Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
  • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
  • B29C59/005—Surface shaping of articles, e.g. embossing; Apparatus therefor characterised by the choice of material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
  • B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/12—Chemical modification
  • C08J7/123—Treatment by wave energy or particle radiation
• • C—CHEMISTRY; METALLURGY
  • 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
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
  • B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
  • B29C2059/145—Atmospheric plasma
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2083/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2383/04—Polysiloxanes

Definitions

• the field of the invention is that of articles comprising elements of silicone elastomer crosslinked by polyaddition of ⁇ Si-H units on ⁇ Si-alkenyl (preferably ⁇ Si-Vinyl) units belonging to polyorganosiloxanes (POS).
• POS polyorganosiloxanes
• liquid silicone preparations which can be in particular: • POS compositions which can be vulcanized by polyaddition, at room temperature (with possible activation at higher temperature) two-component (RTV II) or even single-component (RTV), having advantageously a viscosity at 25 ° C at most equal to 200 Pa.s, preferably between 10 and 100 Pa.s; • POS compositions vulcanizable by polyaddition, with heat, bicomponents or monocomponents, called LSR and advantageously having a viscosity at 25 ° C of between 100 and 1,000 Pa.s; • POS compositions vulcanizable by polyaddition, with heat (EVC), advantageously having a viscosity at 25 ° C at least equal to 1,000 Pa.s, preferably between 1,000 Pa.s and 10,000 Pa.s.
• POS compositions which can be vulcanized by polyaddition, at room temperature (with possible activation at higher temperature) two-component (RTV II) or even single-component (R
• Bonding is also very useful for assembling large technical molded silicone parts, which cannot be obtained in a single casting, or even for repairing damaged molds or parts.
• the patent US-B-6 265 690 discloses an apparatus for the treatment of plasma surfaces of materials constituted by synthetic resins and to which are intended to be applied liquids formed by adhesives or printing inks.
• the plasma surface treatment delivered by this device aims to improve the surface "wettability" of the resins concerned, by modifying the surface structure so as to ultimately increase the surface tension.
• the plasma spraying device according to this patent is presented as allowing rapid and efficient continuous surface treatment on large surfaces.
• This device comprises a rotary head comprising one or more plasma nozzles eccentric with respect to the axis of rotation of the head and each capable of generating a plasma jet of axis parallel to this axis of rotation.
• Treat ® is described as a process for producing a homogeneous and potential-free atmospheric plasma jet (connected to earth).
• one of the essential objectives of the present invention is to propose an advantageous solution to the problem of the low surface energy ("wettability") of the silicones, and in particular of the silicones constituted of POS crosslinked by polyaddition of ⁇ Si-H patterns on ⁇ Si-alkenyl patterns.
• Another essential objective of the invention is to provide a method of surface treatment of an article comprising crosslinked silicone, so as to facilitate the application of liquids, and in particular of adhesives on the treated silicone surface.
• Another essential objective of the invention is to provide a process for producing a crosslinked silicone article treated to increase its surface tension, without harming the mechanical properties and / or the water-repellency properties and / or the properties of oleophobia and / or the aesthetic qualities of the crosslinked silicone elements.
• Another essential objective of the present invention is to provide a method of assembling articles comprising crosslinked and pretreated silicone to increase the surface tension of the silicone and facilitate the application of the adhesive.
• Another objective targeted by the inventors was the development of a composite constituted by a flexible support (in particular fibrous, eg textile or polymer) coated with a multilayer coating of crosslinked silicone elastomer, the surface of which is provided with a large surface tension and therefore good wettability with respect to liquids such as glues or paints, as well as a high adhesion force (measured according to a bonding test T), this coating also having good cohesion, good mechanical properties, good wrinkle resistance, the usual water repellency / oleophobization properties of silicones and a good external appearance.
