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
• • 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
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • 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
  • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/07—Aldehydes; Ketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2312/00—Crosslinking
  • C08L2312/06—Crosslinking by radiation

Definitions

• the subject of the present invention is the use of a type II photoinitiator system for the radical crosslinking of silicone compositions, in particular of acrylic silicone compositions.
• plastic films as support materials for the coating of silicone coatings in order to create release coatings requires appropriate 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 furnaces of the silicone layer under the combined effect of the tensile forces and the temperature imposed on the films.
• the crosslinking technology for functional silicone oils under ultraviolet (UV) radiation makes it possible to dispense with the use of high temperatures and thus to crosslink non-stick layers without impacting the supports. In addition, this technology has the advantage of achieving high productivity without being energy-consuming and without using solvents.
• Plastic substrates are materials of choice for many applications and their use is constantly growing. Also, an effort of research and innovations is essential in the field of the crosslinking under UV of thin films of silicone.
• the silicone compositions are generally crosslinked under UV or visible radiation emitted by doped or non-doped mercury vapor lamps whose emission spectrum 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 a specific UV or visible light can also be used.
• the crosslinking under irradiation is promoted by a photoinitiator molecule.
• a large literature describes photoinitiators and their uses.
• type I photoinitiators In the field of the radical polymerization of acrylic silicone compositions, the photoinitiator molecules commonly used are so-called type I photoinitiators. Under irradiation, these molecules split and produce free radicals. These radicals induce the polymerization initiation reaction which results in the curing of the compositions. Many efforts have been made to ensure that Type I photoinitiators have characteristics allowing their use in acrylic silicone formulations to obtain release coatings.
• the term "type I photoinitiators” means compounds well known to those skilled in the art, capable of generating free radical initiators of polymerization under UV excitation by intramolecular homolytic fragmentation.
• type II photoinitiator systems including a radical photoinitiator and a co-initiator.
• the photoinitiators used are capable of generating polymerization initiator free radicals by reaction with another compound called co-initiator, said reaction causing the transfer of a hydrogen from the co-initiator to said photoinitiator.
• the photoinitiators used in type II photoinitiator systems are referred to as "type II photoinitiators".
• the object of the present invention is to provide a radically polymerizable or crosslinkable silicone composition comprising a type II photoinitiator system suitable for crosslinking silicone compositions, in particular by exposure to radiation.
• the present invention also aims to provide a radically polymerizable or crosslinkable silicone composition comprising a type II photoinitiator system adapted for the crosslinking of silicone compositions, in particular by exposure to radiation, miscible in the silicone composition and having good properties. absorption of light radiation at the wavelengths considered for the application, namely between 200 nm and 450 nm.
• the present invention also aims to provide a method for preparing a film or a coating on a substrate from the radical-polymerizable silicone composition according to the invention.
• the present invention also aims to provide a substrate coated with a film or a coating obtained from the radical-polymerizable silicone composition according to the invention.
• Another object of the present invention is to provide silicone compositions which make it possible to obtain non-stick coatings which crosslink under radiation, and in particular under UV radiation, from organopolysiloxanes.
• organopolysiloxanes comprising (meth) acrylate groups, especially (meth) acrylic ester groups or epoxy acrylates or polyether acrylates.
• the present invention relates to a silicone composition C crosslinkable by exposure to a wavelength of radiation between 200 nm and
• At least one radical photoinitiator A at least one radical photoinitiator A
• At least one co-initiator B chosen from compounds comprising at least one hydrogen atom bonded to a silicon atom;
• At least one organopolysiloxane D comprising at least one group
• co-initiator B comprises at least 0.05 moles of Si-H functional groups per 100 g of co-initiator B.
• a hydrogen atom bonded to a silicon atom is understood to mean an Si function -H or a Si-H bond.
• the present invention is therefore based on the use of a specific type II photoinitiator system comprising the combination of a radical photoinitiator A and a co-initiator B chosen from compounds comprising at least one hydrogen atom bound to a silicon atom.
