# US 11,441,007 B2 · Fluoropolymer composition for multilayer assemblies

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- Number: US 11,441,007 B2
- Document ID: US11441007B2
- Status: Granted
- Kind: B2
- Application number: 14/131,747
- Filed: 2012-07-10
- Published: 2014-05-08
- Granted: 2022-09-13
- Earliest claimed: 2011-07-15
- Assignees: Solvay Specialty Polymers Italy S.P.A.
- Applicants: Stefano Mortara; Julio A. Abusleme
- Inventors: Stefano Mortara; Julio A. Abusleme
- Web page: https://patentgrep.com/patent/US11441007B2

## CPC

- C08K 3/22: of metals
- B29C 48/21: the layers being joined at their surfaces
- B32B 27/304: {comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF}
- B32B 27/36: comprising polyesters
- C08F 14/22: Vinylidene fluoride
- C08K 3/30: Sulfur-, selenium- or tellurium-containing compounds
- C08L 27/16: Homopolymers or copolymers or vinylidene fluoride
- C09D 127/16: Homopolymers or copolymers of vinylidene fluoride
- C08J 2427/16: Homopolymers or copolymers of vinylidene fluoride
- C08K 2003/2296: {of zinc}
- Y10T 29/49826: Assembling or joining
- Y10T 428/1352: Polymer or resin containing [i.e., natural or synthetic]
- Y10T 428/1393: Multilayer [continuous layer]
- Y10T 428/31515: As intermediate layer
- Y10T 428/3154: Of fluorinated addition polymer from unsaturated monomers
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The invention pertains to a composition (C1) comprising: at least one (meth)acrylic modified VDF polymer [polymer (A)] comprising recurring units derived from comprising recurring units derived from vinylidene fluoride (VDF) monomer and at least one hydrophilic (meth)acrylic monomer (MA) of formula (I), wherein each of R1, R2, R3, equal or different from each other, is independently a hydrogen atom or a C1-C3 hydrocarbon group, and ROH is a hydrogen or a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group; at least one inorganic UV blocker compound in an amount not exceeding 5% wt, with respect to the weight of polymer (A), to multilayer assemblies comprising one layer made from said composition (C1), to a method for manufacturing said multilayer assemblies and to the use of the same in different field of use, including protection of PV modules.

## Claims

### Claim 1

A multilayer assembly comprising:
a first layer (L1) made from a composition (C1), wherein the composition (C1) comprises:
at least one acrylic modified VDF polymer (A) comprising at least 90% moles of recurring units derived from at least one vinylidene fluoride (VDF) monomer and at least 0.05% moles and at most 10% moles of recurring units derived from at least one hydrophilic acrylic monomer (MA) selected from the group consisting of:
hydroxyethylacrylate (HEA) of formula:
2-hydroxypropyl acrylate (HPA) of either of formulae:
acrylic acid (AA) of formula:
and mixtures thereof, and
at least one inorganic UV blocker compound comprising ZnO, wherein the inorganic UV blocker compound is present in an amount not exceeding 5% wt, with respect to the weight of polymer (A), and wherein the average particle size of said inorganic UV blocker compound is less than 150 nm; and
a second layer (L2) made from a second composition (C2), wherein composition (C2) comprises at least one polyester (P) selected from the group consisting of:
polyglycolide, polyglycolic acid (PGA) and copolymers thereof, optionally in admixture with other polycondensable comonomer(s);
polylactic acid (PLA) and copolymers thereof, optionally in admixture with other polycondensable comonomer(s);
polycaprolactone (PCL) and copolymers thereof, optionally in admixture with other polycondensable comonomer(s);
polyethyleneadipate (PEA) and other copolymers;
polyhydroxyalkanoate (PHA), which are the result of polycondensation of hydroxy fatty acids with chain lengths from 3 to 15 carbon atoms;
polyethylene terephthalate (PET) and copolymers thereof, optionally in admixture with other polycondensable comonomer(s);
polybutylene terephthalate (PBT) and copolymers thereof, optionally in admixture with other polycondensable comonomer(s);
polytrimethylene terephthalate (PTT) and copolymers thereof, optionally in admixture with other polycondensable comonomer(s); and
polyethylene naphthalate (PEN) and copolymers thereof, optionally in admixture with other polycondensable comonomer(s).

