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    • 专利摘要:
    The present invention relates to: - a hot-melt adhesive composition comprising a mixture of silylated polymers, a tackifying resin and a catalyst, in particular contents, having self-adhesive properties after crosslinking with moisture, - a self-adhesive article comprising a support layer and at least one self-adhesive layer obtained after moisture crosslinking of the adhesive composition according to the invention, and - their use for bonding substrates of low surface energy, in particular plastic substrates, in particular thermoplastic substrates low surface energy.
    公开号:FR3058152A1
    申请号:FR1660509
    申请日:2016-10-28
    公开日:2018-05-04
    发明作者:David Goubard；Olivier Laferte
    申请人:Bostik SA；
    IPC主号:
    专利说明:

    ® FRENCH REPUBLIC
    NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY © Publication number:
    (to be used only for reproduction orders) (© National registration number
    058 152
    60509
    COURBEVOIE © Int Cl 8 : C 09 J 171/00 (2017.01), C 09 J 175/04, 7/35, B 32 B 7/12, 27/08
    A1 PATENT APPLICATION
    ©) Date of filing: 28.10.16.(® Priority: (© Applicant (s): BOSTIK SA - FR. ©) Date of availability of the request: 04.05.18 Bulletin 18/18. @ Inventor (s): GOUBARD DAVID and LAFERTE OLIVIER. ©) List of documents cited in the preliminary search report: See the end of this booklet (© References to other related national documents: ® Holder (s): BOSTIK SA. ©) Extension request (s): (© Agent (s): ARKEMA FRANCE Public limited company.
    SELF-ADHESIVE COMPOSITION FOR THE BONDING OF LOW-ENERGY SURFACE SUBSTRATES.
    FR 3 058 152 - A1
    a hot-melt adhesive composition comprising a mixture of silylated polymers, a tackifying resin and a catalyst, in particular contents, having self-adhesive properties after crosslinking with humidity,
    a self-adhesive article comprising a support layer and at least one self-adhesive layer obtained after crosslinking with humidity of the adhesive composition according to the invention, and
    - Their use for bonding substrates of low surface energy, in particular of plastic substrates, in particular of thermoplastic substrates of low surface energy.
    i
    Self-adhesive composition for bonding low surface energy substrates
    FIELD OF THE INVENTION
    The subject of the present invention is a hot-melt adhesive composition comprising a mixture of silylated polymers, a tackifying resin and a catalyst, in particular contents, having self-adhesive properties after crosslinking with humidity.
    The present invention also relates to a self-adhesive article, such as a self-adhesive multilayer system, comprising a support layer and at least one self-adhesive layer obtained after crosslinking with moisture of the adhesive composition according to the invention. .
    The present invention also relates to the use of the adhesive composition according to the invention in the crosslinked state and of the self-adhesive article according to the invention for the bonding of low surface energy substrates, in particular of substrates plastics, especially of low surface energy thermoplastic substrates.
    TECHNOLOGICAL BACKGROUND OF THE INVENTION
    Hot melt adhesives (often referred to as Hot Melt adhesives or HM) are solid substances at room temperature that do not contain water or solvents. They are applied in the molten state and solidify upon cooling, thus forming a seal which secures the substrates to be assembled. Certain Hot Melts are formulated so as to give the support which is coated therewith a relatively hard character and devoid of tack. Other Hot Melts provide the support with a relatively soft character and a high tack: these are PSAs which are widely used for the manufacture of self-adhesive labels; the corresponding adhesives are designated by the name of pressure-sensitive hot-melt adhesives or, in English, by that of Hot Melt Pressure Sensitive Adhesive (or HMPSA).
    Pressure sensitive adhesives (also called self-adhesive glues or even, in English, Pressure Sensitive Adhesives or PSA) are substances which give the support layer which is coated with them an immediate tackiness (or tackiness) at room temperature (often designated by the term of tack), which allows its instant adhesion to the substrate under the effect of a light and brief pressure. PSAs are widely used for the manufacture of self-adhesive labels or films which are fixed to products for the purpose of presenting information (such as bar code, name, price) and / or for decorative purposes, whether either during permanent or temporary collages. PSAs are also used in the sustainable labeling of electrical, electronic or mechanical parts, for which the information needs to be fixed over long periods of time - several years - and / or under conditions of use difficult in the presence of solvents, chemicals, natural or artificial light, radiation, with movements and deformations generated regularly or occasionally, by human or machine force. PSAs are also used for the manufacture of self-adhesive tapes of various uses. Mention may be made, for example, in addition to the transparent adhesive tape widely used in everyday life, their use in the construction of objects or buildings, in various industrial applications; such as the shaping and assembly of cardboard packaging; the protection of surfaces for painting work in construction; maintenance of electric cables in the transport industry; bonding of carpets with double-sided adhesive tapes; assembly of elements or equipment in the automobile industry, construction, the textile industry, the wood and plastics industry; the assembly of electrical or electronic devices, tools and professional or consumer equipment.
    In order to manufacture multi-layer systems and in particular self-adhesive labels and / or tapes, PSAs are often applied by continuous coating processes over the entire surface of a support layer (where appropriate printable) of large dimensions, at a rate of a quantity (generally expressed in g / m 2 ) designated below by the term grammage. The support layer consists of paper or film of a polymer material with one or more layers. The adhesive layer which covers the support layer can itself be covered with a protective non-stick layer (often called by the English name of release liner), for example consisting of a silicone film. The multilayer system obtained is generally packaged by winding in the form of large coils up to 2 m in width and 1 m in diameter, which can be stored and transported.
    These multilayer systems can be subsequently converted into self-adhesive labels applicable by the end user, by means of transformation processes which include printing of the desired informative and / or decorative elements on the printable side of the support layer, then cutting to the shape and dimensions desired. The protective non-stick layer can be easily removed without modification of the adhesive layer which remains fixed on the support layer. After separation of its protective non-stick layer, the label is applied to the surface of the substrate to be coated, either manually or using labeling machines on automated packaging lines.
    These multilayer systems can also be transformed into self-adhesive tapes by cutting and packaging in rolls of determined width and length.
    PSAs generally allow, because of their tackiness (“tack” in English) high at room temperature, a quick setting or hanging of the label and / or the self-adhesive tape on the substrate to be coated, suitable for obtaining significant industrial production rates.
    The nature of the surface of a substrate can be characterized by its surface energy. This can be quantified in a manner well known to those skilled in the art from the measurement of the contact angle and calculated according to the Owens & Wendt model.
    At a comparable surface state, a PSA composition suitable for bonding to substrates of high surface energy (or surface tension), such as glass or metals which are inorganic polar substrates, will not necessarily be suitable for bonding to low surface energy substrates, such as substrates comprising polymeric materials based on ethylene or propylene type monomers and co-monomers, substrates commonly called polyethylene (PE) and polypropylene (PP) respectively, which are non-polar organic substrates. Also in the category of low surface energy substrates, polymeric materials based on other olefinic monomers, and in general all coatings on films or objects, which prove difficult to bond with PSA.
    Low surface energy substrates, as mentioned above, are known to be difficult to bond and often require specific treatment of said surface before laminating the self-adhesive part of the label or of the adhesive tape. These treatments are well known to those skilled in the art and consist in chemically and / or physically modifying the surface of the substrate, in order to increase the surface energy and / or the roughness of said surface, and thus improve the adhesion of the adhesive. on the substrate. By way of example, the surface of the substrate can be treated by a plasma or corona treatment, abrasion or else the application to said surface to be treated of a chemical bonding agent (also called primary), in order to modify favorably the surface energy of the substrate.
    Without such surface treatments, the adhesion of the adhesive layer to a substrate of this type is often insufficient to effectively fix the label or the adhesive tape on the surface of said substrate. The effectiveness of such bonding should be considered depending on the type of application targeted. Typically, it is desirable for the adhesive seal ensuring the attachment of the two objects to have minimal resistance to one or more of the following constraints: peeling, tearing, or shearing. It is also desirable that these properties be maintained over a wide temperature range, especially when the adhesive seal (as well, therefore, as the product coated with the label and / or adhesive tape) is likely to be subjected to temperature variations, for example during transport, storage and application. It is also desirable that these advantageous properties are not degraded over time or are at least maintained for a sufficient long time, linked for example to the use or the service life of the self-adhesive article or of the product coated with said self-adhesive article. -adhesive. In certain applications, a certain rupture profile of the adhesive seal is sought with respect to the surface of the substrate. We preferentially seek a rupture of the homogeneous adhesive joint rather than jerky.
    It is for example known from patent application FR3015984 self-adhesive articles comprising a conformable support layer of the foam type, which can be obtained from adhesive compositions based on a silylated polyether or polyurethane (s) or based on a mixture of particular silylated polyethers or polyurethanes.
    These self-adhesive articles are described as being able to be applied to numerous surfaces, including plastic materials or surfaces having properties comparable to the properties of the support layer.
    However, it has been found that the adhesive compositions exemplified in these applications are not entirely satisfactory and remain to be improved, in terms of adhesive performance or bonding efficiency, on substrates with low surface energy.
    However, in certain fields of application of PSAs, it is undesirable to resort to the abovementioned surface treatments to compensate for the poor adhesive performance of the adhesive composition vis-à-vis these substrates. One of the drawbacks of these treatments is that it induces an additional step in the process of manufacturing products coated with a self-adhesive article, thus generating additional costs and constraints in the production lines of these products. In addition, these treatments by modifying the physicochemical properties of the surface of the substrates can lead to embrittlement of the surface of the substrate or even induce esthetically undesirable effects such as a loss of transparency or a modification of the surface color of the substrate. , which can be troublesome when the support layer of the self-adhesive article is for example transparent or translucent, the surface of the substrate being thus visible. These treatments can also lead to heterogeneous surfaces, poorly reproducible and not very durable bonding, which may require re-pretreatment of the substrate surface before affixing the adhesive part of the self-adhesive article.
    Thus, in recent years, new self-adhesive bonding solutions adapted to the manufacture of self-adhesive labels suitable for bonding to low surface energy substrates have appeared.
    For example, pressure-sensitive adhesive compositions based on polymers (or copolymers) of the acrylate type are known, as described in patent application EP 2310470 from 3M.
    However, the preparation of these polymers and their use in the formulation of these adhesive compositions requires the use of a large quantity of solvent which proves to be restrictive for the production of self-adhesive article since this requires an additional step of elimination of the solvent and / or, where appropriate, of the specific dedicated installations. In addition, the use of acrylic polymers also has the disadvantage of generating unpleasant odors due to the presence of residual monomers or residual solvents.
    Thus, there is a need to develop new pressure-sensitive adhesive compositions capable of sticking to any type of surface, including surfaces of low-energy surface substrates known to be difficult to stick, without having all or some of the disadvantages. of the prior art.
    It has now been found that the composition which is the subject of the present application makes it possible to stick more effectively to any type of surface, including substrates of low surface energy, regardless of its surface condition.
    In particular, the adhesive composition according to the invention has, in the crosslinked state, improved adhesive performance, in particular in terms of cohesion, on surfaces of low surface energy substrates, with a comparable surface state, compared to the compositions. pressure-sensitive adhesives of the prior art based on disilylated polymer alone (that is to say comprising no monosilylated polymer).
    In particular, the adhesive composition according to the invention has, in the crosslinked state, excellent adhesion performance for bonding surfaces of substrates based on low surface energy plastic, preferably at least comparable to the performance measured. for current self-adhesive acrylic type solutions.
    In particular, the adhesive composition according to the invention has, in the crosslinked state, an adhesive strength measured according to the 180 ° peel test of at least 3N / cm, preferably at least 3.5N / cm, more preferably at least 4N / cm, on a substrate having a surface energy less than or equal to 40mN / m, and in particular a plastic substrate of polyolefin type, such as HDPE and PP.
    In particular, the adhesive composition according to the invention also makes it possible to manufacture self-adhesive articles capable of adhering quickly and durably to such surfaces.
    In particular, the adhesive composition according to the invention is easy to implement and makes it possible to manufacture self-adhesive articles on production lines having high line speeds.