• crosslinking is understood to mean the hardening of the composition by polymerization reactions of the meth (acrylate) functions.
• crosslinkable silicone composition by exposure to radiation means a composition comprising at least one organopolysiloxane capable of curing by exposure to radiation of wavelength between 200 nm and 450 nm, in particular UV radiation.
• the composition comprises a type II photoinitiator system which, under the effect of the absorption of the incident light energy, releases free radicals into the medium.
• These radicals act as initiators of radical polymerization of (meth) acrylic functions. Since it is the motor of the hardening of the composition, the photoinitiator system is an essential key of this application.
• the type II photoinitiator system according to the invention comprising a photoinitiator molecule A in combination with a co-initiator molecule B comprising at least one hydrogen atom bonded to a silicon atom, introduced into a silicone composition C, comprising at least an organopolysiloxane D with (meth) acrylic functions makes it possible to obtain crosslinked films under irradiation, in particular with anti-adhesion properties.
• the co-initiator B used is a compound comprising at least one hydrogen atom bonded to a silicon atom.
• the co-initiator B is preferably an organosilicon compound comprising at least one hydrogen atom bonded to a silicon atom.
• the silicone compositions C according to the invention comprise a mixture of co-initiators.
• organosilicon compounds comprising at least one hydrogen atom bonded to a silicon atom
• the groups R can also represent radicals -SiR ' 3 , the groups R', which are identical or different, being chosen from the radicals (CrC 10 ) alkyls and the radicals (C 6 -C 10 ) aryls.
• R may represent a phenyl group or an alkyl group, especially methyl, ethyl or octadecyl.
• R can also represent a group -SiMe 3 .
• silanes S that may be used as co-initiators B according to the invention, mention may be made of 2-triethylsilane, dimethylphenylsilane, diphenylsilane, triphenylsilane and tris (trimethylsilyl) silane.
• silanes S mention may also be made of N, N-diethyl-1,1-dimethylsilylamine, 1,1,3,3-tetramethyldisilazane,
• the co-initiator B according to the invention is chosen from the group consisting of tris (trimethylsilyl) silane (TTMSS), triphenylsilane (TPSi) and octadecylsilane (OctaSi).
• the co-initiator B according to the invention comprises at least one siloxane bond and at least one hydrogen atom bonded to a silicon atom.
• siloxane bond is meant a ⁇ Si-O-Si ⁇ bond.
• the co-initiator B according to the invention is chosen from organohydrogenpolysiloxanes H.
• the organohydrogenpolysiloxane H comprises at least two, and preferably three, hydrogen atoms each bonded to different silicon atoms.
• the organohydrogenpolysiloxane H comprises:
• L represents a monovalent radical different from a hydrogen atom
• H represents the hydrogen atom
• d and e represent integers, d being 1 or 2, e being 0, 1 or 2 and (d + e) being 1, 2 or 3;
• f represents an integer equal to 0, 1, 2 or 3.
• L may preferably represent a monovalent radical selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, optionally substituted by at least one atom halogen, and a aryl group. L may advantageously represent a monovalent radical chosen from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl. Examples of units of formula (H1) are as follows:
• the organohydrogenpolysiloxane H can have a linear, branched, cyclic or network structure.
• linear organohydrogenpolysiloxanes these can essentially consist of:
• siloxyl units "M” selected from units of formulas HL 2 Si0 1/2 (also called pattern M ') and L 3 Si0 2/2,
• These linear organohydrogenpolysiloxanes H may be oils having a dynamic viscosity at 25 ° C of between 1 mPa.s and 100 000 mPa.s, preferably between 1 mPa.s and 5000 mPa.s, and even more preferably between 1 mPa. s and 2,000 mPa.s.
• cyclic organohydrogenpolysiloxanes may consist of "D" siloxyl units selected from the units of formulas HLSiO 2/2 and L 2 SiO 2/2 , or of siloxyl units of formula HLSiO 2 / 2 only.
• the units of formula L 2 SiO 2/2 may especially be dialkylsiloxy or alkylarylsiloxy.
