepared by hydrosilylation of unsaturated dioxolanes.
- siicones best suited to the subject of the invention are described below and have at least one epoxide, alkenyl ether or oxetane group.
- X can represent an alkyl group; cyclohexyl; trifluoropropyl; perfluoroalkyl; alkoxy or hydroxypropyl, R a C 10 to C 10 alkyl radical, cyclohexyl, trifluoropropyl or C 10 to C 10 perfluoroalkyl and (0 ⁇ a ⁇ 1000); (1 ⁇ b ⁇ 1000)
- reaction conditions for polymerization and / or crosslinking by photoactivation are the usual conditions. They are generally initiated in the presence of a photoinitiator incorporated in the silicone matrix.
- photoinitiators those described in patent EP 562 897 are particularly suitable. They may also be iodonium or sulfonium salts corresponding to hexafluorophosphate or hexafluoroantimorate.
- This initiator is of course present in a sufficient and effective amount to activate the photopolymerization and / or crosslinking.
- effective amount of initiator is meant according to the invention the amount sufficient to initiate the polymerization and / or crosslinking.
- This amount is generally between 0.001 and 1 parts by weight, most often between 0.005 and 0.5 parts by weight to polymerize and / or crosslink 100 parts by weight of the silicone coating.
- the silicone coating is a matrix based on an epoxidized silicone oil.
- the components of the silicone coating can be combined with other additives.
- They may, for example, be mineral or non-mineral fillers and / or pigments such as synthetic or natural fibers of calcium carbonate, talc, clay, titanium dioxide or fumed silica.
- Soluble dyes, oxidation inhibitors and / or any other material which does not interfere with the catalytic activity of the platinum complex as well as the activity which regulates the release force of the additive can also be added to the component of the silicone matrix.
- an acrylic adhesive in the aqueous phase, in the solvent phase, a rubber in the aqueous phase or in solvent phase, in acrylics or in hot-melt gums, in latex or other suitable adhesives is included.
- acrylic adhesives in the aqueous phase or preferably in the solvent phase are emulsions called pressure-sensitive adhesive emulsions (PSA) which are derived from acrylic polymers . They give the material the ability to adhere to the surface of a support, without requiring activation other than low pressure.
- PSA pressure-sensitive adhesive emulsions
- PSAs are obtained by polymerization mainly of alkyl acrylate monomers which are generally present in an amount of 50 to about 99% and preferably in an amount of 80 to 99% by weight and of polar copolymerizable monomers such as for example acrylic acid, in smaller proportions.
- the monomers used to prepare these PSAs are selected according to their glass transition temperature, Tg, to give the polymers incorporating them the expected behavior in terms of adhesion and viscoelasticity.
- Tg glass transition temperature
- the monomers advantageously have a sufficiently low glass transition temperature, generally between -70 and -10 ° C and preferably is less than -30 C.
- these monomers are chosen from the group consisting of - (meth) acrylic esters such as the esters of acrylic acid and of methacrylic acid with hydrogenated or fluorinated C C 2 alkanols, preferably CC 8 , in particular l acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, tert-butyl acrylate, l hexyl acrylate, heptyl acrylate, octyl acrylate, iso-octyl acrylate, decyl acrylate, dodecyl acrylate, methacrylate methyly, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; vinyl nitriles including more particularly those having 3 to 12 carbon atoms, such as in particular acrylonitrile
- the monomers used in the emulsion polymerization are mainly alkyl (meth) acrylate monomers, present in an amount of 50% to about 99% and preferably in an amount of 80% to 99% by weight. relative to the weight of monomers present in the emulsion.
- they are chosen from 2-ethylhexyl acrylate, butyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, iso-octyl acrylate , decyl acrylate, isobutyl acrylate, dodecyl acrylate or mixtures thereof, methacrylates such as n-butyl methacrylate, methacrylic acid, acrylic acid, itaconic acid, maleic acid and / or acrylamide.
- the PSAs considered according to the present invention are generally prepared by emulsion polymerization by the radical route at atmospheric pressure and at a temperature generally between 10 and 90 ° C., of the corresponding monomers.
