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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
  • C09D5/1662—Synthetic film-forming substance
  • C09D5/1675—Polyorganosiloxane-containing compositions
• • 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
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • 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 hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/148—Polysiloxanes
• • 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
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • 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
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
• • 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
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
• • 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
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
• • 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
  • 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
  • C09D183/10—Block or graft copolymers containing polysiloxane sequences
• • 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
  • C09J183/00—Adhesives 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; Adhesives based on derivatives of such polymers
  • C09J183/04—Polysiloxanes
  • C09J183/06—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
  • C09J183/00—Adhesives 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; Adhesives based on derivatives of such polymers
  • C09J183/10—Block or graft copolymers containing polysiloxane sequences

Definitions

• Radiation-crosslinkable silicone composition comprising an adhesion modulator
• the present invention relates to a radiation-curable silicone composition comprising an adhesion modulator, which is an organopolysiloxane resin comprising Si—OH groups.
• an adhesion modulator which is an organopolysiloxane resin comprising Si—OH groups.
• the invention relates to a silicone composition comprising at least one organopolysiloxane A comprising at least one (meth)acrylate group, at least 25% by weight of an organopolysiloxane resin B comprising Si—OH groups, and, optionally, at least one C-radical photoinitiator.
• the compositions of the present invention can be used to form release coatings.
• plastic films as support materials for the coating of silicone coatings in order to create release coatings requires suitable technology. Indeed, most of these plastic films are heat sensitive. Thus, a dimensional deformation of the film occurs during the coating and drying in thermal ovens of the silicone layer under the combined effect of the tensile forces and the temperature imposed on the films.
• the technology of crosslinking functional silicone oils under irradiation, in particular under ultraviolet (UV) radiation, makes it possible to dispense with the use of high temperatures and therefore to crosslink non-stick layers without impacting the supports. In addition, this technology has the advantage of achieving high productivity without being energy-intensive and without using solvents.
• Plastic substrates are materials of choice for many applications and their use is constantly growing.
• non-stick silicone coatings are generally carried out as follows: a silicone composition is applied to a support in an industrial coating device comprising cylinders operating at very high speed (for example 600 m/min ). Once applied to the support, the silicone composition crosslinks to form a solid coating in non-stick silicone (eg elastomer).
• the coated support obtained is also called a silicone liner.
• This silicone liner can in particular be complexed with an adhesive, because the non-stick silicone coating facilitates the removal of adhesive materials reversibly laminated on these supports.
• these silicone liners can be used in the field of self-adhesive labels, tapes including envelopes, graphic arts, medical care and hygiene.
• the silicone compositions used to form non-stick coatings are generally crosslinked under irradiation, in particular under UV or visible radiation emitted by doped or undoped mercury vapor lamps, the emission spectrum of which extends from 200 nm to 450 n.
• Light sources such as light-emitting diodes, better known by the acronym "LED” (Light-Emitting Diodes) which deliver point UV or visible light can also be used.
• crosslinking under irradiation of functionalized silicone oils can be done according to 2 approaches: the cationic polymerization of epoxy groups or the radical polymerization of acrylic functions. Free radical polymerization is inhibited neither by bases nor by humidity. Thus, coating supports and additives can be more diversified and interest in these radical systems is growing.
• document FR2632960 describes polysiloxanes with (meth)acrylic ester groups linked by SiC groups.
• chain lengths and acrylate levels of polysiloxane oils it is possible to modulate the adhesion of these crosslinking systems under UV.
• this approach it is necessary to synthesize a new siloxane oil for each level of anti-adhesion targeted, making the possibility of adjustment difficult.
• the present invention aims to satisfy at least one of the following objectives.
• One of the essential objectives of the invention is to provide a silicone composition which can be crosslinked by irradiation comprising an adhesion modulator additive (“RCA” release control agent) and which can be used to form anti- members.
• RCA adhesion modulator additive
• Another essential objective of the invention is to provide a silicone composition that can be crosslinked by irradiation with improved properties.
• Another essential objective of the invention is to provide a silicone composition that can be crosslinked by irradiation, the properties of adhesion of which to an adhesive of the coating obtained after crosslinking of the silicone composition can be modulated.
• Another essential objective of the invention is to provide a silicone composition that can be crosslinked by irradiation which is easy to prepare industrially and is economical.
• Another essential objective of the invention is to provide a silicone composition that can be crosslinked by irradiation which can be used without a solvent for an ecological aspect.
• Another essential objective of the invention is to provide a silicone composition that can be crosslinked by irradiation with a viscosity compatible with the coating tools used to prepare non-stick silicone coatings.
• Another essential object of the invention is to provide a silicone composition that can be crosslinked by irradiation which makes it possible to obtain a coating having a detachment profile which is "smooth", that is to say with little or no noise when pulling, i.e. the peeling forces remain stable throughout the complex delamination step (separation between the adhesive and the silicone liner).
• Another essential objective of the invention is to provide a silicone composition that can be crosslinked by irradiation which makes it possible to obtain a coating having peeling forces which are stable with aging.
