# US 10,245,812 B2 · Dual cure stain resistant microsphere articles

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- Number: US 10,245,812 B2
- Document ID: US10245812B2
- Status: Granted
- Kind: B2
- Application number: 15/117,478
- Filed: 2015-02-13
- Published: 2016-12-01
- Granted: 2019-04-02
- Earliest claimed: 2014-02-13
- Assignees: 3M Innovative Properties Company
- Applicants: 3M Innovative Properties Company
- Inventors: Christopher B. Walker, Jr.; John C. Clark; Thomas P. Klun; Steven J. McMan; Abdullahi A. Mohamud; Alexander J. Kugel; Vivek Krishnan
- Web page: https://patentgrep.com/patent/US10245812B2

## CPC

- B32B 27/322: {comprising halogenated polyolefins, e.g. PTFE}
- B32B 3/00: Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B 3/02: characterised by features of form at particular places, e.g. in edge regions {(non-uniform thickness B32B3/263)}
- B32B 3/16: secured to a flexible backing
- B32B 3/30: characterised by a layer formed with recesses or projections, e.g. {hollows, grooves, protuberances, ribs (apertured layer B32B3/266; layer with cavities or internal voids B32B3/26)}
- B32B 7/00: Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B 7/027: Thermal properties
- B32B 7/12: using interposed adhesives or interposed materials with bonding properties
- B32B 9/00: Layered products comprising a {layer of a} particular substance not covered by groups B32B11/00 - B32B29/00
- B32B 27/00: Layered products comprising {a layer of} synthetic resin {(fibrous or filamentary layer made of a synthetic resin B32B5/02; particulate layer made of a synthetic resin B32B5/16; foamed layer made of a synthetic resin B32B5/18)}
- B32B 27/06: as the main or only constituent of a layer, {which is} next to another layer of {the same or of} a {different material (next to a layer of a particular substance B32B9/045; next to a bituminous or tarry layer B32B11/046; next to a water setting substance layer B32B13/12; next to a metal layer B32B15/08; next to a glass layer B32B17/10; next to a layer formed of natural mineral fibres or particles B32B19/045; next to a wood layer B32B21/08; next to a cellulosic plastic layer B32B23/08; next to a natural or synthetic rubber layer B32B25/08)}
- B32B 27/08: of synthetic resin
- B32B 27/14: next to a particulate layer
- B32B 27/18: characterised by the use of special additives
- B32B 27/20: using fillers, pigments, thixotroping agents
- B32B 27/30: comprising vinyl {(co)polymers; comprising acrylic (co)polymers}
- B32B 27/304: {comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF}
- B32B 27/308: {comprising acrylic (co)polymers}
- B32B 27/36: comprising polyesters
- B32B 27/38: comprising epoxy resins
- B32B 3/14: characterised by a face layer formed of separate pieces of material {which are juxtaposed side-by-side (B32B5/02 takes precedence)}
- B32B 2260/00: Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B 2260/025: Particulate layer
- B32B 2264/00: Composition or properties of particles which form a particulate layer or are present as additives
- B32B 2307/308: Heat stability
- B32B 2307/50: having particular mechanical properties
- B32B 2307/54: Yield strength; Tensile strength
- B32B 2451/00: Decorative or ornamental articles
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM

## Abstract

There is provided a thermoformable article comprising at least a first surface having a binder resin layer comprising a fluorine-containing polymer, where the binder resin layer has a first major surface opposite a second major surface; and a plurality of microspheres partially and adhered to the first major surface of the binder resin layer; where the fluorine-containing polymer is a partially fluorinated polymer derived from at least one fluorine containing monomer and two or more non-fluorinated monomers having at least one active hydrogen functional group, and further wherein at least one but not all of the active hydrogen functional groups are reacted with at least one curing agent having latent functionality. In some instances the curing agent comprises polyisocyanate. There is also provided a thermoset article derived from such thermoformable articles.