    In the present application, the expression “low surface energy substrate” means a substrate having at least one surface having a surface energy, measured at 23 ° C. at 50% relative humidity, at atmospheric pressure of 1 bar, in the air, less than or equal to 40 millinewtons per meter (mN / m) or millijoules per square meter (mJ / m 2 ). The surface energy of a substrate can be quantified in a manner well known to those skilled in the art from the measurement of the contact angle and calculated according to the Owens & Wendt model.
    The substrates of low surface energy on which the adhesive according to the invention is intended to be applied preferably have a surface energy ranging from 23 to 38 mN / m (or mJ / m 2 ), more preferably ranging from 25 to 35 mN / m.
    SUMMARY OF THE INVENTION
    The present invention therefore relates primarily to an adhesive composition comprising:
    A1) at least 4% by weight of one or more polysilylated polymers having a number average molecular mass (Mn) of at least 6,000 g / mol, and chosen from polymers comprising a main chain of polyether type and / or polyurethane and at least two hydrolyzable silylated end groups, said silylated end groups being attached to the main chain of the polymer by a urethane or ether function (said connector group), and
    A.2) at least 13% by weight of one or more monosilylated polymers having a number average molecular mass (Mn) of at least 1000 g / mol, and chosen from polymers comprising a main chain of polyether type and / or polyurethane and a hydrolyzable silylated end group, said silylated end group being attached to the main chain of the polymer by a urethane or ether function (said connector group),
    B) at least 25% by weight of one or more tackifying resin having (each) a hydroxyl number less than or equal to 100, preferably less than or equal to 50, and more preferably equal to zero,
    C) at least 0.2% of a crosslinking catalyst, the contents in% by weight being expressed relative to the total weight of the adhesive composition, and the sum of the contents of all the ingredients of the adhesive composition being equal to 100% .
    According to one embodiment, the polysilylated polymer (s) Al) corresponds (s) to formula (I) or (II), as defined below, or to their mixture, and preferably corresponding to formula (II).
    According to one embodiment, the monosilylated polymer (s) A.2) corresponds (s) to the formula (Ibis) or (Ilbis), as defined below, or to their mixture, and preference corresponding to the formula (Ilbis).
    According to a more preferred embodiment, the polysilylated polymer (s) Al) corresponds (s) to formula (II), and the monosilylated polymer (s) A.2) meets the formula (Ilbis).
    According to one embodiment, the connector group is a urethane group.
    According to one embodiment, the polysilylated polymer (s) Al) has (s) a number-average molecular mass (Mn) ranging from 6,000 to 55,000 g / mol, preferably from 15,000 to 50,000 g / mol, more preferably from 25,000 to 45,000 g / mol.
    According to one embodiment, the monosilylated polymer (s) A.2) has (s) a number-average molecular mass (Mn) ranging from 1,000 to 55,000 g / mol, preferably 2 000 to 45,000 g / mol, more preferably from 3,000 to 35,000 g / mol.
    According to one embodiment, the tackifying resin (s) has (each) a hydroxyl number substantially close to zero, preferably equal to, zero.
    According to one embodiment, the tackifying resin (s) has (each) a softening point ranging from 0 ° C. to 140 ° C., more preferably from 50 ° C. to 30 ° C., more preferably between 70 and 120 ° C.
    According to one embodiment, the tackifying resin (s) has a number-average molecular weight ranging from 100 to 6,000 g / mol, preferably from 300 to 4,000 g / mol.
    According to one embodiment, the tackifying resin (s) is (are) chosen from:
    (i) the resins obtained by polymerization or copolymerization, optionally by hydrogenation, of mixtures of unsaturated aliphatic and / or aromatic hydrocarbons having approximately 5, 9 or 10 carbon atoms derived from petroleum fractions;
    (ii) the resins obtained by a process comprising the polymerization of alpha-methyl styrene or the copolymerization of alpha-methyl-styrene with other hydrocarbon monomers;
    (iii) rosins of natural or modified origin, such as for example rosin extracted from the pine gem, rosin of wood extracted from the roots of the tree and their hydrogenated, dimerized, polymerized or esterified derivatives with monoalcohols or polyalcohols, such as glycerol or pentaerythritol; and (iv) their mixtures.
    According to a preferred embodiment, the adhesive composition according to the invention comprises:
    A.l) from 5 to 59.8% by weight of one or more polysilylated polymers as defined above,
    A.2) from 15 to 69.8% by weight of one or more monosilylated polymers as defined above,
    B) from 25 to 79.8% by weight of one or more tackifying resins as defined above, and
    C) from 0.2 to 4% by weight of at least one crosslinking catalyst, the contents in% by weight being expressed relative to the total weight of the adhesive composition, and the sum of the contents of all the ingredients of the adhesive composition being equal to 100%.
    A second object of the present invention is a self-adhesive article comprising a support layer coated with a self-adhesive layer, said self-adhesive layer consisting of an adhesive composition according to the invention in the crosslinked state.
    According to one embodiment, the self-adhesive article is a self-adhesive multilayer system, and in particular a label or a self-adhesive tape.
    A third object of the present invention is a product coated at its surface with a self-adhesive article according to the invention, said surface preferably having a surface energy less than or equal to 40 mN / m, preferably ranging from 23 to 38 mN / m, more preferably ranging from 25 to 35 mN / m, said surface energy being measured at 23 ° C, at 50% relative humidity, at atmospheric pressure of 1 bar, in air.
    According to one embodiment, the surface of the product coated with a self-adhesive article according to the invention is based on plastic, preferably of polyolefin type, such as polyisoprene (PI), polyisobutylene (PIB), polyethylene (PE) , polypropylene (PP) and their copolymers, and in particular HDPE and PP.
    The surface of the product coated with a self-adhesive article according to the invention can also be based on cyclic olefin polymer (s) as obtained by metathesis by ring opening ( ROMP).
    The use of at least one monosilylated polymer used according to the invention within an adhesive composition comprising at least one polysilylated polymer, at least one tackifying resin and at least one crosslinking catalyst, preferably as described herein application, makes it possible to obtain, after crosslinking, an adhesive having an adhesion force measured according to the 180 ° peeling test (carried out according to Finat standard No. 1) of at least 3 N / cm on a low energy substrate surface, in particular based on plastic, as specified above, such as PE and PP.
    In particular, the use of at least one monosilylated polymer used according to the invention within an adhesive composition comprising at least one polysilylated polymer, at least one tackifying resin and at least one crosslinking catalyst, preferably as described in the present application, makes it possible to obtain, after crosslinking, an adhesive having an adhesion force measured according to the 180 ° peeling test (carried out according to Finat standard No. 1) of at least 4 N / cm on PP.
    DETAILED DESCRIPTION OF THE EMBODIMENTS OF THE INVENTION
    In this application, in the absence of any indication to the contrary:
    - the viscosity is measured at 23 ° C using a Brookfteld RTV viscometer, with a needle and a speed adapted to the sensitivity of the sensor.
    the number-average molecular mass of the tackifying resins (expressed in g / mol or in dalton) can be determined by methods well known to those skilled in the art, for example by steric exclusion chromatography (GPC), using example a polystyrene standard.
    the number-average molecular mass of the silylated polymers (expressed in g / mol or in dalton) can be determined by methods well known to those skilled in the art, for example by 1H / 13C NMR and / or by calculation from molar quantities of reagents used and / or by size exclusion chromatography (GPC), for example using a polystyrene standard.
    - The hydroxyl number represents the number of hydroxyl functions per gram of tackifying resin, and is expressed in the present application in the form of the equivalent number of milligrams of potash per gram of tackifying resin (mg KOH / g) for the determination of the functions. hydroxyls, ίο
    - the surface energy of a material or substrate is measured at 23 ° C, 50% relative humidity, at atmospheric pressure of 1 bar, in air,
    - The adhesion strength (or peel resistance) is measured by a 180 ° peel test as described in the examples. The reference test is the Finat 1 standard, the time for laying the article on the support to be tested is 20 minutes, and the grammage of glue deposited is 50 g / m 2 ,
    the polysilylated polymer A.l) is a polymer as described below having at least two hydrolyzable silylated groups,
    the monosilylated polymer A.2) is a polymer as described below having a single hydrolyzable silyl group,
    - the terms "lower" or "higher" not followed by the term "or equal" mean "strictly lower" and "strictly higher" respectively,
    - The various embodiments described in the present application can be taken alone or can be combined together.
    ADHESIVE COMPOSITION
    Polysilylated polymer A.1)
    The adhesive composition according to the invention comprises at least one polysilylated polymer Al) having (each) a number-average molecular mass (Mn) of at least 6000 g / mol, and chosen from polymers comprising a main chain of polyether type and / or polyurethane and at least two hydrolyzable silylated end groups, said silylated end groups being attached to the main chain of the polymer by a urethane and / or ether function.
    According to a first embodiment of the polysilylated polymer A.l), the polysilylated polymer A.l) is of the polyether type having at least two ends each connected to a silylated terminal group hydrolyzable by an ether function. According to this embodiment, the polysilylated polymer A.l) can be obtained by a preparation process comprising:
    - In a first step, the preparation of a polyether having at least two allylether end groups (-O-CH2-CH = CH2), then
    in a second step, the reaction of said polyether obtained at the end of the first step with at least one silane having a SiH group, in an amount sufficient to react each of the terminal groups -O-CH2-CH = CH2 of the polyether with the SiH group of the silane by hydrosilylation in the presence of a platinum catalyst, the number-average molecular mass (Mn) of the polyether obtained at the end of the first step must be high enough to obtain, after reaction with the silane compound, a polymer polysilyl Al) of desired Mn.
    According to a second embodiment of the polysilylated polymer A.l), the polysilylated polymer A.l) is of the polyurethane type having at least two ends each connected to a terminal silylated group hydrolyzable by a urethane function. According to this embodiment, the polysilylated polymer A.l) can be obtained by a preparation process comprising:
    - in a first step, the preparation of a polyurethane having at least two terminal OH groups, then
    in a second step, the reaction of said polyurethane with at least one isocyanatosilane having an NCO group, in an amount sufficient to react each of the terminal groups OH of the polyurethane with the NCO group of an isocyanatosilane, the number average molecular mass (Mn ) of the polyurethane obtained at the end of the first step must be high enough to obtain, after reaction with the isocyanatosilane compound, a polysilylated polymer Al) of desired Mn.
    The polyurethane having at least two OH end groups can be obtained in a manner well known to those skilled in the art, by polyaddition of a stoichiometric excess of at least one polyether polyol with at least one diisocyanate. Preferably, the polyether polyol is a polyether diol.
    During the first step, it is also possible to add, as a mixture with the polyether polyol (s), at least one chain extender having two groups each chosen independently of one another from OH and the primary amines and secondary. The chain extender is different from the polyether polyol (s) used for the preparation of the polyurethane and generally has a molar mass of less than 300 g / mol.
    The amounts of polyether polyol (s), of diisocyanate (s), and if appropriate of chain extender (s) used are adjusted in a manner well known to those skilled in the art in order to obtain, at the end of the first step, a polyurethane having two OH end groups, these quantities being moreover such that the molar ratio of the number of NCO functions to the total number of OH functions added to the primary and secondary amine functions possibly present (denoted r2.1) is strictly lower at 1.
    The amount of isocyanatosilane used is adjusted in a manner well known to those skilled in the art in order to obtain at the end of the second step a polysilylated polymer Al), this amount being such that the molar ratio of the number of NCO functions over the total number of OH, primary or secondary amine functions possibly present (denoted r2.2) is close to 1, ie between 0.95 and 1.05.
    The preparation of the polysilylated polymer A.l) is preferably carried out in the presence of at least one reaction catalyst. In particular, any catalyst capable of accelerating the speed of the reaction and / or of the reactions described above and which takes place in the first step and / or the second step of the above-described preparation process can be used.
    According to a third embodiment of the polysilylated polymer A.l), the polysilylated polymer A.l) is of the polyether type having at least two ends each connected to a silylated terminal group hydrolyzable by a urethane function. According to this embodiment, the polysilylated polymer Al) can be obtained by reacting at least one polyether polyol with at least one isocyanatosilane having an NCO group, in an amount sufficient to govern each of the terminal groups OH of the polyether polyol with the NCO group. of an isocyanatosilane, the number average molecular weight (Mn) of the polyether polyol used in must be high enough to obtain, after reaction with the isocyanatosilane, a polysilylated polymer Al) of desired Mn.