- this polymerization technique requires, in addition to the radical initiator, a mixture of anionic and / or nonionic emulsifiers to stabilize said emulsion. It can also be carried out in the presence of at least one monomer known as a crosslinking agent.
- PSAs can of course be used in a formulated form, that is to say mixed with conventional additives adhesives such as wetting agents, tackifiers, ...
- the complexes according to the invention can also comprise one or more additives chosen as a function of the intended final application.
- the additives can in particular be compounds optionally in the form of polymers, with mobile hydrogens such as alcohols, glycols and polyols, useful for improving the flexibility in particular of the silicone matrix after polymerization and / or crosslinking; polycaprolactones-poiyols, for example the polymer obtained starting from 2-ethyl-2- (hydroxymethyl) -1, 3-propane-diol and 2-oxepanone, such as the product TONE POLYOL-301 sold by the company UNION CARBIDE, or the other commercial polymers TONE POLYOL 201 and TONE POLYOL 12703 from the company UNION CARBIDE.
- fatty esters of unsaturated acids epoxidized or not for example epoxidized soybean oil or epoxidized linseed oil, epoxidized 2-ethylhexylester, 2- ethylhexyl epoxy stearate, octyl epoxystea
- fillers such as in particular ground synthetic fibers (polymers) or natural fibers, calcium carbonate, talc, clay, dioxide titanium, precipitation or combustion silica; soluble dyes; oxidation and corrosion inhibitors; organosilicon adhesion modulators or not; fungicidal, bactericidal, anti-microbial agents; and / or any other material which does not interfere with the activity of the additive according to the invention.
- the quantities of coating deposited on the supports are variable.
- the amounts of silicone coating generally range between 0.1 and 5 g / m 2 of treated surface. These amounts depend on the nature of the supports and on the desired non-stick properties. They are more often between 0.5 and 1.5 g / m 2 for non-porous substrates.
- the supports can be a metallic material such as tinplate, preferably a cellulosic material of the paper or cardboard type for example, or a polymeric material of the vinyl type.
- Thermoplastic polymer films such as polyethylene, prolypropylene or polyester are particularly advantageous.
- this second material can be chosen from the materials offered for the first support and be of an identical nature or not to the first support.
- the adhesive coating can be applied in different ways. It can in particular be deposited by transfer.
- the support on which the silicone coating and / or the adhesive coating is applied may already be coated with an initial coating to which a coating according to the invention is superimposed, provided that this additional coating is transparent to UV.
- the present invention also relates to articles (sheets, ribbons for example) comprising a complex according to the invention. They may in particular be labels, self-adhesive sheets or adhesive tapes.
- a second aspect of the present invention relates to the use of an additive as defined above in a silicone coating in accordance with the invention and intended to form a silicone / adhesive complex as defined above for the stabilization of peeling forces a silicone / adhesive interface by photochemical activation of said additive.
- Figure 1 Evolution of the level of adhesion as a function of the number of passages under the UV lamp, UV formulation without additive. Tesa® 4970 adhesive.
- Figure 2 Evolution of the level of adhesion as a function of the number of passages under the UV lamp of a UV formulation comprising different rates of additives consisting of silicone acrylate. Tesa® 4970 adhesive.
- Figure 3 Evolution of the level of adhesion as a function of the number of passages under the UV lamp before and after an aging cycle of 6 days at 70 ° C. UV formulation with acrylate silicone additive. Tesa® 4970 adhesive.
- Figure 4 Evolution of the level of adhesion as a function of the number of passages under the UV lamp. UV formulation with 5% acrylate oil. Rhodotak® 315P adhesive.
- Figure 5 Evolution of the level of adhesion as a function of the number of passes under the UV lamp. UV formulation with 5% acrylate oil. Rhodotak® 338J adhesive.
- Figure 6 Evolution of the level of adhesion as a function of the number of passages under the UV lamp. UV formulation with 5% acrylate oil. Rhodotak® 300 adhesive.
- Figure 7 Evolution of the level of adhesion as a function of the number of passages under the UV lamp of a formulation containing as an additive 0.34% of TMPTA. Tesa® 4970 adhesive.