• the present invention which relates, first of all, to a method of surface treatment of an article comprising crosslinked silicone preferably chosen from polyorganosiloxanes (POS) crosslinked by polyaddition of ⁇ units Si-H on ⁇ Si-alkenyl units (preferably ⁇ Si-vinyl), in a silicone preparation comprising:
• cold plasma is meant in the sense of the invention low temperatures at the level of contact with the substrate, in particular less than 100 ° C. and, in practice, less than 50 ° C.
• thermoplastic, thermosetting materials, elastomers, composites, ceramics, metals This surface modification is presented as allowing cleaning, an increase in surface tension, electrostatic neutralization, the creation of functional groups and an increase in attachment sites.
• the plasma used is a homogeneous atmospheric plasma, that is to say continuous over time and regular over the surface. It is also a high intensity plasma.
• the plasma surface treatment method is carried out continuously using a plasma spraying apparatus comprising a rotary head comprising one or more plasma nozzles, offset from the to the axis of rotation and each capable of generating a plasma jet of axis parallel to this axis of rotation.
• the mode of implementation preferred above-mentioned include technology Plasma Treat ® marketed by the company of the same name.
• the present invention relates to a process for producing a crosslinked silicone item and treated with plasma as indicated above, this process being characterized in that it comprises the following essential steps:
• Such a method for producing articles of crosslinked plasma-treated silicone can advantageously be declined in a method of coating a single or multilayer silicone on any support, for example a fabric, a nonwoven or a polymer film.
• the article comprising silicone includes a support - preferably flexible - and one or more crosslinked silicone elements forming a mono- or multilayer coating adhering to the support.
• steps (I) and (II) are part of a discontinuous molding process.
• steps (I) and (II) are part of a discontinuous molding process.
• These molded objects can be technical parts intended or not to be assembled to form larger assemblies.
• the latter can also correspond to a silicone mold produced in several stages, or even to a repair of a used mold requiring the assembly of repair parts.
• the surface treatment process with crosslinked silicone plasma is implemented so that the quantity of plasma received by the surface in silicone is such that the surface energy of said surface is greater than 30 mN / m, preferably between 30 and more than 70 rnN / m.
• the intensity of the plasma applied to the crosslinked silicone surface can be adjusted by a person skilled in the art, who can influence the distance between the plasma torch and the surface to be treated, as well as the speed of travel and / or on the exposure time of the surface to be treated.
• the method according to the invention is not limited to a single repetition (IV) of the crosslinking steps (II) of the silicone compositions in order to obtain composites (I) having only two layers of silicone elastomer. It is indeed understood that the application and crosslinking steps (I) and (II) can be repeated as many times as necessary, to obtain the number of layers of silicone elastomer desired, taking care to performs the plasma treatment (III) at least on all of the intermediate crosslinked layers, that is to say up to the penultimate layer, on which the upper outer layer is applied.
• the present invention also relates to a method of assembling articles comprising crosslinked silicone, preferably by polyaddition of ⁇ Si-H units on ⁇ Si-alkenyl units (preferably ⁇ Si-Vinyl), characterized in that at at least one of the articles to be assembled comes from one of the methods defined above and in that liquid glue is used which is applied to at least part of the treated silicone surfaces.
• the POSs (-A-) chosen have siloxyl units of formula:
• the symbols W which are identical or different, each represent an alkenyl group, preferably a C 2 -C 6 alkenyl; - the symbols Z, which are identical or different, each represent a non-hydrolysable monovalent hydrocarbon group, free from any unfavorable action on the activity of the catalyst, optionally halogenated, and preferably chosen from alkyl groups having from 1 to 8 carbon atoms included , as well as among the aryl groups, - a is 1 or 2, b is 0, 1 or 2 and a + b is between 1 and 3,
• the POSs (-A-) can be very predominantly formed of units of formula (1) or can additionally contain units of formula (2). Likewise, they can have a linear structure. Their degree of polymerization is preferably between 2 and 5000.
• Z is generally chosen from methyl, ethyl and phenyl radicals, at least 60 mol% of the radicals Z being methyl radicals.