• These cyclic organohydrogenpolysiloxanes may have a dynamic viscosity at 25.degree. C. of between 1 mPa.s and 5000 mPa.s.
• organohydrogenpolysiloxane H examples are:
• polysimethylsiloxane-co-hydrogenomethylsiloxane with hydrogenodimethylsilyl ends
• polyhydromethylsiloxanes with trimethylsilyl ends
• cyclic hydrogen methylpolysiloxanes
• organohydrogenpolysiloxanes H these may furthermore comprise:
• siloxyl "T" units chosen from the units of formulas HSi0 3/2 and LSi0 3/2 ;
• co-initiator B comprises at least 0.08 mol of Si-H functions per 100 g of co-initiator B, more preferably between 0.08 mol and 2.5 mol of Si-H functions for 100 g co-initiator B, and even more preferably between 0.08 mole and 1.8 moles, of Si-H functions per 100 g co-initiator B.
• the co-initiator B is an organohydrogenpolysiloxane polymer H comprising at least 0.05 mol of Si-H functions per 100 g of polymer, preferably at least 0.08 mol of Si-H functions per 100 g. of polymer, more preferably between 0.08 mole and 2.5 moles of Si-H functions per 100 g of polymer, and still more preferably between 0.08 mole and 1.8 moles, of Si-H functions per 100 g of polymer.
• the concentration of Si-H functions is less than or equal to 0.01 mol / 100 g of composition C, preferably less than 0.006 mol / 100 g of composition C, and more preferably less than 0.005 mol / 100 g of composition C.
• the crosslinkable silicone compositions C according to the invention comprise between 0.0001 mole and 0.01 mole of Si-H functions per 100 g of composition C, especially between 0.0002 mole and 0.01 mole of functions
• Si-H per 100 g of composition C and preferably between 0.0002 mole and 0.006 mole of Si-H functions per 100 g of composition C.
• the photoinitiator used is a radical photoinitiator A.
• a radical photoinitiator A capable of being used in a type II photoinitiator system, absorbing the luminous radiations of length wavelength between 200 nm and 450 nm.
• the radical photoinitiator A is chosen from the group consisting of benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, benzoylate formate esters, camphorquinone, benzil, phenanthrenequinone , coumarines and cetocoumarines and their mixtures.
• Benzophenone derivatives are substituted benzophenones and polymeric versions of benzophenone.
• thioxanthone derivatives By thioxanthone derivatives is meant thioxanthones substituted and anthraquinone derivatives, denotes substituted anthraquinones, especially anthraquinone sulfonic acids and acrylamido-substituted anthraquinones.
• methyl benzoylformate optionally bifunctional.
• free-radical photoinitiators A mention may be made in particular of the following products: isopropylthioxanthone; benzophenone; camphorquinone; 9- xanthenone; anthraquinone; 1-4 dihydroxyanthraquinone; 2-methylanthraquinone;
• radical photoinitiators A examples include benzophenone derivatives, Esacure TZT ® products, Speedcure ® MBP Omnipol ® BP and from derivatives of thioxanthone, Irgacure the products ® 907, Omnipol ® TX and Genopol ® TX-1.
• the radical photoinitiator A according to the invention is chosen from the group consisting of: benzophenone, substituted benzophenones, thioxanthone, substituted thioxanthones, and mixtures thereof.
• R is selected from:
• a 1 represents a (C 1 -C 20 ) alkylene radical, preferably linear.
• the radical photoinitiator A is chosen from the group consisting of: benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, 2,4-dimethyl benzophenone, 4-isopropylbenzophenone and 2-trimethylsilyloxy benzophenone and mixtures thereof.
• the ratio between the number of moles of photoinitiator A and the number of moles of functions Si-H of co-initiator B is greater than or equal to 0.5, preferably between 0 , 5 and 20, and even more preferably between 1 and 10. According to a preferred embodiment, in the composition C, the ratio between the number of moles of photoinitiator A and the number of moles of Si-H functions of the co-initiator B is between 1 and 5.
