# US 11,441,009 B2 · Flexible polyvinyl halide used for injection over-molding

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- Number: US 11,441,009 B2
- Document ID: US11441009B2
- Status: Granted
- Kind: B2
- Application number: 16/469,453
- Filed: 2017-12-13
- Published: 2020-02-06
- Granted: 2022-09-13
- Earliest claimed: 2016-12-14
- Assignees: GEON Performance Solutions, LLC
- Applicants: Geon Performance Solutions, LLC
- Inventors: Sang Lee; Ling Hu; Craig L. Shoemaker; Robert Schilling
- Web page: https://patentgrep.com/patent/US11441009B2

## CPC

- C08K 3/26: Carbonates; Bicarbonates
- B29C 45/0001: {characterised by the choice of material}
- B32B 5/16: characterised by features of a layer formed of particles, e.g. chips, powder {or granules (layer formed of natural mineral particles B32B19/00; layer being formed of wood fibres, chips or particles B32B21/02)}
- B32B 5/18: characterised by features of a layer {of} foamed material
- B32B 27/065: {of foam}
- B32B 27/08: of synthetic resin
- B32B 27/14: next to a particulate layer
- B32B 27/20: using fillers, pigments, thixotroping agents
- B32B 27/22: using plasticisers
- B32B 27/30: comprising vinyl {(co)polymers; comprising acrylic (co)polymers}
- B32B 27/302: {comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers}
- B32B 27/304: {comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF}
- B32B 27/306: {comprising vinyl acetate or vinyl alcohol (co)polymers}
- B32B 27/32: comprising polyolefins {(comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30)}
- B32B 27/36: comprising polyesters
- B32B 27/40: comprising polyurethanes
- C08K 5/12: of cyclic polycarboxylic acids
- C08K 9/04: Ingredients treated with organic substances {(treated with macromolecular compounds C08K9/08)}
- C08K 9/06: with silicon-containing compounds
- C08L 27/06: Homopolymers or copolymers of vinyl chloride
- B29C 45/14: incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles {(B29C45/1671 takes precedence)}
- B29K 2027/06: PVC, i.e. polyvinylchloride
- B29K 2105/0038: {Plasticisers}
- B29K 2509/14: {Stones}
- B32B 2250/02: 2 layers
- B32B 2250/24: All layers being polymeric
- B32B 2264/104: Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
- B32B 2266/0235: Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
- B32B 2270/00: Resin or rubber layer containing a blend of at least two different polymers
- B32B 2307/536: Hardness
- B32B 2307/546: Flexural strength; Flexion stiffness
- B32B 2307/748: Releasability
- C08K 3/013: Fillers, pigments or reinforcing additives
- C08K 5/0016: {Plasticisers}
- C08K 2003/265: {Calcium, strontium or barium carbonate}
- C08K 2201/005: Additives being defined by their particle size in general
- 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
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

## Abstract

A polyvinyl halide compound, alone or alloyed with thermoplastic polyurethane, is used as a flexible layer for over-molding a rigid polymer substrate. Selection of types and amounts of calcium carbonate for the overmolding layer improves peel strength to achieve cohesive failure of the flexible overmolding layer rather than adhesive failure of the interface between the flexible overmolding layer and the rigid polymer substrate.

## Claims

### Claim 1

A polymer compound, comprising:
polyvinyl halide having an inherent viscosity of less than about 0.9, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243;
an effective amount of plasticizer to provide a desired amount of flexibility to the polyvinyl halide and form a plasticized polyvinyl halide compound; and
stearic acid-treated calcium carbonate fillers, or silane-treated calcium carbonate fillers, or both stearic acid-treated calcium carbonate fillers and silane-treated calcium carbonate fillers dispersed in the plasticized polyvinyl halide compound;
wherein, when the plasticized polyvinyl halide compound is overmolded as a layer on to a Rigid PVC Test Substrate and undergoes a Modified ASTM D903 Adhesion Peel Strength Test, the layer of plasticized polyvinyl halide compound experiences cohesive failure; and
wherein the plasticizer is present in an amount of at least about 20 weight parts per hundred weight parts of polyvinyl halide.

### Claim 2 (depends on 1)

The polymer compound of claim 1, wherein the polyvinyl halide is polyvinyl chloride.

### Claim 3 (depends on 1)

The polymer compound of claim 1, wherein the polyvinyl halide has a weight average molecular weight of from about 39,000 to about 150,000 where the molecular weight is measured by size exclusion chromatography.

### Claim 4 (depends on 1)

The polymer compound of claim 1, wherein the polyvinyl halide has an inherent viscosity of from about 0.65 to about 0.85, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243.

### Claim 5 (depends on 1)

The polymer compound of claim 1, wherein the plasticizer is selected from the group consisting of phthalates, citrates, soyates, trimellitates, and combinations thereof.

### Claim 6 (depends on 3)

The polymer compound of claim 3, wherein the plasticizer is selected from the group consisting of phthalates, citrates, soyates, trimellitates, and combinations thereof.

### Claim 7 (depends on 5)

The polymer compound of claim 5, wherein the effective amount of plasticizer ranges from about 20 to about 150 weight parts per one hundred weight parts of polyvinyl halide.

### Claim 8 (depends on 6)

The polymer compound of claim 6, wherein the effective amount of plasticizer ranges from about 20 to about 150 weight parts per one hundred weight parts of polyvinyl halide.

### Claim 9 (depends on 7)

The polymer compound of claim 7, wherein the effective amount of plasticizer ranges from about 40 to about 100 weight parts per one hundred weight parts of polyvinyl halide.

### Claim 10 (depends on 8)

The polymer compound of claim 8, wherein the effective amount of plasticizer ranges from about 40 to about 100 weight parts per one hundred weight parts of polyvinyl halide.