• Another essential objective of the invention is to provide a silicone composition that can be crosslinked by irradiation which makes it possible to obtain a coating having stable peeling forces whatever the peeling speed.
• a silicone composition X that can be crosslinked by irradiation comprising: a. at least one organopolysiloxane A comprising at least one (meth)acrylate group; b. at least 25% by weight of an organopolysiloxane resin B comprising Si-OH groups; etc. optionally, at least one radical photoinitiator C.
• an organopolysiloxane resin B comprising Si—OH groups makes it possible to modulate the anti-adherence of the coating obtained after crosslinking of the silicone composition X, faced with an adhesive. It is therefore possible to use the silicone composition X crosslinkable by irradiation to form non-stick coatings on a support.
• the anti-adherence of the free external face of the silicone coating is expressed through the peeling forces of a standardized adhesive, which must be controlled.
• the detachment forces can in particular be measured by the FINAT 3 (FTM 3) test, well known to those skilled in the art. This test determines the peel forces (also called peel force) needed to peel off the support. coated (also called silicone liner) complexed with an adhesive.
• the compositions according to the invention make it possible to modulate these detachment forces, and therefore the properties of anti-adhesion against an adhesive, easily, according to the intended application, in particular by adjusting the level of resin in the composition.
• the coatings obtained after crosslinking of the compositions according to the invention have a detachment profile which is "smooth", the detachment forces of which remain stable throughout the complex delamination step (separation between the adhesive and the silicone liner).
• these advantages are obtained while maintaining good properties elsewhere (smear, rub off and subsequent adhesion).
• the invention also relates to the use of the silicone composition X crosslinkable by irradiation for the preparation of silicone elastomers capable of being used as an anti-adherent coating on a support.
• the invention also relates to a process for preparing a coating on a support, comprising the following steps:
• the supports which can be coated are, for example, flexible supports made of textile, paper, polyvinyl chloride, polyester, polypropylene, polyamide, polyethylene, polyethylene terephthalate, polyurethane or glass fibers not woven.
• the invention also relates to a coated support which can be obtained according to the method described above.
• the invention also relates to a premix for a silicone composition
• a premix for a silicone composition comprising: a. between 20 and 40% by weight of at least one organopolysiloxane A comprising at least one (meth)acrylate group; b. between 30 and 50% by weight of an organopolysiloxane resin B comprising Si—OH groups, and c. between 10 and 30% by weight of an organic compound D comprising a (meth)acrylate function.
• silicone composition crosslinkable by irradiation means a silicone composition comprising at least one organopolysiloxane capable of curing by electronic or photonic irradiation.
• electronic irradiations we can cite exposure to an electron beam.
• photonic irradiations mention may be made of exposure to radiation with a wavelength of between 200 nm and 450 nm, in particular to UV radiation, or exposure to gamma rays.
• adheresion modulator an additive capable of modifying the adhesion or anti-adhesion properties of the coating obtained after crosslinking of the silicone composition X, faced with an adhesive.
• the oxygen atom belongs to a hydroxyl group bonded to a silicon atom
• this chemical function may be indicated in parentheses in the abbreviated formula.
• the remaining bonds of the silicon atom are considered to be engaged with a carbon atom.
• the hydrocarbon groups bonded to silicon by a C—Si bond are not mentioned and most often correspond to an alkyl group, for example a methyl group.
• the abbreviated formula T(OH)2 represents a unit in which the silicon atom is bonded to three oxygen atoms including two hydroxyl groups, i.e. an alkyldihydroxysiloxyl unit RSi(OH) 2 0i /2 where R may represent various saturated or unsaturated hydrocarbon groups, in particular aromatic, and optionally substituted by heteroatoms. The meaning of R will be specified in the description.
• (meth)acrylate is meant a methacrylate group or an acrylate group.
• organopolysiloxane resin means an organopolysiloxane compound comprising at least one T unit and/or at least one Q unit.
• alkylene is meant a divalent, linear or branched alkyl group.
• the alkylene group preferably comprises between 1 and 18 carbon atoms, and more preferably between 1 and 12 carbon atoms.
• heteroalkylene is meant a divalent, linear or branched heteroalkyl group.
• the heteroalkyl group preferably comprises between 1 and 18 carbon atoms, and between 1 and 6 heteroatoms selected from the group consisting of O, N and S, where N and S can be optionally oxidized. Heteroatoms can be placed at any position of the heteroalkyl group, either in the interior position or at one end.
• cycloalkylene is meant a divalent cycloalkyl.
• the cycloalkyl group preferably comprises between 3 and 12 carbon atoms, preferably between 3 and 6 carbon atoms.
• solvent means an organic solvent.
• Organic solvents are well known to those skilled in the art. Examples of organic solvents include alkanes (such as pentane or hexane), aromatics (such as benzene, toluene or xylene), ethers (such as diethyl ether or tetrahydrofuran), alcohols (such as methanol, ethanol, propanol, or butanol), chloroform, acetone, acetonitrile, pyridine, ethyl acetate, dimethyl formamide, and dimethyl sulfoxide.