    It is also possible to add, as a mixture with the polyether polyol (s), at least one chain extender as described above.
    The quantity of isocyanatosilane used is adjusted in a manner well known to those skilled in the art in order to obtain a polysilylated polymer Al), this quantity being such that the molar ratio of the number of NCO functions to the total number of OH, amine functions primary or secondary possibly present (noted r3) is close to 1, ie between 0.95 and 1.05.
    The preparation of the polysilylated polymer A.l) is preferably carried out in the presence of at least one reaction catalyst. In particular, any catalyst capable of accelerating the speed of the reaction taking place in the preparation process described above can be used.
    Preferably, the polysilylated polymer (s) A.l) corresponds to one of the following formulas, or a mixture thereof:
    - formula (I):
    R- “If (R 4 ) P (OR 5 ) 3.pJ (I) in which:
    - B represents a divalent (for f = 2) or trivalent (for f = 3) hydrocarbon radical comprising from 2 to 66 carbon atoms, linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated, optionally comprising one or more heteroatoms , such as O, N,
    - R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms,
    R ′ 2 represents a linear or branched divalent alkylene radical comprising from 2 to 4 carbon atoms,
    R 4 and R 5 , identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R 4 possibly being able to be engaged in a ring, preferably R 4 is a methyl group,
    - n ”is a non-zero whole number such that the number-average molecular mass of the polyether block of formula - [OR ' 2 ] n ” _ ranges from 150 g / mole to 20,000 g / mole, p is an equal whole number at 0 or 1, f is an integer equal to 2 or 3, the indices n ”and f are such that the number-average molecular mass of the polymer Al) is at least 6000 g / mol;
    - formula (II):
    .o R ^ o.
    -cII o
    -NH-R — NH-C-foR | L O
    Ό-CII o
    -NH-R-Si (R 4 ) p (OR 5 ) ^ (II) in which:
    B represents a divalent (for f = 2) or trivalent (for f = 3) hydrocarbon radical comprising from 2 to 66 carbon atoms, linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated, optionally comprising one or more heteroatoms, such as O, N,
    R 1 represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic,
    R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms,
    R 2 and R ′ 2 , identical or different, each represent a divalent linear or branched alkylene radical comprising from 2 to 4 carbon atoms,
    - R 4 and R 5 , identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R 4 possibly being able to be engaged in a ring, preferably R 4 is a methyl group, n is a non-zero integer such that the number-average molecular mass of the polyether block of formula - [OR 2 ] n- ranges from 300 g / mole to 40,000 g / mole, n 'is a zero or non-zero integer such that the number-average molecular mass of the polyether block of formula - [OR , 2 ] n '- ranges from 0 to 20,000 g / mole, m is an integer which is zero or not zero,
    - p is an integer equal to 0 or 1, f is an integer equal to 2 or 3,
    - the indices m, n, n ’and f are such that the number-average molecular mass of the polymer A.l) is at least 6000 g / mol.
    In formulas (I) and / or (II), preferably:
    - R 2 and / or R ′ 2, which may be identical or different, each represent a linear or branched divalent propylene radical, such as a divalent isopropylene radical,
    - n is an integer such that the number-average molecular mass of the polyether block of formula - [OR 2 ] n - ranges from 6,000 to 25,000 g / mol, and / or
    - n 'is an integer such that the molecular mass in number of the polyether block of formula - [OR' 2 ] n '- ranges from 0 to 12,500 g / mol.
    More preferably,
    - R 2 and / or R ' 2 identical each represent a divalent isopropylene radical,
    - n is an integer such that the number-average molecular mass of the polyether block of formula - [OR 2 ] n - ranges from 8,000 to 20,000 g / mol, and
    - n 'is an integer such that the molecular mass in number of the polyether block of formula - [OR' 2 ] n - ranges from 0 to 10,000 g / mol.
    Preferably, R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, and more preferably a divalent methylene or n-propylene radical.
    Preferably, R 4 represents a methyl radical, when p is equal to 1.
    Preferably, R 5 represents a methyl or ethyl radical.
    According to one embodiment, the adhesive composition comprises a mixture of polysilylated polymer (s) A.l) of formula (I) and / or (II). Preferably, the adhesive composition comprises a mixture of polysilylated polymer (s) A1) comprising at least one polysilylated polymer of formula (I) or (II) such that p = 0, and at least one polysilylated polymer of formula ( I) or (II) such that p = 1. More preferably, the adhesive composition comprises a mixture of polysilylated polymer (s) A1) comprising at least one polysilylated polymer of formula (II) such that p = 0, and at least one polysilylated polymer of formula (II) such as p - 1.
    Preferably, the silylated polymer (s) A.l) is (are) disilylated.
    Preferably, the silylated polymer (s) A.l) corresponds (s) to formula (II).
    According to a preferred embodiment, the polysilylated polymer (s) A.l) is a disilylated polymer (s) corresponding to formula (II) in which f = 2 and m is non-zero. It has been observed that the use of a disilylated polymer A.l) of formula (II) according to this embodiment leads to an improvement in adhesive performance, in particular on PE and PP.
    According to an even more preferred embodiment, the polysilylated polymer (s) Al) is a disilylated polymer (s) corresponding to formula (II) in which f = 2, m is non-zero , and p = 1. In particular, it has been observed that the use of a disilylated polymer Al) of formula (II) according to this embodiment, leads to an improvement in adhesive performance, in particular on PP.
    Preferably, the polysilylated polymer (s) Al) has (s) a number-average molecular mass (Mn) ranging from 6,000 to 55,000 g / mol, more preferably from 15,000 to 50,000 g / mol, and more preferably still from 20,000 to 45,000 g / mol. The indices of formulas (I) and (II) above are preferably such that the number average molecular mass (Mn) of the polysilylated polymer (s) A.l) vary within these ranges of values.
    In particular, it has been observed that the use of a higher disilylated polymer Al) of Mn in the mixture of polymers Al) and A.2) leads to an improvement in the adhesive performance on PE and PP, for polymers of same nature.
    The content of polysilylated polymer (s) Al) represents at least 4% by weight of the weight of the adhesive composition according to the invention, preferably it represents from 5 to 59.8% by weight, more preferably still from 15 to 54.8% by weight, and better still from 20 to 44.8% by weight, of the total weight of the adhesive composition.
    Monosilylated polymer A.2)
    The adhesive composition according to the invention comprises at least one monosilylated polymer A.2) having a number average molecular mass (Mn) of at least 1000 g / mol, and chosen from polymers comprising a main chain of polyether type and / or polyurethane and a hydrolyzable silylated end group, said silylated end group being attached to the main chain of the polymer by a urethane and / or ether function (said connector group).
    According to a first embodiment of the monosilylated polymer A.2), the monosilylated polymer A.2) is of the polyether type, one of the two ends of which is connected to a terminal silyl group hydrolyzable by an ether function.
    According to this embodiment, the monosilylated polymer A.2) can be obtained by a preparation process comprising:
    - in a first step, the preparation of an alkyl (poly) ether, having an allylether end group of structure (Ilia):
    R — J-Q_- CHj ~~ CHszCH g (IHa) in which:
    -R ° represents a divalent hydrocarbon radical comprising from 1 to 60 carbon atoms which may be aliphatic, aromatic or alkyl aromatic, linear, branched or cyclic, -n '”is a zero or non-zero integer such as the average molecular mass in number of the polyether block of formula - [OR ' 2 ] n ”' - goes from 0 g / mole to 20,000 g / mole, and -R ' 2 has the same meaning as above,
    - In a second step, the reaction of said compound of formula (Ilia) with at least one silane having a SiH group, in an amount sufficient to react the terminal group -O-CH2-CH = CH2 of the polyether monoallylether with the group SiH d a silane by hydrosilylation, the number-average molecular mass (Mn) of the monoallylether polyether obtained at the end of the first stage must be high enough to obtain, after reaction with the silane compound, a monosilylated polymer A.2) of desired Mn.
    According to a second embodiment of the monosilylated polymer A.2), the monosilylated polymer A.2) is a polyurethane one of the two ends of which is connected to a silylated terminal group which can be hydrolyzed by a urethane function. According to this embodiment, the monosilylated polymer A.2) can be obtained in-situ during the synthesis of the polysilylated polymer A.l) by a preparation process comprising:
    - In a first step, the preparation of a mixture comprising a polyurethane having a single OH terminal group and a polyurethane comprising two OH terminal groups, then
    in a second step, the reaction of said mixture of polyurethanes obtained in the first step with at least one isocyanatosilane having an NCO group, in an amount sufficient to react all of the terminal OH groups of the mixture of polyurethanes with the NCO group of a isocyanatosilane, the number-average molecular weight of the polyurethane obtained at the end of the first step must be high enough to obtain, after reaction with the silane compound, the polysilylated polymers A1) and monosilylated A.2) of Mn desired.
    The mixture of polyurethanes having respectively two OH end groups and one OH end group can be obtained in a manner well known to those skilled in the art, by polyaddition of a stoichiometric excess of a mixture of polyether diol and monol with at least one diisocyanate.
    The polyether diol (s) and the diisocyanate (s) that can be used to prepare the polyurethane having two terminal OH groups can be chosen from those described in the second mode for producing the polysilylated polymer Al).
    The monol (s) which can be used for the in-situ synthesis of polyurethane having a single OH terminal group can be chosen from the compounds of structure (IIIb) below:
    (IIIb) in order to obtain a polyurethane having a single terminal OH group of sufficient molecular weight. In the formula (Illb), R ° and R ' 2 are as defined in the formula (Ilia), n ”' is a zero or non-zero integer such as the number-average molecular mass of the polyether block of formula - [ OR , 2 ] n '”- ranges from 0 g / mole to 20,000 g / mole.
    The chain extender can be added in the first step in admixture with the polyether diol (s) and the monol (s).
    The chain extender can be chosen from those described in the first embodiment.
    The amounts of polyether dioi (s), monol (s), diisocyanate (s), and if appropriate chain extender (s) used are adjusted in a manner well known to those skilled in the art in order to obtain at the end of the first step, a mixture comprising a polyurethane having a single OH terminal group and a polyurethane having two OH terminal groups, these quantities being moreover such that the molar ratio of the number of NCO functions to the total number of OH functions added primary and secondary amine functions possibly present (noted r2.1) is strictly less than 1.
    The quantity of isocyanatosilane used is adjusted in a manner well known to those skilled in the art in order to obtain, at the end of the second step, a mixture of polysilylated polymer A1) and of monosilylated polymer A.2), this quantity being such that the molar ratio of the number of NCO functions to the total number of OH, primary or secondary amine functions possibly present (denoted r2.2) is close to 1, ie between 0.95 and 1.05.
    The mixture of polysilylated polymer A.l) and monosilylated polymer A.2) is preferably prepared in the presence of at least one reaction catalyst. In particular, any catalyst capable of accelerating the speed of the reaction and / or of the reactions described above and which takes place in the first step and / or the second step of the preparation process described above can be used.
    According to a third embodiment of the monosilylated polymer A.2), the monosilylated polymer A.2) is a polyether one of the two ends of which is connected to a terminal silyl group hydrolysable by a urethane function. According to this embodiment, the monosilylated polymer A.2) can be obtained by reacting at least one compound of structure (Illb), as defined below:
    (Mb) with at least one isocyanatosilane having an NCO group, in an amount sufficient to govern each OH group of the compound (IIIb) with the NCO group of an isocyanatosilane, the number-average molecular mass of the polyether monol used being chosen so to obtain a monosilylated polymer A.2) of desired Mn. In the formula (Illb), R ° and R ' 2 are as defined in the formula (Ilia), n' ”is a zero or non-zero integer such as the number-average molecular mass of the polyether block of formula [OR ' 2 ] n ”' - ranges from 0 g / mole to 20,000 g / mole.
    The quantity of isocyanatosilane used is adjusted in a manner well known to those skilled in the art in order to obtain a monosilylated polymer A.2), this quantity being such that the molar ratio of the number of NCO functions to the total number of OH functions , primary or secondary amine possibly present (noted r2.2) is close to 1, ie between 0.95 and 1.05.
