Adhesive bonding agent for PVDF, its application as barrier mate

Stock material or miscellaneous articles – Composite – Of fluorinated addition polymer from unsaturated monomers

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4284769, 428500, 5263184, B32B 2700

Patent

active

061434159

DESCRIPTION:

BRIEF SUMMARY
TECHNICAL FIELD

The present invention relates; to an adhesive bonding agent for PVDF and to its application as barrier material, as well as to the materials obtained from the latter.


BACKGROUND ART

EP 3449 describes coextrusion of PVDF with polyurethanes (PU); use of a bonding agent is unnecessary. FR 2 436 676 describes coextrusion of PVDF with polymethyl methacrylate (PMMA) and an acrylonitrile-butadiene-styrene (ABS), the PMMA film being between the PVDF and ABS films. Another example was made with poly(vinyl chloride) (PVC) instead of ABS. EP 450,994 describes an improvement to the above technique, which employs as coextrusion bonding agent the mixture: (a) 27 to 50 parts of PMMA and (b) 73 to 50 parts of a product itself consisting, per 100 parts, of 35 to 50 parts of PVDF and 65 to 50 parts of acrylic or methacrylic elastomer. This improvement increases the adhesiveness of PVDF to ABS.
FR-A-2,457,180 describes polyalkyl methacrylate as an agent for bonding PVDF to incompatible polymers. Among the incompatible polymers are mentioned ABS, polyurethane, polystyrene, polycarbonate, PVC and styrene/acrylic copolymers. However, this bonding agent, in particular PMMA, is not suitable or exhibits a low adhesion towards certain incompatible polymers.
Thus, there is no satisfactory coextrusion bonding agent for adhesively bonding a PVDF film to all the polymers which are incompatible with the latter, in particular polyamide or to a polyamide-based product.


DISCLOSURE OF THE INVENTION

The inventors has now found an adhesive bonding agent for PVDF, including a specific polymer.
Thus, the present invention provides an adhesive bonding for PVDF agent enabling it to be made to adhere to polymers which are incompatible with it, characterized in that it includes a polymer A containing units: ##STR1## in which: R.sub.1 denotes H or a linear or branched alkyl containing from 1 to 20 carbon atoms, and does not denote H, denotes a linear or branched alkyl containing from 1 to 20 carbon atoms, ##STR2## in which: R.sub.3 denotes H or a linear or branched alkyl containing from 1 to 20 carbon atoms,
When the unit (2) is present in its anhydride form, it is denoted by the formula: ##STR3## in which R.sub.4 and R.sub.5, which are identical or different, denote H or a linear or branched alkyl containing from 1 to 20 carbon atoms.
The term "units (2) in acidic form or its anhydride derivatives or mixtures of these" covers especially the following cases: the units (2) are substantially in acidic form; the units (2) are substantially in anhydride form, mixtures of units (2) in acidic form and in anhydride form, mixtures of units (2) where the radicals R.sub.3 or R.sub.4 and R.sub.5 are variable. The formula given for the unit (2) also includes generally the units bearing an acidic functionality. Similarly the units (1) may be mixtures when radicals R.sub.1 and R.sub.2 are variable.
According to an embodiment, the polymer A includes, on a molar basis, up to 30% of unit (2), in acidic form, or its anhydride derivative or their mixtures. Advantageously, the polymer A includes, on a molar basis, up to 15% of unit (2), in acidic form, or its anhydride derivative or their mixtures.
According to another embodiment, the polymer A contains chiefly the unit (2) in acidic form.
According to still another embodiment, in the unit (1) of the polymer A, R.sub.1 and R.sub.2 denote the methyl radical. In this case the bonding agent is a bonding agent based on PMMA.
According to yet another embodiment, in the unit (2) of the polymer A, R.sub.3 denotes the hydrogen or methyl radical in the case where the unit (2) is in acidic form, and R.sub.4 and R.sub.5 denote the hydrogen or methyl radical in the case where the unit (2) is in anhydride form.
The abovementioned polymers A can be prepared by any suitable process known in the art. For example, the process described in EP-A-216,505 will be mentioned.
For the purposes of the present invention, PVDF denotes a homopolymer or a copolymer containing at least 70% by weight of vinylidene fluoride res

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