# US 2019/0168495 A1 · Rubber replacement articles and their use as footwear components

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- Number: US 2019/0168495 A1
- Document ID: US20190168495A1
- Status: Published application
- Kind: A1
- Application number: 16/266,894
- Filed: 2019-02-04
- Published: 2019-06-06
- Earliest claimed: 2016-11-09
- Assignees: PPG Industries Ohio, Inc.
- Applicants: Ppg Industries Ohio, Inc.
- Inventors: EDWARD R. MILLERO, JR.; CYNTHIA KUTCHKO; BENJAMIN KABAGAMBE; CHRISTINA WINTERS; RONALD J. KRALIC, JR.; SUSAN FUNDY DONALDSON; JONATHAN P. BREON; HONGYING ZHOU; XUDONG FENG
- Web page: https://patentgrep.com/patent/US20190168495A1

## CPC

- B32B 27/40: comprising polyurethanes
- A43B 5/10: Tennis shoes
- A43B 13/04: Plastics, rubber or vulcanised fibre
- A43B 13/12: Soles with several layers of different materials
- A43B 23/081: {Toe stiffeners}
- B29C 64/106: using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B32B 7/12: using interposed adhesives or interposed materials with bonding properties
- B32B 27/28: comprising synthetic resins not wholly covered by any one of the sub-groups {B32B27/30 - B32B27/42}
- B33Y 10/00: Processes of additive manufacturing
- B33Y 70/00: Materials specially adapted for additive manufacturing
- C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G 18/3234: {cycloaliphatic}
- C08G 18/5024: {containing primary and/or secondary amino groups}
- C08G 18/725: {Combination of polyisocyanates of C08G18/78 with other polyisocyanates}
- C08G 18/755: {and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate}
- C08G 18/792: {formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates}
- C08K 3/22: of metals
- C08L 75/04: Polyurethanes
- C08L 75/08: from polyethers
- C08L 79/02: Polyamines
- C09J 11/04: inorganic
- C09J 163/00: Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- B32B 2375/00: Polyureas; Polyurethanes
- B32B 2379/00: Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
- B32B 2437/02: Gloves, shoes
- C08K 5/37: Thiols
- C08K 2003/2237: {of titanium}
- C08K 2003/2244: {of zirconium}
- Y10T 428/31551: Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- A43B: CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- 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)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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)
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Rubber replacement articles prepared from curable compositions are provided. The curable compositions comprise: (a) an isocyanate-functional prepolymer; (b) a curing agent comprising a mixture of polyamines, wherein at least one polyamine has an amine equivalent weight of 125 to 250; and (c) an abrasion resistant additive comprising organic particles demonstrating a volume average particle size of at least 5 microns. The isocyanate-functional prepolymer is (i) a reaction product of a polyisocyanate and a polyamine having primary and/or secondary amino groups; and/or (ii) a reaction product of a polyisocyanate and a polyol.

## Claims

### Claim 1

A rubber replacement article prepared from a curable composition comprising:
(a) an isocyanate-functional prepolymer, wherein the isocyanate-functional prepolymer comprises (i) a reaction product of a polyisocyanate and a polyamine having primary and/or secondary amino groups; and/or (ii) a reaction product of a polyisocyanate and a polyol;
(b) a curing agent comprising a mixture of polyamines, wherein at least one polyamine in the curing agent has an amine equivalent weight of 125 to 250; and
(c) an abrasion resistant additive comprising organic particles, wherein the organic particles demonstrate a volume average particle size of at least 5 microns.

### Claim 2 (depends on 1)

The rubber replacement article according to claim 1, wherein at least one polyamine in the curing agent having an amine equivalent weight of 125 to 250 is a non-cyclic polyamine which comprises secondary amino groups.

### Claim 3 (depends on 1)

The rubber replacement article according to claim 1, wherein the abrasion resistant additive is present in the composition in an amount ranging from 0.25 to 9 percent by weight, based on the total solids weight of the composition.

### Claim 4 (depends on 1)

The rubber replacement article according to claim 1, wherein the polyisocyanate used to prepare the isocyanate-functional prepolymer is aliphatic.