• composition without solvent one means a composition comprising less than 10% by weight of solvent, preferably less than 5%, and more preferably less than 1%.
• the radiation-curable silicone composition X comprises: a. at least one organopolysiloxane A comprising at least one (meth)acrylate group; b. at least 25% by weight of an organopolysiloxane resin B comprising Si-OH groups, and c. optionally, at least one radical photoinitiator C.
• the silicone composition X is crosslinkable by electronic or photon irradiation, preferably by exposure to an electron beam, by exposure to gamma rays, or by exposure to radiation of wavelength between 200 nm and 450 nm, in particular to UV radiation.
• the radiation-crosslinkable silicone composition X is solvent-free.
• the radiation-curable silicone composition X may have a viscosity of between 200 and 2500 mPa.s, preferably between 500 and 1500 mPa.s, it is therefore possible to use it with the coating tools used for prepare non-stick silicone coatings.
• the crosslinkable silicone compositions X according to the invention comprise at least one organopolysiloxane A comprising at least one (meth)acrylate group, preferably at least 2 (meth)acrylate groups.
• (meth) acrylate functions carried by the silicone and very particularly suitable for the invention mention may more particularly be made of acrylate derivatives, methacrylates, ethers of (meth) acrylates and esters of (meth) acrylates linked to the polysiloxane chain by an Si-C bond.
• the organopolysiloxane A comprises: a) at least one unit of formula (I) below:
• R symbols which are identical or different, each represent a linear or branched C1 to C18 alkyl group, a C6 to C12 aryl or aralkyl group, said alkyl and aryl groups possibly being substituted, preferably by halogen atoms , or an -OR 5 group with R 5 being a hydrogen atom or a hydrocarbon group comprising from 1 to 10 carbon atoms,
• - y represents a polyvalent C1-C18 alkylene or heteroalkylene group, said alkylene and heteroalkylene groups possibly being linear or branched, and possibly being interrupted by one or more cycloalkylene groups, and possibly being extended by bivalent oxyalkylene or polyoxyalkylene C1 radicals at C4, said alkylene, heteroalkylene, oxyalkylene and polyoxyalkylene groups possibly being substituted by one or more hydroxy groups,
• - Y' represents a monovalent alkenylcarbonyloxy group
• - n is equal to 1, 2 or 3
• - - a is an integer equal to 0, 1, 2 or 3.
• the symbols R which are identical or different, each represent a linear or branched C1 to C18 alkyl group or a C6 to C12 aryl or aralkyl group.
• the symbol R represents a monovalent group chosen from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl, and preferentially the symbol R represents a methyl.
• the organopolysiloxane A can have a linear, branched, cyclic or network structure.
• the organopolysiloxane A has a linear structure.
• linear organopolysiloxanes these can essentially consist of:
• the organopolysiloxane A comprises at least 2 Y′ alkenylcarbonyloxy groups, preferably at least 3 Y′ alkenylcarbonyloxy groups.
• R' which is a C1 -C6 -(CH 2 ) 3 -OCH 2 -alkyl group
• the organopolysiloxane A corresponds to the following formula (III): [Chem. 1] formula in which:
• R 1 which are identical or different, each represent a linear or branched Ci to Cis alkyl group, an aryl or Ce to Ci 2 aralkyl group, said alkyl and aryl groups possibly being substituted, preferably by atoms of halogen, or an -OR 5 group with R 5 being a hydrogen atom or a hydrocarbon group comprising from 1 to 10 carbon atoms,
• - y represents a polyvalent C1-C18 alkylene or heteroalkylene group, said alkylene and heteroalkylene groups possibly being linear or branched, and possibly being interrupted by one or more cycloalkylene groups, and possibly being extended by bivalent oxyalkylene or polyoxyalkylene C1 radicals at C4, said alkylene, heteroalkylene, oxyalkylene and polyoxyalkylene groups optionally being substituted by one or more hydroxy groups, - Y' represents a monovalent alkenylcarbonyloxy group, and
• - n is equal to 1, 2 or 3
• R 2 or R 3 symbol represents the monovalent group of formula Z, preferably at least two R 2 or R 3 symbols represent a monovalent group of formula Z.
• the organopolysiloxane A according to the invention corresponds to one of the following formulas (IV), (V), (VI) or (VII):
• - x1 is between 1 and 1000; preferably x1 is between 1 and 500 or between 1 and 499,
• - n1 is between 1 and 100, preferably n1 is between 2 and 100,
• - x2 is between 1 and 1000, preferably x2 is between 1 and 500 or between 1 and 499,
• - n2 is between 1 and 100, preferably n2 is between 2 and 100, - x3 is between 1 and 1000, preferably x3 is between 1 and 500, and
• - x4 is between 1 and 1000, preferably x4 is between 1 and 500.
• the radiation-crosslinkable silicone X composition may comprise between 25 and 75% of organopolysiloxane A, relative to the total weight of the radiation-crosslinkable silicone X composition.
• the organopolysiloxane A can have a molar content depending on
• (meth)acrylate greater than or equal to 30 mmol/100 g of organopolysiloxane A, preferably between 35 and 250 mmol/100 g of organopolysiloxane A.