- Figure 8 Evolution of the level of adhesion as a function of the number of passages under the UV lamp of a formulation containing as an additive 5% of TMPTA. Tesa® 4970 adhesive.
- Figure 9 Evolution of the level of adhesion as a function of the number of passages under UV before and after an aging cycle (6 days at 70 ° C), UV formulation with 5% TMPTA. Tesa® 4970 adhesive.
- Figure 10 Graphic representation of the intensity of the UV irradiation dose emitted as a function of the number of passages under the UV lamp (IST bench / speed 50m / min / P160W / cm). Materials and Method
- the UV non-stick system consists of: - an epoxidized oil of formula:
- the additives in accordance with the invention tested are: - a silicone oil with acrylate functions, of range
- Rhodia Silcolease ® resin 21621 an organic acrylic monomer trymethyipentanedioitriacryiate.
- the formulations are coated at a speed of 50 m / min on a polypropylene film using a Rotomec coating pilot.
- the corresponding silicone coating is crosslinked by passing under a UV Fusion lamp of 80W / cm (H + tube).
- the deposits are of the order of 1.2 g / m 2 to ensure good coverage of the support.
- the coating is then adhesive-coated with TESA® 4970 acrylic adhesive tape.
- the complex thus formed is then subjected to irradiation with a UV lamp (IST lamp / mercury arc tube), at a speed of 50 m / min. This irradiation is carried out through the polypropylene support film and the silicone layer.
- a UV lamp IST lamp / mercury arc tube
- FIG. 10 shows the dose received as a function of the number of passages made under UV lamp, this measurement is carried out using a Power Puck® from the company EIT. The complex is then separated by a peel test. This peeling test is carried out with an angle of 180 ° and a speed of 300 mm / min as described in the FINAT3 standard.
- the adhesion value is compared with that obtained on an unirradiated complex.
- the silicone formulation used is the epoxidized oil identified in "Materials and method”.
- the additive used is the silicone acrylate oil described above. It is added at 3 different concentrations: 5, 10 and 20% by weight of the silicone coating.
- the additive is perfectly miscible.
- the coating on the polypropylene support as well as the polymerization of the corresponding mixtures does not raise any problem: no manifestation of oily appearance, dewetting or rub off (scrub to the touch).
- TESA® 4970 adhesive tape Two types of application of the adhesive are carried out: either instantly after polymerization (according to a process known as "in one"), or 15 minutes after coating / polymerization (according to a process known as "off line”). They then undergo, within the hour following the manufacture of the complex, different irradiation cycles. These cycles consist in carrying out one or more successive passages under the UV lamp of the IST bench adjusted to a power of 160W / cm and at a passage speed of 50m / min. The adhesion strength of TESA® 4970 is measured during the day using the peel test defined above. The results obtained are presented in Figures 1 and 2.
- the irradiation causes an increase in the release force for the formulations containing the additive according to the present invention.
- the additive concentration a also an impact on the release force.
- the release force varies in effect depending on the concentration of additive.
- the release force increases practically linearly with the number of passes under the UV lamp. Forces of 100 g / cm (40 cN / inch) are thus reached after 4 passes.
- the formulation in accordance with the invention was moreover tested at the end of an accelerated aging cycle.
- This cycle is imposed in particular by subjecting the complex for 6 days at a temperature of 70 ° C. These conditions are supposed to represent natural aging! of the complex lasting 6 months.
- Rhodotak® 315P non tackified permanent acrylic adhesive
- Rhodotak® 338J tackified permanent acrylic adhesive
- Rhodotak® 300 removable acrylic adhesive
- the additive tested is trimethylpentanedioltriacrylate (TMPTA).
- TMPTA was added to it at two rates: 0.34 and 5% by weight.
- the 0.34% mixture is miscible while the 5% mixture is not.
