Stock material or miscellaneous articles – Hollow or container type article – Glass – ceramic – or sintered – fused – fired – or calcined metal...
Reexamination Certificate
1997-07-03
2001-07-03
Kiliman, Leszek (Department: 1773)
Stock material or miscellaneous articles
Hollow or container type article
Glass, ceramic, or sintered, fused, fired, or calcined metal...
C428S034700, C428S035200, C428S035700, C428S035900, C428S036900, C428S036910, C428S412000, C428S413000, C428S414000, C428S416000, C428S418000, C428S457000, C428S461000, C428S501000, C428S515000, C428S524000
Reexamination Certificate
active
06254944
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a multilayer structure comprising a layer of a binder and, directly attached thereto, a layer of polyketone. The binder is either a polymer containing hydroxyl functions or a polymer containing epoxy functions or a copolymer of ethylene and of an alkyl (meth)acrylate. The invention also relates to the above structure and, directly attached thereto on the binder side, a layer (F) of a thermoplastic polymer, such as polyethylene, of a rubber or alternatively a metal layer.
Thus, the invention provides a binder to bring about adhesion of a layer of polyketone and either a metal layer or a layer of a thermoplastic or of a rubber. The structures of the invention are useful for manufacturing flexible or rigid packages such as sachets or bottles, or for manufacturing pipes. These products may be manufactured by coextrusion, lamination or coextrusion blow-moulding. The polyketones are linear alternating copolymers of carbon oxide and of at least one unsaturated monomer.
BACKGROUND OF THE INVENTION
Application WO 95/09212 describes multilayers consisting of a layer of polyketone and a layer of polyolefin; the binder placed between these two layers is the reaction product of a polyolefin grafted with maleic anhydride and a diamine.
U.S. Pat. No. 5,369,170 describes a similar binder. The manufacture of the binders of the prior art may lead to crosslinking, which complicates their use, in particular the melt index (MFI) may be such that coextrusion can no longer be carried out.
DESCRIPTION OF THE INVENTION
The binder of the present invention is much simpler; it may be:
either a thermoplastic polymer containing at least one hydroxyl function, which may be a polymer having a hydroxyl function, a mixture of polymers each having at least one hydroxyl function or a mixture of a polymer having at least one hydroxyl function with another polymer or any other combination.
or a thermoplastic polymer containing at least one epoxy function, which may be a polymer having an epoxy function, a mixture of polymers each having at least one epoxy function or a mixture of a polymer having at least one epoxy function with another polymer or any other combination.
or a thermoplastic polymer comprising ethylene units and at least one alkyl (meth)acrylate unit.
As regards the binder containing a hydroxyl function, the hydroxyl function is integrated into the polymer either by polymerization or by grafting of one or more appropriate monomers, or by chemical modification of an appropriate function which is already present in the polymer, or by reaction of the polymer which has been functionalized or of a functionalized polymer with a product providing at least one hydroxyl function.
The various reactions (polymerization, grafting or modification) are carried out according to the rules of the art in the solid or molten state or in solution.
The hydroxyl function is generally provided either by functional acrylic monomers such as, for example, HEA or HEMA (hydroxyethyl acrylate or methacrylate), or by alcohols bearing a polymerizable or graftable function (for example vinyl) such as, for example, vinylphenol. These monomers may also bear other functionalities that are sparingly reactive or unreactive with hydroxyl functions, such as an amide or an amine.
The hydroxyl function may also be obtained from an appropriate function which is already present in the polymer, by means of a suitable reaction, such as, for example, the catalysed hydrolysis of a vinyl alkylate function.
Other monomers may also be present in the polymer, such as one or more olefins (ethylene, propylene, butene, hexene, octene, 4-methylpentene, vinylnorbornene, etc.), an alkyl acrylate or methacrylate or a vinyl alkyl. These monomers may be present together.