• the crosslinkable silicone compositions C according to the invention comprise at least 0.0003 moles of radical photoinitiator A, per 100 g of composition C, and preferably at least 0.0005 moles of radical photoinitiator A, per 100 g of composition C.
• the mole content of radical photoinitiator A in the compositions C of the invention is between 0.0003 and 0.015 mole per 100 g of composition C, and even more preferentially between 0.0005 and 0.015 mole per 100 g of composition C.
• the crosslinkable silicone compositions C according to the invention comprise at least one organopolysiloxane D comprising at least one (meth) acrylate group.
• (meth) acrylate functional groups carried by silicone and particularly suitable for the invention mention may be made more particularly of acrylate, methacrylate and ether derivatives of (meth) acrylates and esters of (meth) acrylates linked to the chain. polysiloxane via an Si-C bond.
• the organopolysiloxane D comprises:
• R identical or different, each represent a linear or branched C 18 to C 18 alkyl group, a C 6 to C 12 aryl or aralkyl group, optionally substituted, preferably with halogen atoms, or a radical alkoxy -OR 4 with R 4 being a hydrogen atom or a hydrocarbon radical comprising from 1 to 10 carbon atoms,
• Z are monovalent radicals of formula -y- (Y ') n in which:
• Y is a linear or branched C 1 -C 18 alkylene radical optionally extended by divalent oxyalkylene or polyoxyalkylene d-C 4 radicals optionally substituted with a hydroxy radical
• ⁇ Y ' represents a monovalent alkenylcarbonyloxy radical
• R represents an alkyl group Ci-Ci 8 linear or branched, aryl or aralkyl group C 6 to C 2, optionally substituted, preferably by halogen atoms, and
• - - a is an integer equal to 0, 1, 2 or 3.
• R may advantageously represent a monovalent radical chosen from the group consisting of: methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl.
• the organopolysiloxane D can have a linear, branched, cyclic or network structure.
• linear organopolysiloxanes these can essentially consist of:
• siloxy units "D" selected from the units of formula R 2 Si0 2/2, 2/2 RZSi0 and Z 2 Si0 2/2;
• siloxy units "M” selected from units of the formulas R 3 SiO / 2, R 2 ZSiOi / 2, RZ SiO 2 / SiO 2 and Z 3/2, and
• the organopolysiloxane D has the following formula (III):
• R 1 which are identical or different, each represent a linear or branched C 18 to C 18 alkyl group, a C 6 to C 12 aryl or aralkyl group, optionally substituted, preferably with halogen atoms, or alkoxy radical -OR 4 with R 4 being a hydrogen atom or a hydrocarbon radical comprising from 1 to 10 carbon atoms,
• W represents a C 1 -C 8 linear or branched C 1 -C 8 alkylene polyvalent radical optionally extended by bivalent oxyalkylene or C 1 -C 4 polyoxyalkylene radicals optionally substituted with a hydroxyl radical,
• Y ' represents a monovalent alkenylcarbonyloxy radical
• N is equal to 1, 2 or 3
• R 2 represents the monovalent radical of formula Z and the symbols R 1 and R 3 have the same meaning as above.
• the organopolysiloxane D according to the invention has the following formula:
• x is between 1 and 1000;
• n is between 1 and 100.
• the crosslinkable silicone compositions C according to the invention may also comprise at least one additive.
• at least one additive for controlling the release force of a silicone / adhesive interface can be included in the composition which is chosen from:
• Suitable organic (meth) acrylate derivatives are epoxidized (meth) acrylates, (meth) acryloglyceropolyesters, (meth) acrylureaganes, (meth) acrylopolyethers, (meth) acrylopolyesters, and (meth) acryloacrylic compounds. More particularly preferred are trimethylolpropane triacrylate, tripropylene glycol diacrylate and pentaerythritol tetraacrylate. According to a preferred variant of the invention, the additive used is a silicone with (meth) acrylate function (s).