    The mixture of polysilylated polymer A.l) and monosilylated polymer A.2) is preferably prepared in the presence of at least one reaction catalyst. In particular, any catalyst capable of accelerating the speed of the reaction and / or of the reactions described above and which takes place in the first step and / or the second step of the preparation process described above can be used.
    Preferably, the monosilylated polymer (s) A.2) corresponds to one of the following formulas, or to a mixture thereof:
    - formula (Ibis):
    R ^ -foRH-OL J
    -R-Si (R 4 ) p (OR 5 ) ap (Ibis) in which:
    R ° represents a divalent hydrocarbon radical comprising from 1 to 60 carbon atoms which can be aliphatic, aromatic or alkyl aromatic, linear, branched or cyclic,
    - R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms,
    - R ' 2 represents a linear or branched divalent alkylene radical comprising from 2 to 4 carbon atoms,
    R 4 and R 5 , which may be identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R 4 possibly being able to be engaged in a ring, preferably R 4 is a methyl group,
    - n '”is a zero or non-zero integer such that the number-average molecular mass of the polyether block of formula- [OR' 2 ] n ” '- ranges from 0 g / mole to 20,000 g / mole,
    - p is an integer equal to 0, 1 or 2.
    - R ° and n ’” are such that the number average molecular weight of the polymer A.2) is at least 1000 g / mol;
    - formula (Ilbis):
    rLIor’ÏI — L
    L D -m L
    O ~ c — NH ~ R — NH ~ C ~ foR ^ il 11 L J
    O O
    -om
    -C — NH -R-Si {R 4 ) p (OR 5 ) 3-p (Ilbis) in which:
    R ° represents a divalent hydrocarbon radical comprising from 1 to 60 carbon atoms which can be aliphatic, aromatic or alkyl aromatic, linear, branched or cyclic,
    R 1 represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which can be aromatic or aliphatic, linear, branched or cyclic,
    - R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms,
    R 2 and R ′ 2 , identical or different, each represent a linear or branched divalent alkylene radical comprising from 2 to 4 carbon atoms,
    R 4 and R 5 , identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R 4 possibly being able to be engaged in a ring, preferably R 4 is a methyl group,
    - n is an integer such that the number-average molecular mass of the polyether block of formula - [OR 2 ] n - ranges from 300 g / mole to 40,000 g / mole,
    - n '”is a zero or non-zero integer such that the number-average molecular mass of the polyether block of formula - [OR' 2 ] n ·” - ranges from 0 to 20,000 g / mole, m is an integer null or not null,
    - p is an integer equal to 0, 1 or 2.
    - R ° and the indices m, n and n ’” are such that the number average molecular weight of the polymer A.2) is at least 1000 g / mol.
    Preferably, p is an integer equal to 0 or 1. More preferably, p is equal to 1.
    Preferably, the monosilylated polymer (s) A.2) corresponds to the formula (Ilbis).
    Preferably, the monosilylated polymer (s) A.2) corresponds to the formula (Ilbis) in which p = 1.
    Preferably, the monosilylated polymer (s) A.2) has (s) a number-average molecular mass (Mn) ranging from 1,000 to 55,000 g / mol, preferably from 2,000 to 45 000 g / mol, more preferably from 3,000 to 35,000 g / mol. R ° and the indices of the formulas (Ibis) and (Ilbis) mentioned above are preferably such that the number-average molecular mass (Mn) of the monosilylated polymer (s) A.2) vary in these ranges of values.
    The content of monosilylated polymer (s) A.2) represents at least 13% of the total weight of the adhesive composition according to the invention, preferably it represents from 15 to 69.8% by weight, more preferably from 15 to 54.8% by weight, and better still from 20 to 44.8% by weight relative to the total weight of the adhesive composition.
    In particular, it has been observed that the use of a higher content of monosilylated polymer A.2) in the mixture of polymers A.l) and A.2) leads to an improvement in the adhesive performance on PE and PP.
    In the variants of polysilylated polymer mixtures A.l) and monosilylate A.2) as described above, the mixture of polymers of formula (II) and (Ilbis) is preferred.
    The adhesive compositions according to these variants lead to better adhesion performance on polyolefin type substrates such as PE and PP, in particular HDPE and PP, and more particularly on PP.
    The adhesion strength measured by the 180 ° peel test (made according to the Finat standard
    1) adhesive compositions according to these variants is greater than or equal to 3 N / cm, more preferably greater than or equal to 3.5 N / cm and better still greater than or equal to 4 N / cm, on PE and in particular HDPE.
    The adhesion strength measured by the 180 ° peel test (made according to the Finat standard
    1) adhesive compositions according to these variants is greater than or equal to 4 N / cm, more preferably to 5 N / cm, or more preferably greater than 6 N / cm, more preferably still greater than or equal to 7 N / cm, on PP .
    The processes for the preparation of the polysilylated polymers A.l) and monosilylated A.2) described above are carried out under anhydrous conditions, so as to avoid hydrolysis of the hydrolyzable silylated groups. Likewise, the use of these polymers is preferably carried out under such conditions.
    Tackifying resin B)
    The tackifying resin (s) B) which can be used in the adhesive composition according to the invention are compatible with the polysilylated polymers A.l) and monosilylated A.2)
    By compatible tackifying resin is meant a tackifying resin which, when mixed in the proportions 50% / 50% by weight with the mixture of polysilylated polymers A.l) and monosilylated A.2), gives a substantially homogeneous mixture.
    Preferably, the tackifying resin (s) B) has (each) a hydroxyl number less than or equal to 50, more preferably substantially close to zero, and better still equal to zero.
    The tackifying resin (s) B) preferably has (each) a softening point ranging from 0 ° C. to 140 ° C., more preferably from 50 ° C. to 130 ° C., more preferably between 70 and 120 ° C.
    The tackifying resin (s) B) preferably has a number-average molecular weight ranging from 100 to 6,000 g / mol, preferably from 300 to 4,000 g / mol.
    Preferably, the tackifying resin (s) is (are) chosen from:
    (i) the resins obtained by polymerization or copolymerization, optionally by hydrogenation, of mixtures of unsaturated aliphatic and / or aromatic hydrocarbons having approximately 5, 9 or 10 carbon atoms derived from petroleum fractions;
    (ii) resins obtained by a process comprising the polymerization of alpha-methyl styrene or the copolymerization of alpha-methyl-styrene with other hydrocarbon monomers;
    (iii) rosins of natural or modified origin, such as for example rosin extracted from the pine gem, rosin of wood extracted from the roots of the tree and their hydrogenated, dimerized, polymerized or esterified derivatives with monoalcohols or polyalcohols, such as glycerol or pentaerythritol; and (iv) their mixtures.
    According to a preferred embodiment, the tackifying resin B) is a tackifying resin of type (i) or a mixture of tackifying resins comprising at least one tackifying resin of type (i) and / or (ii). Even more preferably, the tackifying resin B) is a mixture of tackifying resins comprising at least one tackifying resin of type (i) and (ii). In particular, it has been observed that the use of a mixture of tackifying resins comprising at least one resin of type (i), and preferably a mixture comprising at least one resin of type (i) and (ii), according to this embodiment, led to an improvement in adhesive performance, in particular, at least on PP.
    Such resins are commercially available. The following products may be mentioned, for example:
    - resins of type (i): PICCO® AR-100 (available from the company EASTMAN) which is obtained by polymerization of aromatic hydrocarbon mixtures having mainly 9 carbon atoms from petroleum fractions, having a zero IOH, a mass molecular in number of 600 g / mol and having a softening point of 100 ° C or the PICCO® AR-85 resin (available from the company EASTMAN) which is obtained by polymerization of mixtures of aromatic hydrocarbons having mainly 9 atoms of carbon obtained from petroleum fractions, having a zero IOH, a number-average molecular mass of 520 g / mol and a softening point of 85 ° C. or else the resin NORSOLENE® Μ1090 (available from the company CRAY VALLEY) which is a aromatic modified aliphatic resin having a zero IOH and a softening point of 90 ° C. or alternatively the PICCO® A-10 resin (available from the company EASTMAN) with a molecular weight of 420 g / mol and liquid at room temperature;
    - resins of type (ii): NORSOLENE® W110 (available from the company CRAY VALLEY), which is obtained by polymerization of alpha-methyl styrene without the action of phenols, having a zero IOH, with a number molecular mass of 750 g / mol and having a softening point of 110 ° C; NORSOLENE® W85 (available from the company CRAY VALLEY) corresponding to an alpha methyl styrene resin, having a zero IOH, a number average molecular weight of approximately 600 g / mol and a softening point of 85 ° C .;
    - resins of type (iii): SYLVALITE® RE 100 (available from the company ARIZONA CHEMICAL) which is an rosin and pentaerythritol ester, having an IOH of 50 mg KOH / g, with a number molecular mass of 974 g / mol, and having a softening point of 100 ° C.
    The content of tackifying resin (s) B) represents at least 25% by weight of the total weight of the adhesive composition according to the invention, preferably it represents from 25 to 79.8% by weight, more preferably still from 30 to 69.8% by weight, and better still 35 to 59.8% by weight, of the total weight of the adhesive composition.
    Crosslinking catalyst C)
    The crosslinking catalyst (s) (C) which can be used in the composition according to the invention can be any catalyst known to those skilled in the art for the condensation of silanol. Examples of such catalysts that may be mentioned are organic titanium derivatives such as titanium acetyl acetonate (commercially available under the name TYZOR® AA75 from DuPont), aluminum such as aluminum chelate (commercially available under the name K-KAT® 5218 from the company KING INDUSTRIES), amines such as 1,8-diazobicyclo (5.4.0) undecene-7 or DBU.
    The content of crosslinking catalyst (s) C) ranges from 0.2 to 4% by weight of the total weight of the adhesive composition.
    According to a preferred embodiment, the adhesive composition according to the invention comprises:
    - at least 5% by weight of one or more polysilylated polymers A.l),
    - at least 15% by weight of one or more monosilylated polymers A.2),
    - from 25 to 79.8% by weight of one or more tackifying resins B), and
    from 0.2 to 4% by weight of at least one crosslinking catalyst C), the content of silylated polymers Al) and A.2) representing from 20 to 74.8% by weight of the total weight of the adhesive composition .
    According to an even more preferred embodiment, the adhesive composition according to the invention comprises:
    - at least 15% by weight of one or more disilylated polymers A.l),
    - at least 15% by weight of one or more monosilylated polymers A.2),
    - from 30 to 69.8% by weight of one or more tackifying resins B), and
    from 0.2 to 4% by weight of at least one crosslinking catalyst C), the content of silylated polymers Al) and A.2) representing from 30 to 69.8% by weight of the total weight of the adhesive composition .
    According to an even more preferred embodiment, the adhesive composition according to the invention comprises:
    - at least 20% by weight of one or more disilylated polymers A.l),
    - at least 20% by weight of one or more monosilylated polymers A.2),
    - from 35 to 59.8% by weight of one or more tackifying resin B), and
    from 0.2 to 4% by weight of at least one crosslinking catalyst C), the content of silylated polymers Al) and A.2) representing from 40 to 64.8% by weight of the total weight of the adhesive composition .
    The adhesive composition according to the invention may also or may not include, in combination with the mixture of polysilylated polymers A1) and monosilylated A.2), at least one thermoplastic polymer chosen from those used in the preparation of HMPSAs, such as Ethylene Vinyl Acetate (EVA) or styrenic block copolymers (such as SIS, SBS, SIBS, SEBS, SEPS, and their derivatives grafted with in particular maleic anhydride). These thermoplastic polymers are not silylated.
    The adhesive composition according to the invention may also or may not comprise at least one hydrolyzable, non-polymeric alkoxysilane derivative, with a molar mass of less than 500 g / mol, as a drying agent, and preferably a trimethoxysilane derivative. Such an agent advantageously prolongs the shelf life of the adhesive composition according to the invention during storage and transport, before its use. Mention may be made, for example, of gamma-metacryloxypropyltrimethoxysilane available under the trade name SILQUEST® A-174 from the company MOMENTIVE. The content of desiccant (s) can be up to 3% by weight of the weight of the adhesive composition.