• siloxyl units of formula (1) are the vinyldimethylsiloxane unit, the vinylphenylmethylsiloxane unit and the vinylsiloxane unit.
• siloxyl units of formula (2) are the Si ⁇ 4 / 2, dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, methylsiloxane and phenylsiloxane units.
• POS (A) examples are dimethylpolysiloxanes with dimethylvinylsilyl ends, methylvinyldimethylpolysiloxane copolymers with trimethylsilyl ends, methylvinyldimethylpolysiloxane copolymers with dimethylvinylsilyl ends, cyclic methylvinylpolysiloxanes.
• the dynamic viscosity ⁇ d of this POS (-A-) is between 0.01 and 500 Pa.s, preferably between 0.01 and 300 Pa.s.
• the POS (-A-) comprises at least 98% of siloxyl units D: -R 2 Si0 2/2 with R corresponding to the same definition as Z, this percentage corresponding to a number of units per 100 silicon atoms .
• the alkenyl units W are vinyls carried by siloxy units D and optionally M and / or T.
• POS (-B-) the preferred are chosen from those comprising siloxyl units of formula:
• the symbols L which are identical or different, each represent a non-hydrolysable monovalent hydrocarbon group, free from any adverse action on the activity of the catalyst, optionally halogenated, and preferably chosen from alkyl groups having from 1 to 8 carbon atoms included , as well as among the aryl groups,
• - d is 1 or 2, e is 0, 1 or 2 and d + e has a value between 1 and 3;
• POS poly (dimethylsiloxy) (methylhydrogenosiloxy) ⁇ , ⁇ -dimethylhydrogenosiloxane.
• the POSs (-B-) can only be formed of units of formula (1) or additionally comprises units of formula (2).
• POS (-B-) can have a linear, branched, cyclic or network structure.
• the degree of polymerization is greater than or equal to 2. More generally, it is less than 100.
• the dynamic viscosity ⁇ d of this POS (-B-) is between 5 and 1000 mPa.s, preferably between 10 and 500 mPa.s.
• Group L has the same meaning as group Z above.
• Examples of units of formula (1) are: H (CH 3 ) 2 Si0 1/2 , HCH 3 Si0 2/2 , H (C 6 H 5 ) Si0 2/2 .
• These groups can be optionally halogenated or alternatively can be chosen from cyanoalkyl radicals.
• halogens are for example fluorine, chlorine, bromine and iodine, preferably chlorine or fluorine.
• POS (-A-) & (-B-) can consist of mixtures of different silicone oils.
• POS (-A-) & (-B-) can be: - RTVs as defined above and in the patents
• the alkenyl groups W of the POS (-A-) and / or the POS resins (-D-) are vinyl groups Vi, carried by siloxyl units D optionally M and / or T.
• POS resins (-D-) it is preferable to select them from those containing at least one alkenyl residue in its structure and having a content by weight of alkenyl group (s) of between 0.1 and 20% by weight and preferably between 0.2 and 10% by weight.
• resins are well known and commercially available branched organopolysiloxane oligomers or polymers. They are in the form of solutions, preferably siloxane. They have, in their structure, at least two different patterns chosen from those of formula
• the radicals R ′ are identical or different and are chosen from linear or branched Ci-Cg alkyl radicals, alkenyl radicals in
• C2 - C4 phenyl, trifluoro-3,3,3 propyl Mention may be made, for example: as alkyl radicals R ', methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals, and as alkenyl radicals R, vinyl radicals.
• branched organopolysiloxane oligomers or polymers mention may be made of MQ resins, MDQ resins, TD resins and MDT resins, the alkenyl functions possibly being carried by the M, D and / or T units.
• resins which are particularly suitable mention may be made of vinylized MDQ or MQ resins having a weight content of vinyl groups of between 0.2 and 10% by weight, these vinyl groups being carried by the units M and / or D.