• (meth) acrylate functional groups carried by silicone and particularly suitable for the invention mention may be made more particularly of acrylate, methacrylate and meth (meth) acrylate derivatives and meth (acrylate) esters linked to the chain. polysiloxane via an Si-C bond.
• Such acrylate derivatives are in particular described in patents EP 0 281 718, FR 2 632 960 and EP 0 940 458.
• additives such as thiols or aromatic amines can be added to accelerate the crosslinking of the composition.
• the composition C does not include platinum.
• the present invention also relates to the use of the composition C according to the invention, for the preparation of silicone films with anti-adherent properties.
• compositions C as defined above are used, in which the ratio between the number of moles of photoinitiator A and the number of moles of Si-H functions of co-initiator B is included. between 0.5 and 20, preferably between 1 and 5, said co-initiator B preferably comprising at least 0.08 mol, preferably between 0.1 mol and 2.5 mol, of Si-H functions per 100 g.
• the present invention also relates to a silicone elastomer obtained by crosslinking a crosslinkable composition C as defined above.
• the present invention also relates to a process for preparing silicone films with anti-adhesive properties, comprising a step of crosslinking a crosslinkable composition C as defined above.
• compositions C as defined above, in which the ratio between the number of moles of radical photoinitiator A and the number of moles of Si-H functions of the co-initiator, are used.
• B is between 0.5 and 20, preferably between 1 and 5, said co-initiator B preferably comprising at least 0.08 mol, preferably between 0.1 mol and 2.5 mol, of Si-H functions for 100 g of co-initiator B.
• the crosslinking step is carried out under air or under 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 radiation with a wavelength of between 200 nm and 450 nm, preferably under an inert atmosphere.
• the present invention also relates to a process for preparing a coating on a substrate, comprising the following steps:
• the UV radiation can be emitted by doped or non-doped mercury vapor lamps whose emission spectrum 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 a specific UV or visible light can also be used.
• the radiation is ultraviolet light with a wavelength of less than 400 nanometers.
• the radiation is ultraviolet light having a wavelength greater than 200 nanometers.
• 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 the 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.
• composition C according to the invention without solvent that is to say undiluted, can be applied using devices able to deposit, in a uniform manner, small amounts of liquid.
• the device called “sliding helio" comprising in particular two superimposed cylinders: the role of the lowest placed cylinder, immersed in the coating tank where the compositions are located, is to impregnate into one very thin layer the cylinder placed highest, the role of the latter is then to deposit on the paper the desired quantities of the compositions which it is impregnated, such a dosage is obtained by adjusting the respective speed of the two cylinders which rotate in direction reverse one another.
• composition C deposited on the supports are variable and generally range from 0.1 to 5 g / m 2 of treated surface. These amounts depend on the nature of the supports and the desired anti-adherent properties. They are most often between 0.5 and 1.5 g / m 2 for non-porous supports.
• This method is particularly suitable for preparing a non-stick silicone coating on a substrate which is a flexible support in textile, paper, polyvinyl chloride, polyester, polypropylene, polyamide, polyethylene, polyethylene terephthalate, polyurethane or non-woven fiberglass.
• These coatings are particularly suitable for their use in the field of anti-adhesion.
• the present invention therefore also relates to a coated substrate capable of being obtained according to the process as defined above.
• the substrate may be a flexible support of textile, paper, polyvinyl chloride, polyester, polypropylene, polyamide, polyethylene, polyethylene terephthalate, polyurethane or nonwoven glass fibers.
• the coated substrates have an anti-adherent, water-repellent, or improved surface properties such as slipperiness, stain resistance or softness.
• Another subject of the invention relates to the following compounds (2), (4), (5), (6), (7), (7a), (9), (15), (16) and (17). :
• the invention also relates to the use of the compounds (2), (4), (5), (6), (7), (7a), (9), (15), (16) and (17) described above as radical photoinitiators, and preferably the use of compounds (2), (4), (5), (6), (7), (7a), (9), (15), (16) and (17) described above as radical photoinitiators for the crosslinking of silicone compositions.