• the organopolysiloxane A can have a molar content depending on
• (meth)acrylate greater than or equal to 60 mmol/100 g of organopolysiloxane A, preferably between 65 and 250 mmol/100 g of organopolysiloxane A.
• the radiation-curable silicone composition X may comprise a single organopolysiloxane A or a mixture of several organopolysiloxanes A having for example different acrylate contents.
• the radiation-crosslinkable composition X comprises a mixture of several organopolysiloxanes A, several embodiments are possible.
• the organopolysiloxane A may for example comprise:
• organopolysiloxane having a high molar content of (meth)acrylate function for example, greater than or equal to 30 or 60 mmol/100 g of organopolysiloxane
• organopolysiloxane with a low molar content of (meth)acrylate function (for example, less than 30 or 60 mmol/100 g of organopolysiloxane respectively).
• the organopolysiloxane A comprises: a1. at least one organopolysiloxane A1 comprising at least one group
• (meth)acrylate and having a molar content of (meth)acrylate function greater than or equal to 30 mmol/100 g of organopolysiloxane A1, preferably between 35 and 250 mmol/100 g of organopolysiloxane A1; and a2. at least one organopolysiloxane A2 comprising at least one group
• (meth)acrylate and having a molar content of (meth)acrylate function of less than 30 mmol/100 g of organopolysiloxane A2, preferably between 1 and 30 mmol/100 g of organopolysiloxane A2, and even more preferably between 15 and 25 mmol/100 g organopolysiloxane A2.
• the organopolysiloxane A comprises: a1. at least one organopolysiloxane A1' comprising at least one group
• (meth)acrylate and having a molar content of (meth)acrylate function greater than or equal to 60 mmol/100 g of organopolysiloxane A1′, preferably between 65 and 250 mmol/100 g of organopolysiloxane A1′; and a2. at least one organopolysiloxane A2' comprising at least one group
• (meth)acrylate and having a molar content of (meth)acrylate function of less than 60 mmol/100 g of organopolysiloxane A2′, preferably between 1 and 60 mmol/100 g of organopolysiloxane A2′, and even more preferably between 15 and 55 mmol/100 g of organopolysiloxane A2′.
• the (meth)acrylate function content is expressed in mmol/100 g of organopolysiloxane A, A1, A1′, A2 or A2′.
• organopolysiloxanes A1, A1′, A2 and A2′ can be as described above for organopolysiloxane A.
• the combination of two organopolysiloxanes A1 and A2, or A1′ and A2′, having a different molar acrylate content makes it possible to modulate the adhesion of the coating obtained after crosslinking, facing an adhesive. Indeed, it is possible to modulate the adhesion of the coating obtained after crosslinking, facing an adhesive, according to the desired application by adjusting the amount of organopolysiloxane A2 or A2' in the silicone composition X.
• the silicone composition X may comprise between 0.1 and 10% by weight of organopolysiloxane A2 or A2′, preferably between 1 and 8% by weight, relative to the total weight of the silicone composition X which can be crosslinked by irradiation.
• the silicone composition X may comprise:
• organopolysiloxane A1 or A1′ preferably between 25 and 65% by weight, relative to the total weight of the silicone composition X crosslinkable by irradiation
• organopolysiloxane A2 or A2′ preferably between 1 and 8% by weight, relative to the total weight of the silicone composition X that can be crosslinked by irradiation.
• the proportion of organopolysiloxane A2 or A2′ relative to the organopolysiloxane A1 or A1′ can be expressed by a mass ratio A2:A1 or A2′:A1′.
• this ratio is between 1:65 and 1:2, preferably between 1:50 and 1:3, and even more preferably between 1:40 and 1:5.
• Orqanopolvsiloxane resin B comprising Si—OH groups
• the organopolysiloxane resin B comprising Si—OH groups makes it possible to modulate the adhesion of the coating obtained after crosslinking, faced with an adhesive.
• the organopolysiloxane resin B also makes it possible to obtain a coating whose detachment profile is "smooth", that is to say whose detachment forces remain stable throughout the complex delamination step (separation between the adhesive and the silicone liner).
• the radiation-curable silicone composition X comprises between 25 and 60% by weight of resin B, preferably between 25 and 50% by weight.
• the organopolysiloxane resin B is a branched organopolysiloxane oligomer or polymer that is well known and commercially available.
• the resin comprises at least one T unit and/or at least one Q unit. It also comprises at least one OH function bonded to a silicon atom in its structure, it therefore comprises Si—OH groups.
• R 4 alkyl group of the methyl, ethyl, isopropyl, tert-butyl and n-hexyl groups.
• the R 4 group is a methyl radical.
• organopolysiloxane B resins examples include MDT resins, DT resins and MQ resins.
• the R 4 groups are as described above.
• the R 4 groups are as described above.
• the R 4 groups are as described above.
• the R 4 groups are chosen independently of each other from linear or branched C1 - C6 alkyl groups, and the 3,3,3-trifluoropropyl group.