### Claim 2 (depends on 1)

The multilayer assembly of claim 1, wherein the acrylic modified VDF polymer (A) comprises recurring units derived from the at least one vinylidene fluoride (VDF) monomer, from at least one additional monomer selected from the group consisting of trifluoroethylene, trifluorochloroethylene, hexafluoropropylene, and fluoroalkyl vinyl ether, and from the at least one hydrophilic acrylic monomer (MA), wherein the amount of vinylidene fluoride (VDF) monomer is at least 90% mol, with respect to the total of the vinylidene fluoride (VDF) monomer and the additional monomer.

### Claim 3 (depends on 1)

The multilayer assembly of claim 1, wherein the average particle size of said inorganic UV blocker compound is less than 120 nm.

### Claim 4 (depends on 1)

The multilayer assembly of claim 1, wherein said inorganic UV blocker compound comprises ZnO in combination with at least one other inorganic oxide compound.

### Claim 5 (depends on 1)

The multilayer assembly of claim 1, said composition comprising said inorganic UV blocker compound in an amount not exceeding 4% wt, with respect to the weight of polymer (A).

### Claim 6 (depends on 1)

The multilayer assembly of claim 1, wherein composition (C2) further comprises at least one polyolefin (O) selected from the group consisting of polymers comprising recurring units derived from ethylene, propylene and mixtures thereof.

### Claim 7 (depends on 1)

A tube, pipe, cladding, film, sheet, profile, plaque or hollow body comprising the multilayer assembly according to claim 1.

### Claim 8 (depends on 1)

The multilayer assembly of claim 1, wherein polymer (A) comprises at least 0.2% moles, and at most 3% moles of recurring units derived from said hydrophilic acrylic monomer (MA).

### Claim 9 (depends on 1)

The multilayer assembly of claim 1, wherein the average particle size of said inorganic UV blocker compound is less than 80 nm.

### Claim 10

A multilayer assembly comprising:
a first layer (L1) made from a composition (C1), wherein the composition (C1) comprises:
at least one acrylic modified VDF polymer (A) comprising at least 90% moles of recurring units derived from at least one vinylidene fluoride (VDF) monomer and at least 0.05% moles and at most 10% moles of recurring units derived from at least one hydrophilic acrylic monomer (MA) selected from the group consisting of:
hydroxyethylacrylate (HEA) of formula:
2-hydroxypropyl acrylate (HPA) of either of formulae:
acrylic acid (AA) of formula:
and mixtures thereof, and
at least one inorganic UV blocker compound comprising ZnO, wherein the inorganic UV blocker compound is present in an amount not exceeding 5% wt, with respect to the weight of polymer (A), and wherein the average particle size of said inorganic UV blocker compound is less than 150 nm; and
a second layer (L2) made from a second composition (C2),
said assembly additionally comprising a third layer (L3), said layer (L3) adhering to layer (L1) on one side and to layer (L2) on the opposite side, wherein layer (L3) is made from a composition (C3) comprising at least one of:
(C3-A) alpha-olefin polymers modified by grafting of at least one monomer comprising a functional group selected from the group consisting of a carboxyl acid in its acid, ester, salt, amide, anhydride form, a hydroxyl, and an epoxide; and
(C3-B) linear copolymers comprising recurring units derived from monoethylenic monomers which carry an alkyl carboxylate functional group.

### Claim 11 (depends on 10)

The multilayer assembly of claim 10, said assembly additionally comprising at least one layer (L4) made from at least one metal compound (M).

### Claim 12 (depends on 1)

A method for manufacturing the multilayer assembly of claim 1, said method comprising coextruding a layer (L1), a layer (L2) and optionally, a layer (L3).

### Claim 13 (depends on 1)

A method for protecting a PV module comprising covering said module with at least one multilayer assembly according to claim 1.