• the mixture is filtered through Celite TM, and the filtrate is concentrated on a rotary evaporator.
• the product is then purified on a silica column with a 90/10 cyclohexane / ethyl acetate eluent.
• the product is left under vacuum for 2 days to remove traces of bromohexane.
• the product obtained is a white crystalline solid with a yield of 70.7%
• the solid hydroxide hydroxide (4 equivalents per hydroxyl function) is added to anhydrous dimethylsulfoxide (DMSO) (2mL per mmol of hydroxyl function). After stirring for 5 minutes, 5 mmol of 4-hydroxybenzophenone and the Different halogenated compounds for each compound (2 equivalents per hydroxyl function) are added dropwise to the reaction mixture. The mixture is then left overnight at room temperature with stirring and under argon. The mixture is then added with 20 ml of water and extracted three times with dichloromethane (20 ml per extraction). The organic phases are then washed five times with water (10 ml per wash). The organic phase is dried over MgSO4. The solvent is then evaporated on a rotary evaporator and then under a pallet pump vacuum.
• DMSO dimethylsulfoxide
• the compound (5) was obtained from 4-hydroxybenzophenone and bromodecane, with a yield of 89%;
• the compound (6) was obtained from 4-hydroxybenzophenone and bromododecane, with a yield of 71%;
• the compound (7) was obtained from 4-hydroxybenzophenone and 1,5-dibromopentane, with a yield of 63%;
• reaction medium is supplemented with 10 ml of water and extracted three times with diethyl ether (10 ml by extraction).
• diethyl ether 10 ml by extraction.
• the combined ethereal phases are then washed with water and then dried over MgSO 4 .
• the solvent is evaporated on a rotary evaporator and then under a pallet pump vacuum.
• This compound was obtained with a yield of 20% from 5 mmol of 4-hydroxybenzophenone.
• reaction medium is extracted with CH 2 Cl 2 and then washed with 1 N of HCl, water and brine before being dried over anhydrous magnesium sulphate.
• the organic phase is then concentrated on a rotary evaporator.
• the product obtained is then purified by column of silica with a 90/10 cyclohexane ether eluent. The yield is 65%.
• Step 2 Synthesis of BP-0 Hexa-Acrylate
• step 1 In a 100 mL single-neck flask, introduce 8.26 mmol of 4-hydroxybenzophenone in 30 mL of acetone with 12 mmol of pure K 2 CO 3 . To the mixture, 8.20 mmol of Br-Hex-acrylate (step 1) is added with stirring. The mixture is brought to 60 ° C with stirring for 24 hours.
• reaction When the reaction is complete, 100 ml of water are introduced. The reaction mixture is then extracted with 3 times 40 ml of dichloromethane and then washed with water. The organic phase is then dried over sodium sulfate before being evaporated.
• Compounds S1, S2 and S3 are silanes.
• the compounds H1 to H10 are linear methylhydrogensiloxanes in which the Si-H functions can be found in the silicone chain, at the end of the silicone chain.
• Compound H1 1 is a resin comprising siloxyl units "Q” of formula Si0 4/2 and siloxyl units "M” of formula H (CH 3 ) 2 SiOi / 2 .
• Acrylic silicones (Table 3)
• the acrylic silicones used A1 and A2 have the above-mentioned formula (III) in which:
• This example relates to the use of the H3 oil (see Table 2 above) as a co-initiator in combination with the benzophenone photoinitiator in order to initiate the polymerization of acrylic silicones (A1 and A2, described in Table 3 below). -above).
• Irgacure ® 1 173 (CAS nr: 7473-98-5) with the following structure:
• the preparations are carried out as follows: The benzophenone was weighed and introduced into the A1 or A2 resin, and the mixture was stirred until a homogeneous product (-30 minutes) was obtained.
• organohydrogenpolysiloxane H3 was introduced.
• the preparations thus obtained were then crosslinked under UV radiation with a Mercure-Xenon lamp with a reflector at 365 nm.