### Claim 11 (depends on 9)

The polymer compound of claim 9, wherein:
the calcium carbonate is Caribbean micritic limestone having a particle size of less than about 10 micrometers and having a purity of above 98%; and
the limestone is treated with coupling agents comprising stearic acid or silane or both.

### Claim 12 (depends on 10)

The polymer compound of claim 10, wherein:
the calcium carbonate is Caribbean micritic limestone having a particle size of less than about 10 micrometers and having a purity of above 98%; and
the limestone is treated with coupling agents comprising stearic acid or silane or both.

### Claim 13 (depends on 11)

The polymer compound of claim 11, wherein the amount of calcium carbonate ranges from about 64 to about 150 weight parts per one hundred weight parts of polyvinyl halide.

### Claim 14 (depends on 12)

The polymer compound of claim 12, wherein the amount of calcium carbonate ranges from about 64 to about 150 weight parts per one hundred weight parts of polyvinyl halide.

### Claim 15 (depends on 1)

An overmolded polymer article comprising a layer comprising the polymer compound of claim 1 and a layer of rigid polyvinyl halide.

### Claim 16 (depends on 2)

The polymer compound of claim 2, wherein the polyvinyl chloride is alloyed with thermoplastic polyurethane.

### Claim 17 (depends on 16)

The polymer compound of claim 16, wherein the plasticizer is selected from the group consisting of phthalates, citrates, soyates, trimellitates, and combinations thereof.

### Claim 18 (depends on 16)

The polymer compound of claim 16, wherein:
the calcium carbonate is Caribbean micritic limestone having a particle size of less than about 10 micrometers and having a purity of above 98%; and
the limestone is treated with coupling agents comprising stearic acid or silane or both.

### Claim 19 (depends on 1)

The polymer compound of claim 1, wherein the polyvinyl halide is suspension polymerized vinyl chloride.

### Claim 20

A composition comprising:
polyvinyl halide; and
a plasticizer;
wherein, when the composition is overmolded as a layer on to a Rigid PVC Test Substrate and undergoes a Modified ASTM D903 Adhesion Peel Strength Test, the layer experiences cohesive failure; and
wherein the plasticizer is present in an amount of at least about 20 weight parts per hundred weight parts of polyvinyl halide.

### Claim 21 (depends on 20)

The composition of claim 20, wherein the polyvinyl halide has an inherent viscosity of less than about 0.9, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243.

### Claim 22 (depends on 21)

The composition of claim 21, wherein the polyvinyl halide has an inherent viscosity of from about 0.65 to about 0.85, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243.

### Claim 23 (depends on 20)

The composition of claim 20, wherein the polyvinyl halide has a weight average molecular weight of from about 39,000 to about 150,000 where the molecular weight is measured by size exclusion chromatography.

### Claim 24 (depends on 20)

The composition of claim 20, wherein the polyvinyl halide is polyvinyl chloride.

### Claim 25 (depends on 20)

The composition of claim 20, wherein the polyvinyl halide is suspension polymerized vinyl chloride.

### Claim 26

A composition, comprising:
polyvinyl halide having an inherent viscosity of less than 0.9, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243;
plasticizer; and
calcium carbonate present in an amount of from 64 weight parts to 150 weight parts per 100 weight parts of the polyvinyl halide;
wherein the plasticizer is present in an amount of at least about 20 weight parts per hundred weight parts of polyvinyl halide.

### Claim 27 (depends on 26)

The composition of claim 26, wherein the polyvinyl halide has an inherent viscosity of from about 0.65 to about 0.85, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243.

### Claim 28 (depends on 26)

The composition of claim 26, wherein the polyvinyl halide has a weight average molecular weight of from about 39,000 to about 150,000 where the molecular weight is measured by size exclusion chromatography.

### Claim 29 (depends on 26)

The composition of claim 26, wherein the polyvinyl halide is polyvinyl chloride.

### Claim 30 (depends on 26)

The composition of claim 26, wherein the polyvinyl halide is suspension polymerized vinyl chloride.

### Claim 31

An article, comprising:
a layer comprising polyvinyl halide and plasticizer; and
a rigid substrate comprising polyvinyl halide, the rigid substrate in contact with the layer comprising the polyvinyl halide and the plasticizer;
wherein, when a peel force is applied to the layer, the layer experiences cohesive failure before being peeled away from the rigid substrate.

### Claim 32 (depends on 31)

The article of claim 31, wherein the polyvinyl halide has an inherent viscosity of less than about 0.9, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243.

### Claim 33 (depends on 31)

The article of claim 31, wherein the polyvinyl halide has an inherent viscosity of from about 0.65 to about 0.85, as measured by using 0.2 grams of resin in 100 ml of cyclohexanone at 30° C. according to test method ASTM D 1243.

### Claim 34 (depends on 31)

The article of claim 31, wherein the polyvinyl halide is polyvinyl chloride.

### Claim 35 (depends on 31)

The article of claim 31, wherein the polyvinyl halide has a weight average molecular weight of from about 39,000 to about 150,000 where the molecular weight is measured by size exclusion chromatography.

### Claim 36 (depends on 31)

The article of claim 31, wherein the polyvinyl halide is suspension polymerized vinyl chloride.

### Claim 37 (depends on 20)

The composition of claim 20, wherein the plasticizer is present in an amount ranging from about 20 to about 150 weight parts per hundred weight parts of polyvinyl halide.

### Claim 38 (depends on 26)

The composition of claim 26, wherein the plasticizer is present in an amount ranging from about 20 to about 150 weight parts per hundred weight parts of polyvinyl halide.