The products obtained may be used alone or as a mixture with polymers which themselves may or may not contain hydroxyl functions. The use of an additive or of another polymer may be necessary in the case of mixtures in order to ensure good mixing and good compatibilization of the polymers.
It is also possible to start with a polymer bearing a carboxylic acid or carboxylic acid anhydride function, this function having been provided, for example by copolymerization or by grafting, to neutralize this function with a diol such as ethylene glycol or with a polyether diol such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
Advantageously, the polymers on which the hydroxyl function is provided by grafting are polyolefins. The monomers which are polymerized with monomers bearing a hydroxyl function or a function which may be converted into a hydroxyl function are advantageously olefins. The polymers bearing carboxylic acid or carboxylic acid anhydride functions are also advantageously polyolefins.
The term polyolefins is understood to refer to:
homopolymers of ethylene or of propylene;
copolymers of ethylene and of vinyl acetate;
copolymers of ethylene and of at least one alkyl (meth)acrylate. The alkyl group of the alkyl (meth)acrylate has up to 10 carbon atoms and may be linear, branched or cyclic. By way of illustration of the alkyl (meth)acrylate, mention may be made in particular of n-butyl acrylate, methyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate. Among these (meth)acrylates, ethyl acrylate, methyl acrylate, n-butyl acrylate and methyl methacrylate are preferred.
copolymers of ethylene and of butene or of ethylene and of hexene.
amorphous poly-alpha-olefins (APAOs).
Preferably, APAOs derived from ethylene, propylene, butene or hexene are used. Either ethylene propylene butene copolymers with a high butene content or ethylene propylene butene with a high propylene content or butene homo- or copolymers are advantageously used.
Ethylene/alkyl (meth)acrylate copolymers are advantageously used.
Thus, the binder containing a hydroxyl function may be, for example, an ethylene/(meth)acrylate/hydroxyethyl (meth)acrylate copolymer, an ethylene/vinyl acetate/hydroxyethyl (meth)acrylate copolymer or ethylene/alkyl or ethylene (meth)acrylate/vinyl acetate copolymers grafted with hydroxyethyl (meth)acrylate.
The hydroxyethyl polyacrylates or polymethacrylates are not always thermoplastic. It is thus advantageous to mix them with other polymers so that the resin has a thermoplastic nature. Since the resin is thermoplastic, it may readily be converted into a film in order, for example, to be coextruded.
It is also possible, even if the polymer having at least one hydroxyl function is thermoplastic, to mix it with other thermoplastic polymers.
As examples of polymers which may be mixed with the polymers having a hydroxyl function, mention may be made of:
polyethylene, polypropylene;
copolymers of ethylene with at least one product chosen from (i) salts and esters of unsaturated carboxylic acids, (ii) vinyl esters of saturated carboxylic acids, (iii) alpha-olefins, it being possible for the monomers (i) to (iii) to be grafted or copolymerized;
styrene/ethylene-butene/styrene (SEBS) block copolymers;
styrene/butadiene/styrene (SBS) block copolymers;
styrene/isoprene/styrene (SIS) block copolymers.
The composition of the mixtures, the comonomer content, the amount of hydroxyl functions and the structure of the polymers are optimized with regard to the desired adhesion and implementation properties.
It may be necessary to add compatibilizing agents to the resin in order to promote the homogeneity of the resin. These products are known per se; they are, for example, functionalized polyolefins such as copolymers of ethylene with at least one product chosen from (i) unsaturated carboxylic acids, salts thereof and esters thereof, (ii) unsaturated dicarboxylic acids, salts thereof, esters thereof, hemiesters thereof and anhydrides thereof, (iii) vinyl esters of saturated carboxylic acid, (iv) alpha-olefins, it being possible for the monomers (i) to (iv) to be grafted or copolymerized.
As examples of thermoplastic resins containing at least one hydroxyl function,
Le Roy Christophe
Robert Patrice
Elf Atochem S.A.
Kiliman Leszek
Smith Gambrell & Russell
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