• the power of the UV lamp was set at 510 mW.cm "2 .
• the manipulations were carried out under air or laminate in order to overcome any action of inhibition of the reactive species with oxygen.
• the manipulations are made of laminate, the formulation is placed between two sheets of polypropylene, then between two pellets of CaF 2 .
• RT-FTIR Real-Time Fourier Transform Infra-Red
• Table 4 expresses mixtures made on a basis of 2 g of A1 or A2 resin. The data are expressed in% weight. These manipulations were carried out in laminate.
• the combination of the two elements to constitute the type II photoinitiator system according to the invention is effective (test 5 vs 3C & 4C and test 10 vs 8C & 9C).
• Table 5 expresses mixtures made on a basis of 2 g of A1 or A2 resin. The data are expressed in% weight. These manipulations were performed under air.
• Examples denoted C correspond to comparative examples and Examples 12 and 14 correspond to compositions according to the invention.
• Example 1 is reproduced by replacing the benzophenone with a benzophenone derivative or an isopropylthioxanthone derivative.
• the co-initiator is H1 oil (see Table 2).
• the photoinitiators tested are BP-OH, BP-OMe, BP-OHexa, BP-OTMeSi, TX-TMVSi, BP-Acrylate, BP-OHexa-Acrylate, BP-O-CO-Neodeca and BP-0-C 6 H 12. -0- BP whose structures are described in Table 1.
• Example 2 Polymerization tests were carried out under the same conditions as those of Example 1, modifying the nature of the co-initiator.
• the organohydrogenpolysiloxane oil was replaced by a silane selected from S1, S2 or S3 described in Table 2.
• the photoinitiator used is benzophenone (BP), as in example 1, or isopropylthioxanthone (ITX).
• the silanes tested also allow, in combination with benzophenone or with isoproprylthioxanthone, to polymerize the acrylic silicones tested.
• silicone compositions according to the invention were coated and crosslinked by exposure to radiation on flexible supports. The anti-adhesion performance of the supports thus obtained were evaluated.
• the formulations are prepared by mixing the various components described in Examples 5 to 9, and then coated with a Rotomec coating pilot on different supports under the conditions described in the various examples.
• Smear Qualitative control of surface polymerization by the fingerprint method which consists of:
• the scrub is the appearance of a fine white powder or small balls that roll under the finger.
• the assessment is qualitative.
• the scrub is quantified with the following notations:
• the note is the number of round trips (from 1 to 10) from which a scrub appears.
• Dewetting Assessment of the degree of polymerization of the silicone layer by evaluating the transfer of silicone onto an adhesive contacted with the coating using a standard surface tensioning ink. The method is as follows:
• Extractables Measurement of the amount of silicone that is not grafted to the network formed during the polymerization. These silicones are extracted from the film by immersing sample from the machine exit in the MIBK for a minimum of 24 hours. This is measured by flame absorption spectroscopy.
• TESA 7475 adhesive adhesion preservative verification measure having been in contact with the silicone coating according to the FINAT 11 test (FTM 11) known to those skilled in the art.
• FTM 11 FINAT 11 test
• the reference specimen is PET and the adhesives remained in contact with the silicone surface to be tested 1 day at 70 ° C. and 7 days at 70 ° C.
• Fm2 average tensile strength tape after contact 20 h with silicone support
• Loop-tack The loop-tack test consists of determining the force required to separate, at 300 mm / min, a loop of adhesive (TESA 7475) placed in contact and without pressure with a standard material. The ratio of the result between a clean adhesive and an adhesive complexed for 1 day at 23 ° C. makes it possible to assess the loss of adhesiveness according to the FINAT 9 test (FTM9) known to those skilled in the art.
• the peel force is expressed in cN / inch and is measured with a dynamometer, after pressurizing the samples either at room temperature (23 ° C) or at a higher temperature for accelerated aging tests ( in general 70 ° C).
• benzophenone was used as photoinitiator and, as co-initiator, compound H9 (see Table 2).