• resin B is an MDT or MQ resin.
• resins with a Q pattern When resins with a Q pattern are used, they can have a molar ratio M/(T+Q) of between 0.5 and 1.5, preferably between 0.7 and 1.2.
• the OH function content of resin B can be between 0.2 and 5% by weight. According to one embodiment, the OH function content is at least 0.5% by weight. Preferably, the content of OH function is between 0.5 and 5% by weight, preferentially between 0.6 and 4.5% by weight, and more preferentially between 0.7 and 4% by weight. The OH function content is expressed in weight of OH functions relative to the total weight of resin B.
• Resin B generally has an average molecular weight between 500 and 10,000 g/mol, preferably between 1,000 and 6,000 g/mol.
• the radiation-curable silicone composition X may comprise a single resin B or a mixture of several resins B.
• the silicone composition which can be crosslinked by irradiation may comprise a radical photoinitiator C. This is particularly the case when the composition is crosslinkable by photon irradiation, under radiation with a wavelength of between 200 nm and 450 nm, in particular under radiation UV.
• the radical photoinitiator C releases free radicals in the medium, under the effect of the absorption of the incident light energy. These radicals act as radical polymerization initiators of the (meth)acrylic functions.
• the radical photoinitiators are, among others, aromatic ketones which, after exposure to ultraviolet (UV) radiation:
• photoinitiators are well known to those skilled in the art.
• type I photoinitiators mention may be made of: ⁇ -hydroxyketones, benzoin ethers, and ⁇ -amino aromatic ketones.
• type II photoinitiators mention may be made of isopropylthioxanthone (ITX), benzophenone and camphorquinone (CQ).
• co-initiators include: phenyltetrazolethiol, tris(trimethylsilyl)silane and aromatic amines such as ethyldimethylaminobenzoate (EDB)
• photoinitiators are for example described in patents FR2632960, EP0940422-B1, EP0979851-B1, EP1544232-B1, and
• EP1411095A2 The photoinitiator conventionally used is Irgacure ® 1173 (formerly Darocur ® 1173) from BASF.
• C radical photoinitiators By way of examples of C radical photoinitiators, mention will be made in particular of the following products: isopropylthioxanthone; benzophenone; camphorquinone; 9-xanthenone; anthraquinone; 1-4 dihydroxyanthraquinone; 2-methylanthraquinone; 2,2'-bis(3-hydroxy-1,4-naphthoquinone);2,6-dihydroxyanthraquinone;1-hydroxycyclohexylphenylketone;1,5-dihydroxyanthraquinone;1,3-diphenyl-1,3-propanedione;5,7-dihydroxyflavone;dibenzoylperoxide; 2-benzoylbenzoic acid; 2-hydroxy-2-methylpropi-phenone; 2-phenylacetophenone; anthrone; 4,4'-dimethoxybenzoin;phenanthrenequinone;2-ethy
• radical photoinitiators C As examples of commercial products of radical photoinitiators C according to the invention, mention may also be made, among the benzophenone derivatives, of the products Esacure ® TZT, Speedcure ® MBP, Omnipol ® BP and among the derivatives of thioxanthone , the products Irgacure ® 907, Omnipol ® TX and Genopol ® TX-1.
• the radical photoinitiator C is chosen from the group consisting of benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, benzoyl formate esters, camphorquinone, benzil, phenanthrenequinone, coumarins and ketocoumarins and mixtures thereof. Examples of these radicals are for example described in application WO2017/109116.
• benzophenone derivatives is meant substituted benzophenones and polymeric versions of benzophenone.
• thioxanthone derivatives substituted thioxanthones and by anthraquinone derivatives is meant substituted anthraquinones, in particular anthraquinone sulphonic acids and acrylamido-substituted anthraquinones.
• benzoyl formate esters mention may be made of methyl benzoyl formate, optionally bifunctional.
• radical photoinitiator C is chosen from the group consisting of the derivatives (chemical names in English): 2,2-dimethyl-propionyldiphenyl-phosphine oxide,
• the radical photoinitiator C is ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate (CAS No. 84434-11-7).
• the effective amount of radical photoinitiator C is between 0.1% and 20% by weight relative to the total weight of the silicone composition X crosslinkable by irradiation, or of the functionalized organopolysiloxane A, and preferably between 0.1 and 10% by weight, and even more preferably between 0.1% and 5% by weight.
• the radiation-crosslinkable silicone composition X may comprise an organic compound D comprising at least one (meth)acrylate function.
• the radiation-curable silicone composition X may comprise an organic compound D or several different organic compounds D.
• organic compounds D comprising at least one (meth)acrylate function makes it possible to obtain, after crosslinking of the silicone composition X, a coating having detachment forces, faced with an adhesive, which are stable with aging.
• the radiation-crosslinkable silicone composition X comprises between 0.1 and 30% by weight of organic compound D comprising a (meth)acrylate function, preferably between 1 and 25% by weight, and preferably between 3 and 22 % in weight.
• organic compound D comprising at least one (meth)acrylate function is meant any compound comprising one or more (meth)acrylate functions.