### Claim 5 (depends on 1)

The rubber replacement article according to claim 1, wherein isocyanate-functional prepolymer has an isocyanate equivalent weight greater than 300.

### Claim 6 (depends on 1)

The rubber replacement article according to claim 1, wherein the curing agent comprises 5 to 50 percent by weight of an aliphatic polyamine having an amine equivalent weight of 125 to 250, and 50 to 95 percent by weight of an aliphatic polyamine having an amine equivalent weight of 900 to 2,500.

### Claim 7 (depends on 1)

The rubber replacement article according to claim 1, wherein the organic particles comprise chemically inert, untreated and uncoated particles.

### Claim 8 (depends on 1)

The rubber replacement article according to claim 1, wherein the organic particles comprise polyethylene, polypropylene, and/or saturated, linear primary alcohols with an average carbon chain length of C20 to C50.

### Claim 9 (depends on 1)

The rubber replacement article according to claim 1, wherein the rubber replacement article comprises a footwear component.

### Claim 10 (depends on 9)

The rubber replacement article according to claim 9, wherein at least one polyamine in the curing agent having an amine equivalent weight of 125 to 250 is a non-cyclic polyamine which comprises secondary amino groups.

### Claim 11 (depends on 9)

The rubber replacement article according to claim 9, wherein the abrasion resistant additive is present in the composition in an amount ranging from 0.25 to 9 percent by weight, based on the total solids weight of the composition.

### Claim 12 (depends on 9)

The rubber replacement article according to claim 9, wherein the polyisocyanate used to prepare the isocyanate-functional prepolymer is aliphatic.

### Claim 13 (depends on 9)

The rubber replacement article according to claim 9, wherein isocyanate-functional prepolymer has an isocyanate equivalent weight greater than 300.

### Claim 14 (depends on 9)

The rubber replacement article according to claim 9, wherein the curing agent comprises 5 to 50 percent by weight of an aliphatic polyamine having an amine equivalent weight of 125 to 250, and 50 to 95 percent by weight of an aliphatic polyamine having an amine equivalent weight of 900 to 2,500.

### Claim 15 (depends on 9)

The rubber replacement article according to claim 9, wherein the organic particles comprise chemically inert, untreated and uncoated particles.

### Claim 16 (depends on 9)

The rubber replacement article according to claim 9, wherein the organic particles comprise polyethylene, polypropylene, and/or saturated, linear primary alcohols with an average carbon chain length of C20 to C50.

### Claim 17 (depends on 9)

The rubber replacement article according to claim 9, wherein said footwear component demonstrates a dry film thickness of 25.4 to 254 microns.

### Claim 18 (depends on 9)

The rubber replacement article according to claim 9, further comprising an adhesive layer applied to at least one surface of the footwear component, wherein the adhesive layer comprises an adhesion promoter and/or the reaction product of an epoxy resin and a polythiol.

### Claim 19 (depends on 18)

The rubber replacement article according to claim 18, wherein the adhesive layer comprises an adhesion promoter comprising an organic titanate or zirconate.

### Claim 20 (depends on 1)

The rubber replacement article of claim 1, wherein said rubber replacement article is prepared by 3D-printing the article by forming at least one portion or cross-sectional layer of the article by depositing at least two co-reactive components onto a substrate until the article is fully formed, wherein a first co-reactive component comprises the isocyanate-functional prepolymer (a) and a second co-reactive component comprises the curing agent (b).

### Claim 21 (depends on 1)

A method of preparing the rubber replacement article of claim 1 by 3D-printing, comprising:
(a) depositing at least two co-reactive components onto a substrate to form a cross-sectional layer of the article;
(b) if necessary, depositing an additional layer of the co-reactive components over at least a portion of the previously applied layer;
(c) repeating step (b) until the article is fully formed; and
(d) optionally removing the article from the substrate; wherein a first co-reactive component comprises the isocyanate-functional prepolymer (a) and a second co-reactive component comprises the curing agent (b).