• the different formulations are described in the following Table 1 1.
• a type I photoinitiator system which is ethyl (1, 4,6-triethylbenzoyl) phenylphosphinate (PA I) was also tested.
• the coating medium is LDPE of 87 g / m 2 .
• the coating is carried out on the face out of the support.
• the target deposit is between 0.8 and 1.0 g / m 2 .
• the molar content of Si-H in the coating composition was varied in the coating composition the molar content of Si-H in the coating composition and the molar content of photoinitiator.
• 3 molar concentrations of different Si-H functions were used (0.001 - 0.002 and 0.003 mol / 100 g of silicone composition) and, for each, 4 molar concentrations of photoinitiator (0.0017 - 0.0033 - 0.0064 and 0.0129 mol / 100g of silicone composition), with as a control the photoinitiator system type I PA I.
• the photoinitiator used is the Genocure® LBP.
• the coating medium is LDPE of 23 g / m 2 of the coating is carried out on its face OUT.
• the target deposit is between 0.8 and 1.0 g / m 2 .
• EXAMPLE 6 Influence of the Si-H Function Content of the Co-Initiators
• the tests were carried out at a constant concentration of Si-H functions in the starting composition but using organohydrogenpolysiloxane oils with Si-H functional content. variable.
• the oils H4, H9, H8 and H5 were used (see Table 2).
• a constant concentration of Genocure® LBP photoinitiator was used. These formulations were tested at low coating speed and high lamp power.
• the coating medium is LDPE of 23 g / m 2 .
• the coating is carried out on its face OUT.
• the target deposit is between 0.8 and 1.0 g / m 2 (0.90 ⁇ 0.10).
• Table 1 1 summarizes the compositions used and the results obtained following the aforementioned tests.
• the H8 (Ex 03) oil with an Si-H function content of 0.0646 mol / 100 g has a higher extractability level of 24% than those obtained with the co-initiators H4 and H9 (Ex 01 and 02) and release values increase sharply after 1 and 7 days at 70 ° C.
• This example therefore shows that it is preferable to use as co-initiator an organohydrogenpolysiloxane comprising at least 0.05 mole of Si-H functions per 100 g, and preferably at least 0.08 mole of Si-H functions per 100 boy Wut.
• This example concerns the study of the impact on the polymerization of the nature of the co-initiators and in particular the position of the Si-H units (end of chain, in the chain or both).
• the coating medium is white LDPE GLD3 28 g / m 2.
• the coating is carried out on its face OUT.
• the target deposit is between 0.8 g / m 2 and 1.0 g / m 2 .
• Genocure® LBP As a photoinitiator, Genocure® LBP was used (Table 1). The co-initiator is selected from different oils or resins with different structures and content of Si-H functions (see Table 2).
• the Smear is rated A-B to A for the entire series.
• the rub-off is between 9 and 10.
• the dewetting is 10.
• the polymerization of the coated compositions is therefore good for all the formulations and is not significantly affected by the nature of the co-initiator used nor by the positioning of the patterns.
• Example 8 Coating Tests with a Mixture of A1 and A2
• the coating medium is PET 30,01 / 30 Transparent 30 g / m 2 of TORAY.
• the coating is carried out on its face OUT.
• the target deposit is between 0.8 g / m 2 and 1.0 g / m 2 .
• Table 13 summarizes the different compositions used as well as the results obtained following the aforementioned tests.
• the coating medium is LDPE.
• the coating is carried out on its face OUT.
• the target deposit is between 0.8 g / m 2 and 1.0 g / m 2 .
• modified benzophenones were used as photoinitiators and, as a co-initiator, compound H9 (see Table 2).
• the different formulations are described in the following table.
• the benzophenone Genocure LBP and a type I photoinitiator system which is ethyl (1, 4,6-triethylbenzoyl) phenylphosphinate (PA I) were also tested.
• the coating medium is glassine.
• the coating is carried out on the face out of the support.
• the target deposit is between 0.8 and 1.0 g / m 2 .

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