• the organic compound D comprising at least one (meth)acrylate function does not comprise a siloxane structure.
• organic compounds D comprising a (meth)acrylate function, epoxidized (meth)acrylates, (meth)acryloglyceropolyesters, (meth)acrylo-uretanes, (meth)acrylopolyethers, (meth)acrylopolyesters, and (meth)acrylopolyesters, )acrylo-acrylics. More particularly preferred are trimethylolpropane triacrylate, tripropylene glycol diacrylate, hexanediol diacrylate and pentaerythritol tetraacrylate.
• organic compound D comprising a (meth)acrylate function
• the radiation-crosslinkable silicone X composition may also comprise other additives such as polymerization inhibitors, fillers, virucides, bactericides, anti-abrasion additives, and pigments (organic or inorganic).
• additives such as polymerization inhibitors, fillers, virucides, bactericides, anti-abrasion additives, and pigments (organic or inorganic).
• the radiation-curable silicone composition X comprises: a. at least one organopolysiloxane A comprising at least one (meth)acrylate group; said organopolysiloxane A corresponding to the following formula (III): formula in which:
• R 1 which are identical or different, each represent a linear or branched Ci to Cie alkyl group, an aryl or Ce to C12 aralkyl group, said alkyl and aryl groups possibly being substituted, preferably by atoms of halogen, or an -OR 5 group with R 5 being a hydrogen atom or a hydrocarbon group comprising from 1 to 10 carbon atoms,
• - y represents a polyvalent C1-C18 alkylene or heteroalkylene group, said alkylene and heteroalkylene groups possibly being linear or branched, and possibly being interrupted by one or more cycloalkylene groups, and possibly being extended by bivalent oxyalkylene or polyoxyalkylene C1 radicals at C4, said alkylene, heteroalkylene, oxyalkylene and polyoxyalkylene groups optionally being substituted by one or more hydroxy groups,
• - Y' represents a monovalent alkenylcarbonyloxy group
• - n is equal to 1, 2 or 3
• R 2 or R 3 symbol represents the monovalent group of formula Z, preferably at least two R 2 or R 3 symbols represent a monovalent group of formula Z; b. at least 25% by weight of an organopolysiloxane resin B comprising Si-OH groups; etc. optionally, at least one radical photoinitiator C.
• the radiation-crosslinkable silicone composition X comprises an organic compound D comprising at least one (meth)acrylate function
• a premix comprising: a. between 20 and 40% by weight of at least one organopolysiloxane A comprising at least one (meth)acrylate group; b. between 30 and 50% by weight of an organopolysiloxane resin B comprising Si-OH groups; etc. between 10 and 30% by weight of an organic compound D comprising a (meth)acrylate function.
• This premix can then be diluted in the organopolysiloxane A to form the silicone composition X which can be crosslinked by irradiation.
• This premix can have a viscosity of between 500 and 2000 mPa.s, which makes it easy to dilute it in the organopolysiloxane A. This makes it possible to easily form a radiation-crosslinkable silicone composition X having a viscosity compatible with the coating tools .
• this premix it is also possible to easily modulate the concentration of organopolysiloxane resin B in the silicone composition X crosslinkable by irradiation, and therefore to easily modulate the adhesion of the coating obtained after crosslinking, against an adhesive.
• This premix also makes it possible to obtain silicone compositions having better homogeneity, which is important when used on coating devices comprising rollers operating at very high speed.
• An object of the present invention is therefore a premix for a silicone composition
• a silicone composition comprising: a. between 20 and 40% by weight of at least one organopolysiloxane A comprising at least one (meth)acrylate group; b. between 30 and 50% by weight of an organopolysiloxane resin B comprising Si-OH groups; etc. between 10 and 30% by weight of an organic compound D comprising a (meth)acrylate function.
• a subject of the present invention is also a radiation-crosslinkable silicone composition X1 comprising: a. 1) at least one organopolysiloxane A1 comprising at least one (meth)acrylate group, and having a molar content of (meth)acrylate function greater than or equal to 30 mmol/100 g of organopolysiloxane A1, preferably between 35 and 250 mmol /100 g of organopolysiloxane A1; has.
• organopolysiloxane A2 comprising at least one (meth)acrylate group, and having a molar content of (meth)acrylate function of less than 30 mmol/100 g of organopolysiloxane A2, preferably between 1 and 30 mmol/100 g of organopolysiloxane A2, and even more preferably between 15 and 25 mmol/100 g of organopolysiloxane A2;
• organopolysiloxane resin B comprising Si—OH groups, and c. optionally, at least one radical photoinitiator C.
• a subject of the present invention is also a silicone composition X1′ that can be crosslinked by irradiation, comprising: a. 1) at least one organopolysiloxane A1' comprising at least one (meth)acrylate group, and having a molar content of (meth)acrylate function greater than or equal to 60 mmol/100 g of organopolysiloxane A1', preferably between 65 and 250 mmol/100 g organopolysiloxane A1'; has.