    The composition according to the invention may also or may not include at least one plasticizer such as a phthalate or a benzoate, a paraffinic and naphthenic oil (such as Primo 1® 352 from the company ESSO) or also a wax of a homopolymer of polyethylene (such as AC® 617 from HONEYWELL), or a wax from a copolymer of polyethylene and vinyl acetate, or pigments or dyes, or a mixture of these compounds.
    The adhesive composition according to the invention may or may not include fillers. The filler content preferably represents less than 15% by weight, more preferably less than 10% by weight, and more preferably still less than 1% by weight, of the weight of the adhesive composition.
    Finally, an amount of 0.1 to 2% of one or more stabilizers (or antioxidants) is preferably included in the adhesive composition according to the invention. These compounds are introduced to protect the composition from degradation resulting from a reaction with oxygen which is likely to be formed by the action of heat or light. These compounds can include primary antioxidants which scavenge free radicals and are in particular substituted phenols such as irganox® 1076 from CIBA. The primary antioxidants can be used alone or in combination with other secondary antioxidants or UV stabilizers.
    The adhesive composition according to the invention can be prepared by a process which comprises:
    a step of mixing, protected from air, preferably under an inert or empty atmosphere, the polysilylated polymers A1) and monosilylated A.2), with the tackifying resin or resins B), at a temperature ranging from 40 to 170 ° C, preferably ranging from 70 to 150 ° C, then
    a step of incorporating into said mixture at least one crosslinking catalyst C) at a temperature ranging from 40 to 90 ° C and, if necessary, at least one desiccant and one or more * others optional components as described above.
    The adhesive composition according to the invention can be used for the manufacture of a self-adhesive article, comprising a temporary or permanent support layer and an adhesive layer, said adhesive layer being obtained by crosslinking of the adhesive composition.
    The support layer of the self-adhesive article obtained from the adhesive composition according to the invention can be a temporary or permanent support layer.
    In the case where the support layer is a temporary support, the support layer is preferably a plastic film or non-stick protective paper ("release liner" in English). In this case, once the article is glued to a surface, the glued article only includes an adhesive layer, the temporary support being intended to be removed.
    By "non-stick" means a material on which the adhesive composition according to the invention in the crosslinked state has an adhesive strength of less than 200 centinewton per centimeter (cN / cm), and preferably less than 50 cN / cm or even more preferably less than 30 cN / cm or even more preferably less than 10 cN / cm. This value is measured according to the FINAT 3 test carried out at a pulling speed of 300 mm / min and a pulling angle of 180 °.
    The non-stick layer generally has a surface energy less than or equal to 22 mN / m, more preferably less than 20 mN / m.
    In the case where the support layer is a permanent support layer, the support layer may be based on any material which can be used for the manufacture of pressure-sensitive articles or PSA article.
    SELF-ADHESIVE ARTICLE
    The present invention also relates to a self-adhesive article comprising a support layer coated with a self-adhesive layer, said self-adhesive layer consisting of an adhesive composition according to the invention in the crosslinked state.
    For the purposes of the present invention, the term “self-adhesive article” includes any article which can be glued to a surface only by the action of pressure by hand or equipment, without the use of additional glues or adhesives. . The term "self-adhesive article" also includes the expression "pressure sensitive adhesive article" or "pressure sensitive adhesive article". These articles are intended to be applied to a surface to be bonded in order to bring together, maintain, fix, or simply immobilize, expose shapes, logos, images or information. These items can be used in many fields, such as medical, clothing, packaging, automotive or construction. They can be shaped according to their final application, for example in the form of ribbons, such as ribbons for industrial use, DIY tapes or for use in fixing on building sites, single or double-sided tapes, or in the form labels, bandages, dressings, patches or graphic films.
    According to one embodiment, the self-adhesive article is a self-adhesive multilayer system, and in particular a label or a self-adhesive tape, which can be single or double-sided.
    The support layer is flexible enough to be able to be wound and packaged in the form of a coil, for example as described above.
    Preferably, the support layer has an elongation at break greater than zero and strictly less than 100%. More preferably, the support layer has an elongation at break less than or equal to 50%, and even more preferably less than or equal to 40%. More preferably, the support layer has an elongation at break less than or equal to 30%.
    The elongation at break can be measured according to ISO 1926 at 23 ° C, lengthwise or widthwise. Preferably, the elongation at break is measured lengthwise.
    The support layer may for example be based on acrylic polymers, on polyethylene (PE), oriented polypropylene (PP), unoriented or bi-oriented, Polyimide, Polyurethane, Polyester such as Polyethylene terephthalate (PET), or paper.
    Preferably, the support layer has a Young's modulus strictly greater than 300 MPa, more preferably greater than or equal to 400 MPa, and better still greater than or equal to 500 MPa.
    According to one embodiment, the self-adhesive article obtained from the adhesive composition according to the invention comprises a permanent support layer coated with an adhesive layer. Preferably, the adhesive layer is also coated with a non-stick protective plastic film or paper, preferably silicone.
    As an alternative to the non-stick protective film, the rear face of the permanent support layer which is not coated with the adhesive layer, may have a non-stick surface, for example a silicone protective layer.
    The two embodiments described above allow the self-adhesive article to be rolled up and then unrolled without problem of transfer of glue between the adhesive layer and the permanent support layer.
    According to one embodiment, the permanent support layer is coated on its two faces with an adhesive composition, which can be identical or different, at least one of the two adhesive compositions being according to the invention.
    Preferably, the support layer has a thickness ranging from 10 microns to 50 mm, more preferably ranging from 10 microns to 20 mm, preferably ranging from 20 microns to 10 mm, more preferably ranging from 20 microns to 1 mm.
    In some cases, it is necessary to carry out a surface treatment of the support layer to increase the adhesion of the adhesive layer during the coating step thereon, in particular when the support layer and the surface of the substrate. to be bonded have the same surface energy.
    The self-adhesive article according to the invention can be applied to the surface of a low energy surface substrate which has not been subjected to surface pretreatments. These pretreatments aim to chemically and / or physically modify said surface, in order to increase the surface energy and / or the roughness of said surface, and thus improve the adhesion of the adhesive layer on said surface. As an example of known surface treatments, mention may be made of plasma or corona treatment, abrasion or else the application to said surface of a chemical bonding agent (also called primary) capable of imparting to the substrate coated with said agent a higher surface energy.
    The self-adhesive article according to the invention can thus bond two substrates, at least one of which has a low surface energy.
    The substrate on which the self-adhesive article is intended to be applied (designated by "substrate to be bonded") can be flexible or rigid.
    In particular, it may have the same flexibility properties as the support layer described above, so as to be wound and packaged in the form of a coil, for example as described above.
    Alternatively, the substrate to be bonded can be rigid. In this case, the substrate cannot be wound and conditioned in the form of a coil, for example as described above, without becoming brittle.
    The substrate to be bonded can be chosen from substrates of low surface energy, such as substrates of the polyolefin type, which are organic non-polar substrates; or organic non-polar coatings of the varnish, ink or paint type; said substrates having a surface energy less than or equal to 40 mN / m, preferably ranging from 23 to 38 mN / m, more preferably ranging from 25 to 35 mN / m.
    The polyolefin-type substrates can for example be polymeric materials based on monomers and co-monomers such as polyethylene (PE), polypropylene (PP), polyisoprene (PI), polyisobutylene (PIB), and their copolymers ( blocks or statistics), or based on cyclic olefin polymer (s) as obtained by ring opening metathesis (ROMP), or mixtures of these polymers.
    By way of example of polyethylene (PE), mention may in particular be made of high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene and linear ultra low density polyethylene.
    Thanks to the adhesive properties of the adhesive obtained by crosslinking the adhesive composition according to the invention, the self-adhesive article according to the invention can stick to a low surface energy substrate, in particular based on plastic, preferably at polyolefin base, such as PE and PP, and in particular HDPE and PP, with an adhesion strength of at least 3N / cm.
    In particular, the self-adhesive article according to the invention can stick to a PP-based substrate, with an adhesion strength of at least 4N / cm.
    According to one embodiment of the invention, the self-adhesive article also comprises a protective non-stick layer ("release liner" in English).
    According to one embodiment, said non-stick layer is applied to the adhesive layer, after crosslinking of the adhesive composition.
    The support layer can be covered on one of its two faces, the rear face which is not coated with the adhesive layer, by a non-stick protective layer, for example by a silicone film. In this way, the self-adhesive article can be rolled up on itself and then unrolled without problem thanks to the lack of adhesion of the adhesive layer on the silicone face.
    The self-adhesive article according to the invention is capable of being obtained by the process comprising the following steps:
    (a) conditioning the adhesive composition according to the invention as defined above at a temperature ranging from 20 to 130 ° C; then (b) coating with the adhesive composition obtained in step (a) a support surface; then (c) crosslinking the coated adhesive composition, by heating to a temperature ranging from 20 to 200 ° C in a gaseous environment where water molecules are present between 10 and 200 mg per m 3 of gas;
    (d) lamination or transfer of the crosslinked adhesive layer onto a support layer or onto a non-stick protective film, said support layer or non-stick film being able to be the back of the support surface.
    By “supporting surface” within the meaning of the present invention, it is necessary to understand either a conveyor belt covered with a non-stick layer, or a non-stick protective film (“release liner” in English), or a support layer. Thus, the supporting surface is made to become an integral part of the self-adhesive article, either as a non-stick protective film, or as a support layer.
    In the case where the supporting surface is not a support layer, the process for obtaining the self-adhesive article according to the invention comprises the step (d) of transferring the crosslinked adhesive layer onto a support layer.
    In the case where the supporting surface is a support layer, the process for obtaining the self-adhesive article according to the invention can comprise the step (d) of laminating the adhesive layer on a non-stick protective film. .
    According to a preferred variant of the invention, step (d) of the above-described method consists in transferring the crosslinked adhesive layer to a flexible support layer (which may be a plastic film) after the crosslinked adhesive layer has cooled. a temperature below the degradation or softening temperature of the material making up the support layer. According to this variant, it is possible to manufacture a self-adhesive article comprising a support layer made of a temperature-sensitive material, for example a material based on polyolefin, as mentioned above.
    According to one embodiment, the self-adhesive article according to the invention is capable of being obtained by the method as described above, not comprising a pretreatment step of the surface of the support layer. These pretreatments aim to chemically and / or physically modify said surface, in order to increase the surface energy and / or the roughness of said surface, and thus improve the adhesion of the adhesive layer on said surface. By way of example, known surface treatments, mention may be made of plasma, corona treatment, abrasion or else the application to said surface of a chemical bonding agent (also called primary) capable of imparting to the coated substrate. said agent a high surface energy.
    According to one embodiment of the invention, the adhesive layer as described above has an adhesion force on substrates with different surface energies of at least 3 N / cm, preferably at least 3.5 N / cm, more preferably at least 4 N / cm.
    In particular, a self-adhesive article consisting of a support layer of PolyEthyleneTerephthalate (PET) of thickness 50 μm, coated with an adhesive layer according to the invention, at a grammage of 50 g / m 2 , has permanent adhesion to HDPE or PP corresponding to an adhesive power (measured by the 180 ° peel test (carried out according to the Finat 1 standard) advantageously ranging from 3 to 15 N / cm.
    Said adhesion force can be measured after an exposure time of the self-adhesive article on a surface of a defined low-energy surface substrate which can range from a few minutes, to a few hours, or several days, as illustrated in particular. in the examples.
    According to one embodiment, the method of manufacturing the self-adhesive article according to the invention further comprises a step (e) of coating a second layer of adhesive composition according to the invention on the support layer followed by a step (f) of crosslinking the adhesive composition coated in step (e) by heating at a temperature ranging from 20 to 200 ° C. According to this embodiment, a double-sided self-adhesive article is obtained.
    The coating step (b) can be carried out by means of known coating devices, such as for example a lip or curtain type nozzle, or even with a roller. It uses a grammage of adhesive composition ranging from 3 to 2000 g / m 2 , preferably from 5 to 1000 g / m 2 , more preferably from 10 to 500 g / m 2 or more preferably from 12 to 250 g / m 2 .
