# US 11,077,710 B2 · Laminate of thermoplastic resin film and rubber, inner liner material, and pneumatic tire

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- Number: US 11,077,710 B2
- Document ID: US11077710B2
- Status: Granted
- Kind: B2
- Application number: 15/745,532
- Filed: 2016-07-14
- Published: 2018-10-04
- Granted: 2021-08-03
- Earliest claimed: 2015-07-17
- Assignees: The Yokohama Rubber Co., Ltd.
- Applicants: The Yokohama Rubber Co., Ltd.
- Inventors: Hirokazu Shibata
- Web page: https://patentgrep.com/patent/US11077710B2

## CPC

- B60C 1/0008: {Compositions of the inner liner}
- B32B 25/08: of synthetic resin
- B32B 25/14: comprising {synthetic rubber copolymers (B32B25/18 and B32B25/20 take precedence)}
- B32B 25/18: comprising butyl or halobutyl rubber
- B32B 27/18: characterised by the use of special additives
- B32B 27/302: {comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers}
- B32B 27/306: {comprising vinyl acetate or vinyl alcohol (co)polymers}
- B32B 27/308: {comprising acrylic (co)polymers}
- B32B 27/32: comprising polyolefins {(comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30)}
- B32B 27/34: comprising polyamides
- B60C 5/14: with impervious liner or coating on the inner wall of the tyre
- C08K 3/06: Sulfur
- C08K 5/06: Ethers; Acetals; Ketals; Ortho-esters
- C08K 5/17: Amines; Quaternary ammonium compounds
- C08K 5/34: Heterocyclic compounds having nitrogen in the ring
- C08K 5/3492: Triazines
- C08K 5/34922: {Melamine; Derivatives thereof}
- C08L 9/06: Copolymers with styrene
- C08L 21/00: Compositions of unspecified rubbers
- C08L 23/28: by reaction with halogens or halogen-containing compounds (C08L23/32 takes precedence)
- C08L 23/283: Iso-olefin halogenated homopolymers or copolymers
- C08L 29/04: Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
- C08L 61/06: of aldehydes with phenols
- C08L 61/14: Modified phenol-aldehyde condensates
- B32B 2250/02: 2 layers
- B32B 2250/24: All layers being polymeric
- B32B 2264/1025: Zinc oxide
- B32B 2264/108: Carbon, e.g. graphite particles
- B32B 2270/00: Resin or rubber layer containing a blend of at least two different polymers
- B32B 2274/00: Thermoplastic elastomer material
- B32B 2307/748: Releasability
- B32B 2597/00: Tubular articles, e.g. hoses, pipes
- B60C 2005/145: {made of laminated layers}
- C08G 69/08: derived from amino-carboxylic acids
- B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

A laminate of a thermoplastic resin or thermoplastic elastomer composition film and a rubber composition layer, which can be used as an inner liner for a pneumatic tire, with improved adhesive strength at the interface of the thermoplastic resin or thermoplastic elastomer composition film and the rubber composition layer. A laminate comprising a thermoplastic resin or thermoplastic elastomer composition film and a rubber composition layer, the rubber composition containing a rubber component, a condensate of a phenol compound and formaldehyde, and methylene donor and a vulcanizing agent, wherein 2.5-40% by mass of the rubber component is halogenated isomonoolefin-p-alkyl styrene copolymer, the content of the condensate is 0.5-20 parts by mass per 100 parts by mass of the rubber component, and the content of the methylene donor is 0.25-200 parts by mass per 100 parts by mass of the rubber component.

## Claims

### Claim 1

A laminate for a pneumatic tire, comprising a film of a thermoplastic resin or a thermoplastic elastomer composition and a layer of a rubber composition, wherein the rubber composition comprises a rubber component, a condensate of a compound represented by formula (1):
wherein R1, R2, R3, R4, and R5 are each independently hydrogen, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, and formaldehyde, a methylene donor, and a vulcanizing agent, wherein the rubber component comprises a styrene butadiene rubber, natural rubber and a brominated isobutylene/p-methylstyrene copolymer, and wherein the rubber component comprises from 2.5 to 40% by weight of the brominated isobutylene/p-methylstyrene copolymer based on the rubber component, and the rubber composition comprises from 0.5 to 20 parts by weight of the condensate and from 0.25 to 200 parts by weight of the methylene donor, based on 100 parts by weight of the rubber component.