• organopolysiloxane A2' comprising at least one (meth)acrylate group, and having a molar content of (meth)acrylate function of less than 60 mmol/100 g of organopolysiloxane A2', preferably between 1 and 60 mmol /100 g of organopolysiloxane A2', and even more preferably between 15 and 55 mmol/100 g of organopolysiloxane A2'; b. at least one organopolysiloxane resin B comprising Si—OH groups, and c. optionally, at least one radical photoinitiator C.
• silicone compositions X1 and X1′ that can be crosslinked by irradiation can comprise between 0.5 and 60% by weight of resin B, preferably between 10 and 50% by weight.
• the radiation-crosslinkable silicone composition X1 comprises between 0.1 and 10% by weight of organopolysiloxane A2, preferably between 2 and 8% by weight.
• the silicone composition X1 may comprise:
• organopolysiloxane A1 preferably between 25 and 65% by weight, relative to the total weight of the silicone composition X1 crosslinkable by irradiation and
• the radiation-crosslinkable silicone composition X1′ comprises between 0.1 and 10% by weight of organopolysiloxane A2′, preferably between 2 and 8% by weight.
• the silicone composition X1' may comprise:
• organopolysiloxane A1′ preferably between 25 and 65% by weight, relative to the total weight of the silicone composition X1′ crosslinkable by irradiation and
• organopolysiloxane A2′ between 0.1 and 10% by weight of organopolysiloxane A2′, preferably between 1 and 8% by weight, relative to the total weight of the silicone composition X1′ crosslinkable by irradiation.
• the proportion of organopolysiloxane A2 or A2′ relative to the organopolysiloxane A1 or A1′ can be expressed by a mass ratio A2:A1 or A2′:A1′.
• this ratio is between 1:65 and 1:2, preferably between 1:50 and 1:3, and even more preferably between 1:40 and 1:5.
• These silicone compositions X1 and X1′ that can be crosslinked by irradiation can also also comprise an organic compound D comprising a (meth)acrylate function.
• silicone compositions X1 and X1′ crosslinkable by irradiation can also be used for the same applications as those described below for the silicone composition X crosslinkable by irradiation.
• the invention also relates to the use of the silicone composition X crosslinkable by irradiation for the preparation of silicone elastomers. These silicone elastomers can have non-stick properties against adhesives.
• the invention also relates to a process for preparing silicone elastomers, comprising a step of crosslinking a silicone composition X that can be crosslinked by irradiation.
• the crosslinking step is carried out in air or in an inert atmosphere.
• this crosslinking step is carried out under an inert atmosphere.
• the crosslinking step of the process according to the invention is carried out by UV radiation with a wavelength of between 200 nm and 450 nm, preferably under an inert atmosphere.
• the crosslinking step of the process according to the invention is carried out by exposure to an electron beam (electron beam) or to gamma rays.
• UV radiation can be emitted by doped or undoped mercury vapor lamps, the emission spectrum of which extends from 200 nm to 450 nm.
• Light sources such as light-emitting diodes, better known by the acronym “LED” (Light-Emitting Diodes) which deliver spot UV or visible light can also be used.
• the radiation is ultraviolet light with a wavelength of less than 400 nanometers. According to a preferred mode of the invention, the radiation is ultraviolet light with a wavelength greater than 200 nanometers.
• UV LED lamps are used (UV emissions at 365, 375, 385 and/or 395 nm).
• a dose of ultraviolet rays in the range from about 0.1 to about 0.5 joules is generally sufficient to induce crosslinking.
• the irradiation time can be short and is generally less than 1 second and is of the order of a few hundredths of a second for low coating thicknesses.
• the crosslinking obtained is excellent even in the absence of any heating.
• the crosslinking step is carried out at a temperature of between 10°C and 50°C, preferably between 15°C and 35°C.
• the curing speed can be adjusted in particular by the number of U.V. lamps used, by the duration of exposure to U.V. and by the distance between the composition and the U.V. lamp.
• the invention also relates to a process for preparing a coating on a support, comprising the following steps:
• composition X according to the invention without solvent can be applied using devices capable of depositing, in a uniform manner, small quantities of liquids.
• the device called "gliding Helio" comprising in particular two superposed cylinders: the role of the cylinder placed lowest, plunging into the coating tank where the compositions are, is to impregnate in one very thin layer the cylinder placed the highest, the role of the latter is then to deposit on the paper the desired quantities of the compositions with which it is impregnated, such a dosage is obtained by adjusting the respective speed of the two cylinders which rotate in direction reverse of each other.
• the crosslinking which results in a hardening of the silicone composition X, can be carried out continuously by passing the support coated with the composition through irradiation equipment which is designed to ensure that the coated support has a sufficient residence time to complete the hardening of the coating.
• the curing is carried out in the presence of the lowest possible concentration of oxygen, typically at an oxygen concentration of less than 100 ppm, and preferably less than 50 ppm.
• the curing is generally carried out in an inert atmosphere, for example nitrogen or argon.
• the exposure time required to cure the silicone composition X varies with factors such as:
• composition X deposited on the supports are variable and most often range between 0.1 and 5 g/m 2 of treated surface. These quantities depend on the nature of the supports and the anti-adherent properties sought. They are usually between 0.5 and 1.5 g/m 2 for non-porous substrates.