## Claims

### Claim 1

An article comprising at least a first surface having:
(a) a binder resin layer comprising a fluorine-containing polymer, wherein the binder resin layer has a first major surface opposite a second major surface; and
(b) a plurality of microspheres partially embedded and adhered to the first major surface of the binder resin layer;
wherein the fluorine-containing polymer is a partially fluorinated polymer derived from at least one fluorine containing monomer and two or more non-fluorinated monomers having at least one active hydrogen functional group, and further wherein at least one but not all of the active hydrogen functional groups are reacted with at least one curing agent having latent functionality and wherein the partially fluorinated polymer comprises a copolymer of the structure of Formula (I):
RfRXRLRG (I)
wherein Rf must be present as 30 mol % to 60 mol % of the polymer, and wherein RX must be present as 5 mol % to 20 mol % of the polymer, and further wherein the remaining mol % of the polymer are RL, and RG,
(a) Rf is selected from at least one of the following or combinations thereof:
—CF2CF2—,
—CFClCF2—,
—CH2CF2—
wherein Rf2 is fluoroalkyl having 1 to 8 carbon atoms;
(b) RX is:
wherein Q1 is
or
—O—Z—X
wherein Z is optional, or when present, is selected from an alkylene, arylene, aralkylene or alkarylene, in which any are optionally substituted with N, O or S; and wherein X is OH, or SH, or NHR1, where R1 is H, alkyl or cycloalkyl having 1 to 22 carbon atoms;
(c) RL is
wherein Q2 is,
or,
—O—Z-L
wherein Z is optional, or when present, is selected from an alkylene, arylene, aralkylene, or alkarylene, in which any are optionally substituted with N, O or S and
L is
or
—Y—ZA)n,
wherein Y is O, S, NR1, wherein R1 is H, or alkyl or cycloalkyl having 1 to 22 carbon atoms, and
A is
wherein n is 1 to 5 and R2 is H or CH3; and
(d) RG is
wherein Q3 is
or
—O—Z-G
wherein Z is optional, or when present is selected from an alkylene, arylene, aralkylene, or alkarylene in which any are optionally substituted with N, O or S and wherein G is aryl, alkyl, aralkyl or alkaryl.

### Claim 2 (depends on 1)

The article of claim 1 wherein Rf must be present as 30 mol % to 60 mol % of the polymer; RX must be present as 5 mol % to 15 mol % of the polymer; and RL, and RG comprises the remaining mol % of the polymer.

### Claim 3 (depends on 1)

The article of claim 1 wherein the binder resin layer further comprises a condensation polymer or an acrylic polymer.

### Claim 4 (depends on 1)

The article of claim 1 wherein the non-fluorinated monomer is a hydroxy-containing monomer.

### Claim 5 (depends on 1)

The article of claim 1 wherein the partially fluorinated polymer has a number molecular weight of greater than or equal to 9000 g/mol.

### Claim 6 (depends on 1)

The article of claim 1 wherein the binder resin layer further comprises a crosslinker.

### Claim 7 (depends on 6)

The article of claim 6 wherein the crosslinker comprises polyisocyanate with latent functionality.

### Claim 8 (depends on 7)

The article of claim 7 wherein the percent equivalents of crosslinker to equivalents of total active hydrogen functionality is between 7% and 25%.

### Claim 9 (depends on 7)

The article of claim 7 wherein the percent equivalents of crosslinker to equivalents of total active hydrogen functionality is between 10% and 15%.

### Claim 10 (depends on 1)

The article of claim 1 wherein the curing agent comprises polyisocyanate.

### Claim 11 (depends on 1)

The article of claim 1 wherein the plurality of microspheres are selected from at least one of glass, polymers, glass ceramics, ceramics, metals and combinations thereof.

### Claim 12 (depends on 1)

The article of claim 1 wherein at least about 60% of the surface of the article is covered with the plurality of microspheres.

### Claim 13 (depends on 1)

The article of claim 1 further comprising a reinforcing layer disposed along the second major surface of the binder resin layer.

### Claim 14 (depends on 13)

The article of claim 13 wherein the reinforcing layer comprises at least one of polyurethane resins, acrylic resins, polyester resins, epoxy resins, and combinations thereof.

### Claim 15 (depends on 14)

The article of claim 14 wherein the polyurethane material is selected from polyurethane dispersions, two part urethanes coated from solvent, 100% solids two part urethanes, and combinations thereof.

### Claim 16 (depends on 1)

The article of claim 1 wherein the fluorine content along the polymeric backbone of the fluorine-containing polymer is from about 25% to 72% by weight.

### Claim 17 (depends on 1)

The article of claim 1 wherein the article is a thermoformable article.

### Claim 18 (depends on 1)

A thermoset article derived from the articles of claim 1.

### Claim 19 (depends on 18)

The thermoset article of claim 18 is a three-dimensional shaped thermoset article.

### Claim 20 (depends on 18)

The thermoset article of claim 18 wherein curing is accomplished by actinic radiation curing.

### Claim 21 (depends on 18)

The thermoset article of claim 18 wherein the thermoset article exhibits a stain resistance to yellow mustard after 72 hours at a temperature of 66° C. (150° F.) and relative humidity of 80%, as measured by a change in b*, as defined by the International Commission on Illumination (CIE) 1976 Color Space, of less than 50.

### Claim 22 (depends on 18)

The thermoset article of claim 18 wherein the thermoset article exhibits a pencil hardness according to ASTM D 3363 of greater than or equal to 9H at 7.5 Newtons.

### Claim 23 (depends on 18)

The thermoset article of claim 18 wherein the thermoset article is resistant to organic solvents.

### Claim 24 (depends on 18)

The thermoset article of claim 18 wherein the thermoset article comprises a free-standing bead film and exhibits a kinetic coefficient of friction of less than 0.3, as measured using a peel tester.