    The grammage of adhesive composition necessary for the manufacture of self-adhesive labels can range from 10 to 100 g / m 2 , preferably from 20 to 50 g / m 2 . That required for the manufacture of self-adhesive tapes can vary in a much wider range ranging from 3 to 500 g / m 2 , preferably from 15 to 250 g / m 2 per side.
    According to one embodiment, the coated adhesive composition is further subjected, during step (c) to a treatment in a humid atmosphere characterized by its humidity level. Preferably, the humid atmosphere is an atmosphere in which from 2 to 100% of the molecules are water molecules, preferably from 4 to 50%, more preferably from 5 to 10% of the molecules are water molecules .
    The humidity is expressed as a percentage of water per unit volume, which is the number of molecules of water divided by the total number of molecules in a unit of volume. Thanks to the linear nature of this scale, the humidity is easily measured and controlled using, for example, monitors of the P.I.D (ProportionalIntegral-Derivative) type. The percentage by weight can be calculated by multiplying the percentage of the number of water molecules in relation to the total number of molecules by a factor of 0.622. General information on humidity in various environments is described by W. Wagner et al., In "International Steam Tables Properties of Water and Steam based on the Industrial Formulation IAPWS-IF97".
    The time necessary for the crosslinking of step (c) can vary within wide limits, for example between 1 second and 30 minutes, depending on the grammage of adhesive composition deposited on the support surface, the heating temperature, and humidity.
    This thermal crosslinking step has the effect of creating - between the polymer chains of the mixture of polysilylated polymers A1) and monosilylated A.2) as described above and under the action of humidity - siloxane type bonds which lead to the formation of a three-dimensional polymer network. The adhesive composition thus crosslinked is a pressure-sensitive adhesive which gives the support layer which is coated with it the desired adhesive power and tack.
    Preferably, the coating is carried out uniformly on the support layer or on the non-stick protective layer but the coating can also be adapted to the desired shape of the final self-adhesive article.
    According to one embodiment, the coating with the adhesive composition is carried out on at least part of the two faces of the support layer. If the two faces of the support layer are coated, the adhesive composition can be identical or different on the two faces, and the grammage can be identical or different on the two faces.
    According to one embodiment of the invention, the self-adhesive article comprises an adhesive layer on at least a part of one face or on at least a part of the two faces of the support layer, said adhesive layer (s) possibly being coated with a non-stick protective layer. According to one embodiment, the self-adhesive article comprises two non-stick protective layers on each of the two adhesive layers. In this case, the two protective layers can be made of identical or different materials and / or they can have an identical or different thickness.
    The self-adhesive article according to the invention can be used in a bonding method comprising the following steps:
    a) remove the non-stick protective layer, when such a layer is present;
    b) applying the self-adhesive article to a surface of a product; and
    c) apply pressure to said article.
    In step b), the self-adhesive article is applied so that the self-adhesive part of the article (formed by the self-adhesive layer) faces the surface of the product.
    According to an embodiment in which the self-adhesive article is a double-sided article, the bonding method further comprises a step in which either a second surface of a product is applied to the article bonded to the first surface d 'a product, that is the article stuck on the first surface of a product is applied to a second surface of a product.
    PRODUCT COATED WITH A SELF-ADHESIVE ARTICLE
    A third object of the present invention is a product coated at its surface with a self-adhesive article according to the invention.
    Preferably, said surface has not undergone any pretreatment of the surface as described above.
    Preferably, said surface has a surface energy less than or equal to 40 mN / m, preferably ranging from 23 to 38 mN / m, more preferably ranging from 25 to 35 mN / m.
    Preferably, said surface is smooth and homogeneous.
    The surface of the product coated with a self-adhesive article according to the invention may be based on substrates of low surface energy, such as substrates of the polyolefin type, which are organic non-polar substrates; or organic non-polar coatings of the varnish, ink or paint type; said substrates having a surface energy less than or equal to 40 mN / m, preferably ranging from 23 to 38 mN / m, more preferably ranging from 25 to 35 mN / m.
    Polyolefin-type substrates can be, for example, polymeric materials based on monomers and co-monomers such as polyethylene (PE), polypropylene (PP), polyisoprene (PI), polyisobutylene (PIB), and their copolymers ( blocks or statistics), or based on cyclic olefin polymer (s) as obtained by ring opening metathesis (ROMP), or mixtures of these polymers.
    By way of example of polyethylene (PE), mention may in particular be made of high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene and linear ultra low density polyethylene.
    The surface of the product coated with a self-adhesive article according to the invention can be flexible or rigid.
    In particular, the product to be coated may have the same flexibility properties as the support layer described above, so as to be wound and packaged in the form of a coil, for example as described above.
    Alternatively, the product to be coated cannot be wound and packaged in the form of a coil, for example as described above, either because of its rigidity, its shape or its thickness.
    The following examples are given purely by way of illustration of the invention and should not be interpreted to limit its scope.
    EXAMPLES
    The following ingredients were used in the examples:
    As disilylated polymer:
    PDS 1: Disilylated polymer having a number average molecular mass of approximately 16,000 g / mol (or 20 kDa and an Ip of approximately 1.6 if determined by GPC), comprising a main chain of polyurethane type and two terminal groups hydrolyzable propylene-trimethoxysilane, said silylated end groups being attached to the main chain of the polymer by a urethane function. This polymer corresponds in particular to formula (I).
    PDS2: Disilylated polymer having a number average molecular mass of approximately 37,000 g / mol (or 38 kDa an Ip of approximately 1.9 if determined by GPC), comprising a main chain of polyurethane type and two end groups propylene- hydrolyzable trimethoxysilane, said silylated end groups being attached to the main chain of the polymer by a urethane function. This polymer corresponds in particular to formula (I).
    PDS3: GENIOSIL® STP-E 30 (available from Wacker): disilylated polymer having a number average molecular weight of approximately 18,500 g / mol (or 22 kDa and an Ip of approximately 1.2 if determined by GPC) , comprising a main chain of polyether type and two hydrolyzable methylene trimethoxysilane end groups, said silylated end groups being attached to the main chain of the polymer by a urethane function. This polymer corresponds in particular to formula (I).
    PDS4: GENIOSIL® STP-E 35 (available from Wacker): disilylated polymer having a number average molecular weight of approximately 18,600 g / mol (or 22 kDa and an Ip of approximately 1.2 if determined by GPC) , comprising a main chain of polyether type and two hydrolysable propylenetrimethoxysilane end groups, said silylated end groups being attached to the main chain of the polymer by a urethane function. This polymer corresponds in particular to formula (I).
    As monosilylated polymer:
    - PMSI: GENIOSIL®XM20 (available from Wacker): monosilylated polymer having a number average molecular weight of approximately 6,000 g / mol (or 8 kDa if determined by GPC), and has an Ip of approximately 1.1 . It comprises a main chain of polyether type and a hydrolyzable methylene-methyldimethoxysilane end group, said silylated end group being attached to the main chain of the polymer by a urethane function. This polymer corresponds in particular to the formula (Ilbis) in which m = 0 and p = l. PMS2: GENIOSIL®XM25 (available from Wacker): monosilylated polymer having a number average molecular weight of approximately 6000 g / mol (or 8 kDa determined by GPC) and has an Ip of approximately 1.1. It comprises a main chain of polyether type and a hydrolyzable propylene-trimethoxysilane end group, said silylated end group being attached to the main chain of the polymer by a urethane function. This polymer corresponds in particular to the formula (Ilbis) in which m = 0 and p = 0.
    As tackifying resin:
    Tl: SYLVALITE® RE 100 (available from the company ARIZONA CHEMICAL): rosin and pentaerythritol ester type resin, having an IOH of approximately 50 mg KOH / g, a number average molecular weight of approximately 974 g / soft and a softening point of 100 ° C (tackifying resin of type (iii));
    T2: DERTOPHENE® H 150 (available from the company DRT): phenolic terpene type resin, having an IOH of approximately 150 mg KOH / g, a number average molecular mass of approximately 700 g / mol and a softening of 120 ° C;
    - T3: NORSOLENE® W85 (available from the company CRAY VALLEY): alpha methyl styrene resin, having an IOH of 0, a number average molecular weight of approximately 600 g / mol and a softening point of 85 ° C. (tackifying resin of type (ii));
    - T4: NORSOLENE® W110 (available from the company CRAY VALLEY): alpha methyl styrene resin, having an IOH of 0, a number average molecular weight of around 750 g / mol and a softening point of 110 ° C (tackifying resin of type (ii));
    T5: PICCO® AR 100 (available from EASTMAN): resin obtained by polymerization of mixtures of aromatic hydrocarbons mainly having 9 carbon atoms from petroleum fractions, having an IOH of 0, a number average molecular weight of 550 g / mol and a softening point of 100 ° C (tackifying resin of type (i)).
    As crosslinking catalyst:
    - K-KAT® 5218 (available from King Industries): contains an aluminum chelate.
    I - Preparation of disilylated polymers A.l)
    PDS1 synthesis:
    The following are introduced into a glass reactor:
    - 961.2 g (0.1199 mole) of ACCLAIM® 8200 poly (oxypropylene) diol,
    - 12.99 g (0.0582 mole) of isophorone diisocyanate (IPDI), which corresponds to a molar ratio of NCO / OH functions equal to 0.5; and:
    - 0.29 g (corresponding to 300 ppm) of a catalyst of the bismuth and zinc neodecanoate type (commercially available from the company Borchers, under the name Borchi Kat VP 0244).
    This mixture is kept under constant stirring at 85 ° C. and under nitrogen for 3 hours, until the NCO functions of the IPDI have completely reacted.
    To the polyurethane with hydroxyl endings thus obtained are then added 26.05 g (0.1269 mole) of gamma-isocyanato-n-propyl-trimethoxysilane and the mixture is maintained at 85 ° C. until total disappearance of the NCO functions.
    The polyurethane obtained has a viscosity of 55 Pascal second (Pa.s.) approximately (measured with a Brookfield viscometer at 23 ° C, with a needle 7 rotating at the rate of 20 revolutions per minute (rpm)) and an average molecular mass in number of approximately 16,000 g / mol (or 20 kDa and a polymolecularity index of approximately 1.6 determined by GPC).
    PDS2 synthesis:
    The following are introduced into a glass reactor:
    - 884.63 g (0.0457 mole) of ACCLAIM® 18200 poly (oxypropylene) diol,
    - 5.10 g (0.0229 mol) of isophorone diisocyanate (IPDI), which corresponds to a ratio of the numbers of NCO / OH functions equal to 0.5; and:
    - 300 ppm of a catalyst of the bismuth and zinc neodecanoate type (commercially available from the company Borchers, under the name Borchi Kat VP 0244).
    This mixture is kept under constant stirring at 85 ° C. and under nitrogen for 3 hours, until the NCO functions of the IPD1 have completely reacted.
    To the polyurethane with hydroxyl endings thus obtained are then added 10 g (0.0474 mole) of gamma-isocyanato-n-propyl-trimethoxysilane and the mixture is maintained at 85 ° C until complete disappearance of the NCO functions.
    The polyurethane obtained has a viscosity of 510 Pa.s. approximately (measured with the Brookfield viscometer at 23 ° C, with a needle 7 rotating at a rate of 20 rpm) and a number-average molecular mass of approximately 37,000 g / mol (or 38 kDa an Ip of approximately 1, 9 if determined by GPC).
    II - Preparation of the adhesive compositions
    The adhesive compositions 1 to 14 and CEI to CE8 were prepared by following the same operating protocol described below, using the ingredients listed in Table 1 below. The amounts of each ingredient used are indicated as a percentage by weight relative to the total weight of the adhesive composition.
    Compositions 1 to 14 correspond to adhesive compositions according to the invention.
    The compositions CEI to CE8 correspond to comparative adhesive compositions. In particular :
    the compositions CEI and CE2 correspond to the compositions of examples A of application WO 09/106699 and EP 2 336 208 respectively, comprising a single disilylated polymer Al) and a tackifying resin having an IOH greater than 100 mg KOH / g, the compositions CE3 to CE6 correspond to comparative compositions comprising a single disilylated polymer A1), the compositions CE7 and CE8 correspond to comparative compositions comprising a single monosilylated polymer A.2).