• This method is particularly suitable for preparing a non-stick silicone coating on a support which is a flexible support made of textile, paper, polyvinyl chloride, polyester, polypropylene, polyamide, polyethylene, polyethylene terephthalate , polyurethane or non-woven fiberglass.
• the flexible substrates coated with a non-stick silicone coating can be for example:
• the invention also relates to a coated support capable of being obtained according to the process described above.
• the support can be a flexible support made of textile, paper, polyvinyl chloride, polyester, polypropylene, polyamide, polyethylene, polyethylene terephthalate, polyurethane or nonwoven glass fibers.
• coated substrates have an anti-adhesive, water-repellent character, or allow improved surface properties such as slipperiness, resistance to staining or softness.
• Another object of the invention relates to the use of a support at least partially coated with a non-stick coating according to the invention and as defined above in the field of self-adhesive labels, strips including envelopes, graphic arts, medical care and hygiene.
• B1 MQ resin with part of the Q units comprising OH groups, with an OH function content of 2% by weight and an average molar mass of 5500 g/mol
• B2 MQ resin with part of the Q units comprising OH groups, with an OH function content of 3% by weight and an average molar mass of 6000 g/mol
• B4 MDT resin with part of the T units comprising OH groups, with an OH function content of 0.8% by weight and an average molar mass of between 1000 and 6000 g/mol.
• Organic compound D D1 hexanediol diacrylate
• D2 tripropylene glycol diacrylate
• D3 Trimethylolpropane triacrylate
• the resins are diluted in organic solvents, such as toluene, a solvent exchange with the organopolysiloxane A1 is first carried out. The organic solvent is then evaporated, then the other components are added.
• organic solvents such as toluene
• a premix according to the invention is prepared. Since the resins are diluted in organic solvents, of the toluene type, a solvent exchange with the organic compound D is first carried out. The organic solvent is then evaporated and the mixture is diluted in organopolysiloxane A1 to form the premix. The other components are then added to the premix to form the composition.
• X-ray fluorescence of silicon (Lab-X 3000 from Oxford).
• An X-ray tube excites the electronic shell of silicon atoms, which causes an emission of X-rays proportional to the amount of excited silicon. This value or number strokes is converted by calculation (using the calibration line) into quantity of silicone.
• Smear Qualitative control of surface polymerization by the finger mark method which consists of:
• the exfoliation corresponds to the appearance of a fine white powder or small balls which roll under the finger.
• the assessment is qualitative. We quantify the gumming with the following notations:
• the score corresponds to the number of round trips (from 1 to 10) from which a scrub appears.
• Tensile tests are carried out in order to determine the detachment forces before and after aging as well as the subsequent adhesion values. These tests are described below.
• Fm2 Average tape detachment force after contact for 20 h with silicone support
• Fm1 Average tape detachment force without contact with silicone support.
• the peel force measurements were carried out with the standard adhesives TESA 7475 and TESA 7476.
• the specimens of the multilayer article (adhesive in contact with the silicone surface) were kept for 1 day at 23° C. day at 70°C and 7 days at 40°C under the pressure conditions required according to the FINAT 10 test, then tested at low peel speed according to the FINAT 3 (FTM 3) test known to those skilled in the art (Release - Finat 3 in the tables), or at high peel speed according to the FINAT 4 test at room temperature (RT) or at 40°C (Release - Finat 4).
• FTM 3 FINAT 3
• RT room temperature
• 40°C Release - Finat 4
• the peel force is expressed in cN/inch and is measured using a dynamometer, after pressurizing the samples either at ambient temperature (23° C.) or at higher temperature for tests of accelerated aging (generally 70°C).
• Noise-zipping Perception of separation at the force oscillation parameter: noisy, zipped (as opposed to "smooth”). Silent, jerk-free separation is desired.
• compositions according to the invention comprising a resin B and an organic compound D comprising an acrylate function make it possible to obtain coatings having peeling forces stable with aging (examples 3 to 6 and 16).
• the compositions according to the invention are more stable in terms of high-speed pulling and give better results in terms of noise-zipping than the comparative composition without resin (eg comp. 2).
• Examples 7 to 10 make it possible to obtain coatings having peel strengths that are as stable on aging as the compositions without resin (Comparative Example 1-2).
• these results show that it is possible to modify the detachment forces of the coating obtained by modifying the resin content in the composition (examples 7 to 10), and that it is possible to use different radical photoinitiators C (e.g. 10 and 11).
• the compositions according to the invention give better results in terms of noise-zipping than the comparative composition without resin (eg comp. 2).
• Table 7 show that it is possible to modify the peeling forces of the coating obtained by modifying the resin content in the composition (examples 12-13 and 14-15), and by modifying the quantity of acrylate having a low molar content of acrylate (compound A2, cf. examples 12-13 vs. 14-15).
• the compositions according to the invention give better results in terms of zipping than the comparative composition without resin (eg comp. 2).

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• 2022
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