- these coatings are bonded with TESA® 4970 adhesive and the complex is irradiated under different conditions.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Silicon Polymers (AREA)
- Organic Insulating Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU21780/01A AU2178001A (en) | 1999-11-26 | 2000-11-24 | Cation-curable silicone /adhesive complex whereof the interface has release force capable of being modulated |
US10/130,939 US6849340B1 (en) | 1999-11-26 | 2000-11-24 | Carbon-curable silicone/adhesive complex whereof the interface has release force capable of being modulated |
AT00985324T ATE288950T1 (de) | 1999-11-26 | 2000-11-24 | Komplex aus kationisch vernetzbarer silikonverbindung und klebstoff mit modulierbarer trennkraft an deren schnittstelle |
DE60018106T DE60018106T2 (de) | 1999-11-26 | 2000-11-24 | Komplex aus kationisch vernetzbarer silikonverbindung und klebstoff mit modulierbarer trennkraft an deren schnittstelle |
EP00985324A EP1242552B1 (fr) | 1999-11-26 | 2000-11-24 | Complexe silicone reticulable par voie cationique/adhesif dont l'interface possede une force de decollement modulable |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR99/14944 | 1999-11-26 | ||
FR9914944A FR2801600B1 (fr) | 1999-11-26 | 1999-11-26 | Complexe silicone reticulable par voie cationique / adhesif dont l'interface possede une force de decollement modulable |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001038450A1 true WO2001038450A1 (fr) | 2001-05-31 |
Family
ID=9552605
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2000/003293 WO2001038450A1 (fr) | 1999-11-26 | 2000-11-24 | Complexe silicone reticulable par voie cationique/adhesif dont l'interface possede une force de decollement modulable |
Country Status (8)
Country | Link |
---|---|
US (1) | US6849340B1 (fr) |
EP (1) | EP1242552B1 (fr) |
AT (1) | ATE288950T1 (fr) |
AU (1) | AU2178001A (fr) |
DE (1) | DE60018106T2 (fr) |
ES (1) | ES2236019T3 (fr) |
FR (1) | FR2801600B1 (fr) |
WO (1) | WO2001038450A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6881765B2 (en) * | 2003-03-10 | 2005-04-19 | Toagosei Co., Ltd. | Curable release agent and separator using same |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7135535B2 (en) * | 2004-07-29 | 2006-11-14 | National Starch And Chemical Investment Holding Corporation | Siloxane resins with oxetane functionality |
WO2006085421A1 (fr) * | 2005-02-08 | 2006-08-17 | The Yokohama Rubber Co., Ltd. | Dérivé d'oxétane et formule durcissable contenant ledit dérivé |
FR2890967A1 (fr) * | 2005-09-16 | 2007-03-23 | Rhodia Recherches & Tech | Procede de preparation de revetements organiques reticules sur un support |
FR2890970B1 (fr) * | 2005-09-16 | 2008-03-14 | Rhodia Recherches & Tech | Procede de preparation d'un revetement silicone anti- adherent |
CN101085884A (zh) * | 2006-06-06 | 2007-12-12 | 罗门哈斯公司 | 可剥离涂料和工艺 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0476925A2 (fr) * | 1990-09-17 | 1992-03-25 | Shin-Etsu Chemical Co., Ltd. | Composition d'organopolysiloxane durcissable par la lumière UV |
US5616629A (en) * | 1994-08-24 | 1997-04-01 | Avery Dennison Corporation | Radiation-curable organopolysiloxane release compositions |
DE19831775A1 (de) * | 1997-07-15 | 1999-01-21 | Morgan Adhesives Co | Ultraviolette Steuerung des Ablösens eines drucksensitiven Klebstoffes, der sich in Kontakt mit einem Silikon-Abziehliner befindet |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4576999A (en) * | 1982-05-06 | 1986-03-18 | General Electric Company | Ultraviolet radiation-curable silicone release compositions with epoxy and/or acrylic functionality |
JPH07188631A (ja) * | 1993-12-28 | 1995-07-25 | Toyo Ink Mfg Co Ltd | 再剥離型粘着剤組成物 |
US5650453A (en) * | 1995-04-28 | 1997-07-22 | General Electric Company | UV curable epoxysilicone blend compositions |
-
1999
- 1999-11-26 FR FR9914944A patent/FR2801600B1/fr not_active Expired - Fee Related
-
2000