### Claim 2 (depends on 1)

The laminate according to claim 1, wherein a ratio of a content of the methylene donor to a content of the condensate is from 0.5 to 10.

### Claim 3 (depends on 1)

The laminate according to claim 1 wherein the thermoplastic resin is at least one selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon MXD6, and nylon 6T.

### Claim 4 (depends on 1)

The laminate according to claim 1, wherein the thermoplastic elastomer composition is a composition comprising a thermoplastic resin component and an elastomer component dispersed in the thermoplastic resin component; the thermoplastic resin component is at least one selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon MXD6, and nylon 6T; and the elastomer component is at least one selected from the group consisting of a halogenated isomonoolefin-p-alkyl styrene copolymer, a maleic anhydride-modified ethylene-a-olefin copolymer, an ethylene-glycidyl methacrylate copolymer, and a maleic anhydride-modified ethylene-ethyl acrylate copolymer.

### Claim 5 (depends on 1)

The laminate according to claim 1, wherein the methylene donor is at least one selected from the group consisting of modified etherified methylol melamine, paraformaldehyde, hexamethylenetetramine, pentamethylenetetramine, and hexamethoxymethylmelamine.

### Claim 6 (depends on 1)

An inner liner material for a pneumatic tire, comprising the laminate according to claim 1.

### Claim 7 (depends on 1)

A pneumatic tire comprising the laminate according to claim 1 as an inner liner material.

### Claim 8 (depends on 2)

The laminate according to claim 2, wherein the thermoplastic resin is at least one selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon MXD6, and nylon 6T.

### Claim 9 (depends on 2)

The laminate according to claim 2, wherein the thermoplastic elastomer composition is a composition comprising a thermoplastic resin component and an elastomer component dispersed in the thermoplastic resin component; the thermoplastic resin component is at least one selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon MXD6, and nylon 6T; and the elastomer component is at least one selected from the group consisting of a brominated isobutylene-p-methylstyrene copolymer, a maleic anhydride-modified ethylene-α-olefin copolymer, an ethylene-glycidyl methacrylate copolymer, and a maleic anhydride-modified ethylene-ethyl acrylate copolymer.

### Claim 10 (depends on 3)

The laminate according to claim 3, wherein the thermoplastic elastomer composition is a composition comprising a thermoplastic resin component and an elastomer component dispersed in the thermoplastic resin component; the thermoplastic resin component is at least one selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon MXD6, and nylon 6T; and the elastomer component is at least one selected from the group consisting of a brominated isobutylene-p-methylstyrene copolymer, a maleic anhydride-modified ethylene-α-olefin copolymer, an ethylene-glycidyl methacrylate copolymer, and a maleic anhydride-modified ethylene-ethyl acrylate copolymer.

### Claim 11 (depends on 2)

The laminate according to claim 2, wherein the methylene donor is at least one selected from the group consisting of modified etherified methylol melamine, paraformaldehyde, hexamethylenetetramine, pentamethylenetetramine, and hexamethoxymethylmelamine.

### Claim 12 (depends on 3)

The laminate according to claim 3, wherein the methylene donor is at least one selected from the group consisting of modified etherified methylol melamine, paraformaldehyde, hexamethylenetetramine, pentamethylenetetramine, and hexamethoxymethylmelamine.

### Claim 13 (depends on 4)

The laminate according to claim 4, wherein the methylene donor is at least one selected from the group consisting of modified etherified methylol melamine, paraformaldehyde, hexamethylenetetramine, pentamethylenetetramine, and hexamethoxymethylmelamine.

### Claim 14 (depends on 2)

An inner liner material for a pneumatic tire, comprising the laminate according to claim 2.

### Claim 15 (depends on 3)

An inner liner material for a pneumatic tire, comprising the laminate according to claim 3.

### Claim 16 (depends on 4)

An inner liner material for a pneumatic tire, comprising the laminate according to claim 4.

### Claim 17 (depends on 5)

An inner liner material for a pneumatic tire, comprising the laminate according to claim 5.

### Claim 18 (depends on 2)

A pneumatic tire comprising the laminate according to claim 2 as an inner liner material.

### Claim 19 (depends on 3)

A pneumatic tire comprising the laminate according to claim 3 as an inner liner material.

### Claim 20 (depends on 4)

A pneumatic tire comprising the laminate according to claim 4 as an inner liner material.