• This structural resin is advantageously present in a concentration of between 10 and 70% by weight relative to all the constituents of the composition, preferably between 30 and 60% by weight and, more preferably still, between 40 and 60% in weight.
• the polyaddition reaction is well known to those skilled in the art. Furthermore, a catalyst must be used in this reaction. This catalyst can in particular be chosen from platinum and rhodium compounds. It is possible, in particular, to use the complexes of platinum and of an organic product described in patents US-A-3,159,601, US-A-3,159,602, US-A-3,220,972 and European patents EP- A-0 057 459, EP-A-0 188 978 and EP-A-0 190 530, the complexes of platinum and vinyl organosiloxanes described in patents US-A-3,419,593, US-A-3,715,334 , US-A-3,377,432 and US-A-3,814,730.
• the generally preferred catalyst is platinum.
• the quantity by weight of catalyst (C), calculated by weight of platinum- metal is generally between 1 and 400 ppm, preferably between 2 and 100 ppm based on the total weight of POS (-A-) & (-B-).
• the silicone elastomer preparations also comprise at least one retarder (-E-) of the addition reaction (crosslinking inhibitor), chosen from the following compounds:
• polyorganosiloxanes advantageously cyclic and substituted with at least one alkenyl, tetramethylvinyltetrasiloxane being particularly preferred,
• acetylenic alcohols (Cf. FR-B-1 528 464 and FR-A-2 372 874), which are part of the preferred hydrosilylation reaction thermal blockers, have the formula:
• - R is a linear or branched alkyl radical, or a phenyl radical
• R - R ' is H or a linear or branched alkyl radical, or a phenyl radical
• Said alcohols are preferably chosen from those having a boiling point greater than 250 C. Mention may be made, by way of examples: - 1-ethynyl-cyclohexanol 1;
• Such a retarder (-E-) is present at a rate of 3000 ppm at most, preferably at a rate of 10 to 2000 ppm relative to the total weight of the organopolysiloxanes (-A-) & (-B-).
• an adhesion promoter (-F-) can be used.
• This adhesion promoter (-F-) can for example comprise:
• R, R, R- * are hydrogenated or hydrocarbon radicals identical or different from each other and representing hydrogen, a linear branched C1-C4 alkyl or a phenyl optionally substituted by at least one C1-C3 alkyl;
• - A is a linear or branched C1 - C4 alkylene;
• R and R are the same or different radicals and represent a linear or branched C1 - C4 alkyl
• GLYMO Glycidoxypropyltimethoxysilane
• proportions of (-F.1-), (-F.2-) and (-F.3-), expressed in% by weight relative to the total of the three are preferably as follows:
• this adhesion promoter (-F-) is preferably present in an amount of 0.1 to 10%, preferably 0.5 to 5% and more preferably still 1 to 2.5% by weight relative to all the constituents of the preparation.
• the preparations used in the process according to the invention may comprise a filler (-G-) which will preferably be mineral. It can be made up of products chosen from siliceous materials (or not).
• siliceous materials they can play the role of reinforcing or semi-reinforcing filler.
• the reinforcing siliceous fillers are chosen from colloidal silicas, combustion and precipitation silica powders or a mixture thereof.
• These powders have an average particle size generally less than 0.1 ⁇ m and a BET specific surface greater than 50 m 2 / g, preferably between 100 and 300 m 2 / g.
• siliceous fillers such as diatomaceous earth or ground quartz can also be used.
• non-siliceous mineral materials can act as a semi-reinforcing or tamping mineral filler.
• these non-siliceous fillers which can be used alone or as a mixture are carbon black, titanium dioxide, aluminum oxide, hydrated alumina, expanded vermiculite, zirconia, a zirconate, unexpanded vermiculite, calcium carbonate, zinc oxide, mica, talc, iron oxide, barium sulfate and slaked lime.
• These fillers have a particle size generally between 0.01 and 300 ⁇ m and a BET surface area less than 100 mNg.
• the filler used is silica.