- 2000-11-24 AT AT00985324T patent/ATE288950T1/de not_active IP Right Cessation
- 2000-11-24 WO PCT/FR2000/003293 patent/WO2001038450A1/fr active IP Right Grant
- 2000-11-24 DE DE60018106T patent/DE60018106T2/de not_active Expired - Fee Related
- 2000-11-24 US US10/130,939 patent/US6849340B1/en not_active Expired - Fee Related
- 2000-11-24 ES ES00985324T patent/ES2236019T3/es not_active Expired - Lifetime
- 2000-11-24 EP EP00985324A patent/EP1242552B1/fr not_active Expired - Lifetime
- 2000-11-24 AU AU21780/01A patent/AU2178001A/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0476925A2 (fr) * | 1990-09-17 | 1992-03-25 | Shin-Etsu Chemical Co., Ltd. | Composition d'organopolysiloxane durcissable par la lumière UV |
US5616629A (en) * | 1994-08-24 | 1997-04-01 | Avery Dennison Corporation | Radiation-curable organopolysiloxane release compositions |
DE19831775A1 (de) * | 1997-07-15 | 1999-01-21 | Morgan Adhesives Co | Ultraviolette Steuerung des Ablösens eines drucksensitiven Klebstoffes, der sich in Kontakt mit einem Silikon-Abziehliner befindet |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6881765B2 (en) * | 2003-03-10 | 2005-04-19 | Toagosei Co., Ltd. | Curable release agent and separator using same |
Also Published As
Publication number | Publication date |
---|---|
FR2801600B1 (fr) | 2002-03-01 |
ES2236019T3 (es) | 2005-07-16 |
FR2801600A1 (fr) | 2001-06-01 |
DE60018106D1 (de) | 2005-03-17 |
AU2178001A (en) | 2001-06-04 |
EP1242552A1 (fr) | 2002-09-25 |
DE60018106T2 (de) | 2006-01-19 |
EP1242552B1 (fr) | 2005-02-09 |
ATE288950T1 (de) | 2005-02-15 |
US6849340B1 (en) | 2005-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1242553B1 (fr) | Utilisation d' un additif de regulation de la force de decollement d' une interface silicone/adhesif dans un complexe silicone reticulable thermiquement/adhesif | |
EP0703236B1 (fr) | Amorceurs de réticulation, par voie cationique, de polymères à groupements organofonctionnels compositions à base de polyorganosiloxanes réticulables et contenant ces amorceurs et application desdites compositions en antiadhérence | |
US6268404B1 (en) | Radiation-curable organosiloxane coating compositions | |
FR2712297A1 (fr) | Compositions à base d'époxysilicone, durcissables par les rayons UV, antiadhésives. | |
EP1937416A1 (fr) | Procede de preparation d'un revetement silicone anti-adherent | |
EP1278809B1 (fr) | Complexe silicone/adhesif dont l'interface possede une force de decollement modulable par irradiation par faisceau d'electrons | |
EP1226210B1 (fr) | Utilisation d'amorceurs de polymerisation et/ou reticulation de polyorganosiloxanes a groupements fonctionnels reticulables, compositions correspondantes | |
EP1242552B1 (fr) | Complexe silicone reticulable par voie cationique/adhesif dont l'interface possede une force de decollement modulable | |
FR2731007A1 (fr) | Composition de polyorganosiloxanes reticulables | |
WO2002092665A1 (fr) | Composition silicone polymerisable reticulable par voie cationique, sous activation thermique et au moyen d'un amorceur de type adduit acide/base de lewis | |
WO2002042388A1 (fr) | Compositions a base de silicones fonctionnalisees durcissables sous irradiation et revêtements anti-adherents obtenus a partir de ces compositions | |
WO2001030930A1 (fr) | Complexe silicone/adhesif anti-adherent avec additif de stabilisation dans silicone | |
CA2389017A1 (fr) | Complexe silicone/adhesif anti-adherent avec additif de stabilisation | |
US7109251B2 (en) | Compositions based on radiation-curable functionalized silicones and anti-adhesive coatings obtained from same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2000985324 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10130939 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 2000985324 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWG | Wipo information: grant in national office |
Ref document number: 2000985324 Country of ref document: EP |