    Operating procedure :
    The adhesive composition is prepared by first introducing the tackifying resin into a glass vacuum reactor and heated to about 140 ° C. Then, once the resin has melted, the silylated polymer A.l) or A.2) or the mixture of silylated polymers A.l) and A.2) is added.
    The mixture is stirred under vacuum for 15 minutes, then cooled to 80 ° C. The catalyst is then introduced. The mixture is kept under vacuum and with stirring for an additional 10 minutes.
    The viscosity of the mixture is then determined at 100 ° C., using a Brookfield type viscometer (equipped with the Thermosel system intended for viscosity measurements at high temperature) fitted with an A28 needle rotating at a speed adapted to the sensitivity of the sensor. For examples 1 to 14 according to the invention and the comparative examples, the mixtures have a viscosity ranging from 0.5 Pa.s. at 40 Pa.s., measured at 100 ° C.
    II - Preparation of self-adhesive articles
    Each of the adhesive compositions 1 to 14 and CEI to CE8 is used for the manufacture of a self-adhesive article, by following the operating protocol below.
    Operating procedure :
    A rectangular sheet of PolyEthyleneTerephthalate (PET) with a thickness of 50 μm and dimensions of 20 cm by 40 cm is used as the support layer.
    The adhesive composition is preheated to a temperature close to 90 ° C. and it is introduced into a cartridge from which a bead is extruded which is deposited near the edge of the sheet parallel to its width.
    The adhesive composition contained in this bead is then distributed over the entire surface of the sheet, so as to obtain a uniform layer and of substantially constant thickness. A film puller (also called filmograph) is used for this which is moved from the edge of the sheet to the opposite edge. A layer of adhesive composition corresponding to a grammage of 50 g / m 2 is thus deposited, which represents approximately a thickness of the order of 50 μm.
    The PET sheet thus coated is then placed in an oven at 120 ° C for 600 seconds for crosslinking of the composition, then laminated to a protective non-stick layer consisting of another sheet of PET film whose surface is siliconized to serve as an anti- -adhesive, rectangular and of the same dimensions.
    The self-adhesive article thus obtained comprising the adhesive layer crosslinked on the PET support is subjected to the tests described below.
    III - Adhesive test of self-adhesive articles
    The self-adhesive articles prepared above are subjected under the same conditions to the following bonding tests on two types of polyolefin substrates: HDPE and PP. The surface energy of these substrates in contact with the adhesive tested is 27 and 29 mN / m respectively for HDPE and PP. These values were determined from the measurement method described below.
    Determination of the surface energy of the substrates:
    The surface energy of each of the substrates was determined from the measurement of the contact angle of standard solutions on the surface of said substrates. The substrates tested are HDPE or PP plates with a flat, smooth and homogeneous surface, 15 cm long and 2.5 cm wide. The contact angle was measured for three standard solutions (diiodomethane, ethylene glycol and water) with a Digidrop device fitted with a set of syringes intended for depositing standard solutions. The contact angle measuring device is connected to the Windrop ++ software supplied by the company GBX Scientific Instrument for the calculation of the surface energy of the substrate from the measured contact angle. The measurements were carried out in the open air in a room at 23 ° C with a relative humidity of 50%, at atmospheric pressure of 1 bar.
    Preparation of the substrates: The substrate is fixed to a glass plate 15 cm long and 5 cm wide using a layer of double-sided adhesive tape of the same dimensions as the substrate and completely covering the surface of said substrate, by making coincide at least one of the angles of each of the layers formed by the substrate, the adhesive tape and the glass plate. The sample thus formed is smoothed in order to obtain a smooth surface free of air bubbles. The sample is placed under the Digidrop so that the deposition syringes face the substrate surface of the sample and are aligned as close as possible to the edge of the sample.
    Measurement of the contact angle: The Windrop ++ software allows you to launch the deposition program which will simultaneously trigger the deposition of a drop of a standard solution and the automatic taking of a photo of the drop in contact with the surface of the substrate. The picture is taken at 13,000 milliseconds (ms) for water and ethylene glycol, and at 2000 ms for diiodomethane from the start of the program. For each standard solution, three deposits are made. Between each deposit, the sample is moved manually so that the drops are deposited close to each other on the surface of the substrate, near the edge of the sample. The order of depositing the drops is as follows: 3 drops of water, 3 drops of ethylene glycol, 3 drops of diiodomethane.
    Calculation of the contact angle and determination of the surface energy of the substrate: From each of the shots taken, a contact angle is calculated with the "Manual 2" method. Three values of contact angle are thus obtained for each standard solution. The surface energy of the substrate (EN1) is calculated by applying the Owen & Wendt model to the contact angle values found.
    A second series of contact angle measurements is made for each standard solution. As before, we measure the contact angles for 3 drops of each standard solution in the above-mentioned order, then deduce a second surface energy value (EN2).
    A third series of contact angle measurements is carried out for each standard solution, then a third surface energy value (EN3) is deduced therefrom.
    The surface energy of the substrate is obtained by averaging the three values EN 1, EN2 and EN3 obtained.
    180 ° peel test on polyolefin (HDPE, PP):
    The adhesive power is evaluated by the peel test (or peel) at 180 ° as described in the FINAT method n ° 1, published in the FINAT Technical Manual 6 th edition, 2001, on polyolefin. FINAT is the international federation of manufacturers and processors of self-adhesive labels. The principle of this test is as follows.
    A test piece in the form of a rectangular strip (25 mm × 175 mm) is cut from the PET support layer coated with the crosslinked composition constituting the self-adhesive article obtained previously. This specimen is, after its preparation, stored for 24 hours at a temperature of 23 ° C and in an atmosphere at 50% relative humidity. It is then fixed over 2/3 of its length (after removal of the corresponding protective non-stick layer portion) on a substrate made of an HDPE or PP plate. The assembly obtained is left for 20 minutes at room temperature (23 ° C). It is then placed in a traction device capable, from the free end of the rectangular strip, of peeling or peeling off the strip at an angle of 180 ° and with a separation speed of 300 mm by minute. The device measures the force required to take off the strip under these conditions.
    Results:
    The results of the measurements are expressed in N / cm and indicated in Table 2 below. It is observed that the adhesive compositions of Examples 1 to 14 according to the invention make it possible to obtain a self-adhesive article having an adhesive power greater than the comparative adhesive compositions of Examples CEI to CE6. The compositions CE7 and CE8 have not made it possible to obtain a cross-linked self-adhesive article in the desired field and show the need to combine a disilylated polymer with a monosilylated polymer.
    The excellent adhesive performances of the adhesive compositions according to the invention on all of the low surface energy substrates tested result from a synergistic effect between the different ingredients used.
    In particular, thanks to the following series of comparisons, it has been shown that:
    1) the use of a mixture of polymers Al) and A.2) leads to an improvement in adhesive performance on all of the low surface energy substrates tested compared to the use of a polymer Al) alone :
    series (1.1): comparison of the comparative composition CE3 with each of the compositions of Examples 3, 4, 6, 9 and 10 according to the invention series (1.2): comparison of the comparative composition CE5 with the composition of Example 13 according to the invention, series (1.3): comparison of the comparative composition CE6 with the composition of Example 14 according to the invention;
    2) the use of a mixture of polymers Al) and A.2) leads to an improvement in adhesive performance on all of the low surface energy substrates tested compared to the use of a polymer A.2) only :
    - series (2.1): comparison of the comparative composition CE7 with each of the compositions of Examples 4, 10, 12, 13, 14 according to the invention, series (2.2): comparison of the comparative composition CE8 with each of the compositions of Examples 3 , 6, 9, 11 according to the invention;
    3) the use of a higher content of monosilylated polymer A.2) in the mixture of polymers A.l) and A.2) leads to an improvement in adhesive performance on all of the low surface energy substrates tested:
    - series (3.1): comparison of the composition of example 12 and example 11,
    - series (3.2): comparison of the composition of Example 3 and of Example 9;
    4) the use of a disilylated polymer Al) of higher Mn in the mixture of polymers Al) and A.2) leads to an improvement in adhesive performance on all of the low surface energy substrates tested, for polymers of the same nature;
    - series (4.1): comparison of the composition of example 12 and example 3,
    - series (4.2): comparison of the composition of Example 11 and of Example 9;
    5) the use of a disilylated polymer Al) of formula (II) in which m is non-zero leads to an improvement in adhesive performance on all of the low surface energy substrates tested compared to the use of a disilylated polymer Al) of formula (II) in which m is zero, of number-average molecular mass and comparable silylated end groups:
    series (5.1): comparison of the composition of Example 4 and of Example 13;
    6) the use of a disilylated polymer Al) having dialkoxysilane end groups, leads to an improvement in adhesive performance on PP, compared to the use of a disilylated polymer Al) having trialkoxysilane end groups, in admixture with the same monosilylated polymer A.2) dialkoxysilylated:
    series (6.1): comparison of the compositions of Examples 14 and 13;
    7) the use of a monosilylated polymer A.2) having dialkoxysilyl end groups leads to an improvement in adhesive performance at least on PP compared to the use of a monosilylated polymer A.2) having trialkoxysilyl end groups, mixed with the same disilylated polymer Al:
    series (7.1): comparison of the composition of Example 10 and of Example 9: the use of a polymer A.2) having dialkoxysilane end groups improves the adhesion to HDPE and PP compared to use of a polymer A.2) having trialkoxysilane end groups, series (7.2): comparison of the compositions of Examples 4 and 3 according to the invention: the use of a polymer A.2) having dialkoxysilane end groups improves adhesion to PP relative to the use of a polymer A.2) having trialkoxysilane end groups;
    8) the use of at least one resin of type (i) (T5), and preferably of at least one resin of type (i) and (ii) (T5 + T4 or T5 + T3), leads to an improvement in adhesive performance at least on the PP compared to the use of a mixture of tackifying resins not comprising resin (s) of the aforementioned type (s):
    series (7.1): comparison of the compositions of Examples 1 and 9 according to the invention: the mixture T5 and T4 improves the adhesion to PP and HDPE compared to the mixture Tl and T4,
    - series (7.2): comparison of the compositions of Examples 2 and 4 according to the invention:
    the mixture T5 and T4 improves the adhesion to PP compared to the mixture Tl and T4, series (7.3): comparison of the compositions of Examples 2 and 5: the mixture T5 and T3 improves the adhesion to PP compared to the mixture Tl and T3.
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    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. Adhesive composition comprising:
    A1) at least 4% by weight of one or more polysilylated polymers having a number average molecular mass (Mn) of at least 6,000 g / mol, and chosen from polymers comprising a main chain of polyether type and / or polyurethane and at least two hydrolyzable silylated end groups, said silylated end groups being attached to the main chain of the polymer by a urethane or ether function (said connector group),
    A.2) at least 13% by weight of one or more monosilylated polymers having a number average molecular mass (Mn) of at least 1000 g / mol, and chosen from polymers comprising a main chain of polyether type and / or polyurethane and a hydrolyzable silylated end group, said silylated end group being attached to the main chain of the polymer by a urethane or ether function (said connector group),
    B) at least 25% by weight of one or more tackifying resins having (each) a hydroxyl number less than or equal to 100, and
    C) at least 0.2% of one or more crosslinking catalysts, the contents in% by weight being expressed relative to the total weight of the adhesive composition, and the sum of the contents of all the ingredients of the adhesive composition being equal to 100%.
    [2" id="c-fr-0002]
    2. Composition according to claim 1, such as the polysilylated polymer A. 1) or at least one of the polysilylated polymers Al), preferably the polysilylated polymer Al) or all of the polysilylated polymers Al), corresponds (s) to one of the following formulas, or a mixture thereof:
    - formula (I):
    Q-R-SKR UOR b-, (I) in which:
    - B represents a divalent (for f = 2) or trivalent (for f = 3) hydrocarbon radical comprising from 2 to 66 carbon atoms, linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated, optionally comprising one or more heteroatoms , such as O, N,
    R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms,
    - R ' 2 represents a linear or branched divalent alkylene radical comprising from 2 to 4 carbon atoms,
    - R 4 and R 5 , identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R 4 possibly being able to be engaged in a ring, preferably R 4 is a methyl group, n '' is a non-zero integer such that the number-average molecular mass of the polyether block of formula - [OR ' 2 ] n ”- ranges from 150 g / mole to 20,000 g / mole, p is an integer equal to 0 or 1, f is an integer equal to 2 or 3, the indices n ”and f are such that the number-average molecular mass of the polysilylated polymer (s) Al) is as defined in claim 1 ;
    - formula (II):
    , 2 1 2 ^ 3 4 5 B —- OR - 10 C NH R NH C 0R . _ 0 _ c _ NH _ R! _ S | y 0R LL not' L | It * - J n Jm L!