• the charge can be treated with the aid of an appropriate compatibilization agent and in particular hexamethyldisilazane.
• an appropriate compatibilization agent and in particular hexamethyldisilazane.
• an amount of filler of between 5 and 30, preferably between 7 and 20% by weight relative to all of the constituents of the preparation.
• these may be covering products such as, for example, pigments / dyes or stabilizers.
• the composition can, for example, consist of a part A comprising the compounds (-F.1-) and (-F.2-) while the part P2 contains the compound (-F.3 -).
• the two-component silicone elastomer composition PI - P2 In the case where a filler is used, it is advantageous to first prepare a primary pasting by mixing a mineral filler, at least part of the POS (-B-), as well as at least part of the polyorganosiloxane (-AT-).
• This pasting serves as a base to obtain, on the one hand, a PI part resulting from the mixture of the latter with the polyorganosiloxane (-B-) optionally a crosslinking inhibitor and finally the compounds (-F.1-) and (-F .2-) of the promoter (-F-).
• Part P2 is produced by mixing part of the pasting referred to above and polyorganosiloxane (-A-), catalyst (Pt) and compounds (-F.3-) of the promoter (-F-) .
• the viscosity of the parts PI and P2 and their mixture can be adjusted by varying the amounts of the constituents and by choosing the polyorganosiloxanes of different viscosity.
• one or more functional additives (H) are used, they are distributed in the parts PI and P2 according to their affinity with the content of Pl and P2.
• RTV-2 ready-to-use silicone elastomer preparation
• any suitable coating means eg doctor blade or cylinder.
• Another object of the invention consists of a composite or a crosslinked elastomeric coating capable of being obtained by one of the methods defined above, and characterized in that it has an adhesive force, measured according to a peel test T, greater than 2.7 N / cm, preferably greater than or equal to 2.8 N / cm and more preferably still between 3 and 10 N / cm.
• Figure 1 is a diagram of the device used for the peel test and showing the assembly by bonding of two silicone supports through their silicone coatings, on which succeed bands treated according to the invention and untreated control strips.
• Figure 2 is a diagram showing the peeling conditions called 180 °.
• Figure 3 shows the graph of the adhesion forces measured during the peel test.
• the textile veil is a polyamide 66 fabric of 470 dtex.
• silicone it is covered with 50 g / m 2 of silicone by means of a doctor blade; the silicone part is crosslinked by passing through an oven at 160 ° C for 2 minutes.
• the silicone composition is obtained by progressive mixing in a reactor at room temperature, of the following components in the proportions indicated below (parts by weight):
• the composite is prepared several days before the experiment.
• the treatment is carried out using an atmospheric plasma torch from the company PLASMA TREAT®. These torches operate in air; a device by rotation allows a 40 mm strip treatment.
• the torch is positioned above the support to be treated which is scrolled at an imposed speed.
• the conditions are:
• the surface energy of the supports is estimated through the capacity for spreading inks of various surface tensions. We obtain :
• the bonding performance is assessed by a quantitative peel test according to the conditions below.
• a regular layer of silicone glue of 50 g / m 2 is deposited on the silicone side of a first support then the second support is applied to this layer of glue also by its silicone side. It is ensured that the bands which correspond to the treatment carried out by the plasma torch are well superimposed according to the diagram of attached Figure 1, in which:
• the reference 1 corresponds to the first support.
• Reference 2 corresponds to the glue.
• Reference 3 corresponds to the second support.
• the DP reference corresponds to the peeling direction.
• Reference 1 corresponds to the areas treated.
• the glue used corresponds to the following formula:
• the complex tested is produced 24 hours after the treatment of the supports under the plasma torch.
• the entire complex thus prepared is cooked for
• the assembly is tested under peeling conditions T at 180 ° C. using a dynamometer whose cross member moves at the constant speed of
• the adhesion values are expressed in N / cm.
• the repeatability of the test was assessed at ⁇ 3.5%.

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