    (Π) in which:
    - B represents a divalent (for f = 2) or trivalent (for f = 3) hydrocarbon radical comprising from 2 to 66 carbon atoms, linear, branched, cyclic, alicyclic or aromatic, saturated or unsaturated, optionally comprising one or more heteroatoms , such as O, N,
    R 1 represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which can be aromatic or aliphatic, linear, branched or cyclic,
    R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms,
    - R 2 and R ' 2 , identical or different, each represent a divalent linear or branched alkylene radical comprising from 2 to 4 carbon atoms,
    - R 4 and R 5 , identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R 4 possibly being able to be engaged in a ring, preferably R 4 is a methyl group, n is a non-zero integer such that the number-average molecular mass of the polyether block of formula - [OR 2 ] n- ranges from 300 g / mole to 40,000 g / mole, n 'is a zero or non-zero integer such that the number-average molecular mass of the polyether block of formula - [OR , 2 ] n '- ranges from 0 to 20,000 g / mole, m is an integer which is zero or not zero, p is an integer equal to 0 or 1, f is an integer equal to 2 or 3,
    - the indices m, n, n ’and f are such that the number-average molecular mass of the polysilylated polymer (s) A. 1) is as defined in claim 1.
    [3" id="c-fr-0003]
    3. Composition according to claim 1 or 2, such as the monosilylated polymer A.2) or at least one of the monosilylated polymers A.2), preferably the monosilylated polymer A.2) or all of the monosilylated polymers A .2), responds to one of the following formulas, or to their mixture:
    - formula (Ibis):
    (Ibis) in which:
    R ° represents a divalent hydrocarbon radical comprising from 1 to 60 carbon atoms which can be aliphatic, aromatic or alkyl aromatic, linear, branched or cyclic,
    R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms,
    - R ' 2 represents a linear or branched divalent alkylene radical comprising from 2 to 4 carbon atoms,
    - R 4 and R 5 , identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R 4 possibly being able to be engaged in a ring, preferably R 4 is a methyl group, n '''is a zero or non-zero integer such that the number-average molecular mass of the polyether block of formula - [OR' 2 ] n ”- ranges from 0 g / mole to 20,000 g / mole,
    - p is an integer equal to 0, 1 or 2.
    - R ° and n ’” are such that the number-average molecular mass of the monosilylated polymer (s) A.2) is as defined in claim 1;
    - formula (Ilbis):
    R— | -OR— '.Ο_ Ο _ ΝΗ _ Κ _ ΝΗ Ρ_0 (Ilbis) in which:
    R ° represents a divalent hydrocarbon radical comprising from 1 to 60 carbon atoms which can be aliphatic, aromatic or alkyl aromatic, linear, branched or cyclic,
    R 1 represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic,
    R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms,
    - R 2 and R ' 2 , identical or different, each represent a linear or branched divalent alkylene radical comprising from 2 to 4 carbon atoms,
    - R 4 and R 5 , identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, R 4 possibly being able to be engaged in a ring, preferably R 4 is a methyl group, n is a whole number such that the number-average molecular mass of the polyether block of formula - [OR 2 ] n- ranges from 300 g / mole to 40,000 g / mole, n '''is a zero or non-zero integer such that the number average molecular weight of the polyether block of formula - [OR ' 2 ] n ”- ranges from 0 to 20,000 g / mole, m is an integer which is zero or not zero, p is an integer equal to 0, 1 or 2.
    - R ° and the indices m, n and n ’” are such that the number-average molecular mass of the monosilylated polymer (s) A.2) is as defined in claim 1.
    [4" id="c-fr-0004]
    4. Composition according to claim 2 or 3, such that the polysilylated polymer (s) A. 1) corresponds (s) to formula (II), in which m is preferably non-zero.
    [5" id="c-fr-0005]
    5. Composition according to claim 3 or 4, such that the monosilylated polymer (s) A.2) corresponds (s) to formula (Ilbis), in which m is preferably zero.
    [6" id="c-fr-0006]
    6.
    Composition according to any one of Claims 2 to 5, such that p = 0.
    [7" id="c-fr-0007]
    7. Composition according to any one of claims 2 to 5, such p = 1.
    [8" id="c-fr-0008]
    8. Composition according to any one of claims 1 to 7, such that the polysilylated polymer (s) A.l) is (are) disilylated (s).
    [9" id="c-fr-0009]
    9. Composition according to any one of claims 1 to 8, such as:
    the number-average molecular mass of the polysilylated polymer (s) Al) ranges from 6,000 to 55,000 g / mol, preferably from 15,000 to 50,000 g / mol, more preferably from 20,000 to 45,000 g / mol, and
    - the number-average molecular mass of the monosilylated polymer (s) A.2) ranges from 1,000 to 55,000 g / mol, preferably from 2,000 to 45,000 g / mol, more preferably from 3,000 to 35,000 g / mol.
    [10" id="c-fr-0010]
    10. Composition according to any one of claims 1 to 9, such that the tackifying resin (s) has (s) (each) a hydroxyl number less than or equal to 50, and more preferably equal to zero has a number average molecular weight ranging from 100 to 6,000 g / mol, preferably from 300 to 4,000 g / mol, and is (are) chosen from:
    (i) the resins obtained by polymerization or copolymerization, optionally by hydrogenation, of mixtures of unsaturated and / or aromatic aliphatic hydrocarbons having approximately 5, 9 or 10 carbon atoms derived from petroleum fractions;
    (ii) resins obtained by a process comprising the polymerization of alpha-methyl styrene or the copolymerization of alpha-methyl-styrene with other hydrocarbon monomers;
    (iii) rosins of natural or modified origin, such as for example rosin extracted from pine gum, wood rosin extracted from the roots of the tree and their hydrogenated, dimerized, polymerized or esterified derivatives with monoalcohols or polyols, such as glycerol or pentaerythritol; and (iv) their mixtures.
    [11" id="c-fr-0011]
    11. Composition according to any one of claims 1 to 10, such as:
    the content of polysilylated polymer (s) Al) represents from 5 to 59.8% by weight, more preferably from 15 to 54.8% by weight, and better still from 20 to 44.8% by weight, the weight of the adhesive composition,
    the content of monosilylated polymer (s) A.2) represents from 15 to 69.8% by weight, preferably from 15 to 54.8% by weight, and better still from 20 to 44.8% by weight of the weight of the adhesive composition,
    the content of tackifying resin (s) B) ranges from 25 to 79.8% by weight, preferably from 30 to 69.8% by weight, and better still from 35 to 59.8% by weight, the weight of the adhesive composition,
    - The content of crosslinking catalyst (s) C) ranges from 0.2 to 4% by weight of the weight of the adhesive composition.
    [12" id="c-fr-0012]
    12. Self-adhesive article comprising a support layer coated with a self-adhesive layer, said self-adhesive layer consisting of an adhesive composition as defined in any one of claims 1 to 11 in the crosslinked state.
    [13" id="c-fr-0013]
    13. Self-adhesive article according to claim 12, capable of being obtained by the process comprising the following steps:
    (a) conditioning the adhesive composition according to the invention as defined above at a temperature ranging from 20 to 130 ° C; then (b) coating with the adhesive composition obtained in step (a) of a carrier surface; then (c) crosslinking the coated adhesive composition, by heating to a temperature ranging from 20 to 200 ° C in a gaseous environment where water molecules are present between 10 and 200 mg per m 3 of gas;
    (d) lamination or transfer of the crosslinked adhesive layer on a support layer or on a non-stick protective film, said support layer or non-stick film being able to be the back of the support surface.
    [14" id="c-fr-0014]
    14. Self-adhesive article according to claim 12 or 13, characterized in that the support layer has an elongation at break strictly less than 100% and is based on acrylic polymers, oriented Polyethylene (PE), Polypropylene (PP) , non-oriented or bi-oriented, Polyimide, Polyurethane, Polyester such as Polyethylene terephthalate (PET), or paper.
    [15" id="c-fr-0015]
    15. Product coated at its surface with a self-adhesive article as defined in any one of claims 12 to 14, said surface having a surface energy less than or equal to 40mN / m, preferably ranging from 23 at 38 mN / m, more preferably ranging from 25 to 35 mN / m, said surface energy being measured at 23 ° C., at 50% relative humidity, at atmospheric pressure of 1 bar, in air.
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    同族专利:
    公开号 | 公开日
    WO2018078271A1|2018-05-03|
    FR3058152B1|2018-11-16|
    EP3532108B1|2022-01-19|
    CN110087696A|2019-08-02|
    JP2019536859A|2019-12-19|
    EP3532108A1|2019-09-04|
    US20190256745A1|2019-08-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2013136108A1|2012-03-12|2013-09-19|Bostik Sa|Breathable self-adhesive articles|
    EP2889348A1|2013-12-30|2015-07-01|Bostik Sa|Self-adhesive article with foam support|
    EP2889349A1|2013-12-30|2015-07-01|Bostik Sa|Self-adhesive article with foam support|
    FR2925517B1|2007-12-21|2010-01-08|Bostik Sa|ADHESIVE SENSITIVE TO ADHESIVE PRESSURE STABLE IN TEMPERATURE.|
    RU2525904C2|2008-07-02|2014-08-20|ЗМ Инновейтив Пропертиз Компани |Low-surface energy adhesive|
    FR2954341B1|2009-12-21|2014-07-11|Bostik Sa|ADHESIVE COMPOSITION RETICULABLE BY HEATING|US11207919B2|2016-06-21|2021-12-28|Bridgestone Americas Tire Operations, Llc|Methods for treating inner liner surface, inner liners resulting therefrom and tires containing such inner liners|
    FR3075218B1|2017-12-14|2020-10-30|Bostik Sa|MULTI-COMPONENT ADHESIVE COMPOSITION AND ITS USES|
    WO2022006713A1|2020-07-06|2022-01-13|Wacker Chemie Ag|Cross-linkable masses based on silane-terminated polymers|
    法律状态:
    2017-09-18| PLFP| Fee payment|Year of fee payment: 2 |
    2018-05-04| PLSC| Publication of the preliminary search report|Effective date: 20180504 |
    2018-09-13| PLFP| Fee payment|Year of fee payment: 3 |
    2019-09-13| PLFP| Fee payment|Year of fee payment: 4 |
    2020-02-28| CA| Change of address|Effective date: 20200122 |
    2020-09-14| PLFP| Fee payment|Year of fee payment: 5 |
    2021-09-13| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1660509A|FR3058152B1|2016-10-28|2016-10-28|SELF-ADHESIVE COMPOSITION FOR BONDING LOW ENERGY SURFACE SUBSTRATES|
    FR1660509|2016-10-28|FR1660509A| FR3058152B1|2016-10-28|2016-10-28|SELF-ADHESIVE COMPOSITION FOR BONDING LOW ENERGY SURFACE SUBSTRATES|
    PCT/FR2017/052925| WO2018078271A1|2016-10-28|2017-10-24|Self-adhesive composition for the bonding of substrates with low surface energy|
    JP2019523787A| JP2019536859A|2016-10-28|2017-10-24|Adhesive composition for bonding substrates having low surface energy|
    US16/344,067| US20190256745A1|2016-10-28|2017-10-24|Self-adhesive composition for the bonding of substrates with low surface energy|
    CN201780081038.8A| CN110087696A|2016-10-28|2017-10-24|For bonding the self-adhesive composition of the substrate with low-surface-energy|
    EP17797700.6A| EP3532108B1|2016-10-28|2017-10-24|Self-adhesive composition for the bonding of substrates with low surface energy|
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