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Innovation Center Latest Patents

(WO2018136488) WATERBORNE 00:00 05:59

POLYURETHANE COATINGS
 July 28, 2018  Admin  0 Comments
Top Mergers and
Acquisitions in Paints
and Coatings
Pub. No.: WO/2018/136488 International PCT/US2018/014007
Industry (completed)
Application in 2020
No.:

Publication 26.07.2018 International 17.01.2018

Top Mergers an…
an…
Date: Filing Date:

IPC: B32B 27/06 (2006.01) ,B32B 27/08 (2006.01) ,C09D

175/04 (2006.01) ,C09D 175/06 (2006.01) ,C09D 00:00 04:43
175/08 (2006.01) ,C09D 175/10 (2006.01)

Applicants: SUN CHEMICAL CORPORATION[US/US]; 35 Waterview

Boulevard Parsippany, NJ 07054, US

Inventors: ZHA, Yongping; US

SCHOTTLAND, Philippe; US
MATEUSZCZYK, Robert; US

Agent: ACHKAR, Charles, C.; US

FABER, Robert, C.; US
MOSKOWITZ, Max; US Dear readers,
FINDER, James, A.; US
WEINER, Sammel, H.; US The aim of PCE is to provide all

Priority

information about paints and
coatings industry for you. Even
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Data: 62/448,031 19.01.2017 US the smallest amount of support

is hugely appreciated. It is not
necessary to be registered on
Title (EN) WATERBORNE POLYURETHANE COATINGS PayPal to use this service.
(FR) REVÊTEMENTS EN POLYURÉTHANE À L’EAU Thanks in advance!

Abstract: (EN) The present invention provides waterborne $1.00

polyurethane coating compositions. When applied to a
substrate, the coating compositions of the present invention
1
have good adhesion, transparency, scratch resistance, mar
resistance, hardness, solvent resistance, water resistance,
and dishwashing resistance. The coating compositions are
Welcome to PCE
suitable for application to any suitable substrate, including
glass. Welcome to our website
(FR) La présente invention concerne des compositions deabout Paints and Coatings.
revêtement en polyuréthane à l’eau. Lorsqu’elles sont Your opinions are very
important for us in order to
appliquées sur un substrat, les compositions de revêtement
de la présente invention présentent une adhérence, unegive you better service.
*Please give us your
transparence, une résistance aux rayures, une résistance à
comments via contact section.
l’abrasion, une dureté, une résistance aux solvants, une
*Please follow us on LinkedIn
résistance à l’eau et une résistance à la vaisselle and Twitter and subscribe to
satisfaisantes. Les compositions de revêtement sont our webstite and receive
appropriées pour être appliquées sur n’importe quel noti cations of new posts by
substrat approprié, y compris le verre. email.
THANKS FOR YOUR SUPPORT

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CROSS-REFERENCE TO RELATED APPLICATIONS

[001] This application claims priority to U.S. Provisional Application

No. 62/448,031 led 19 January 2017, which is hereby incorporated
herein in its entirety.

FIELD OF THE INVENTION

[002] The present invention is related to waterbome polyurethane

coating compositions. The compositions can be provided as stable
one-component coating systems. When applied to a substrate, the
coating compositions of the present invention have good adhesion,
transparency, scratch resistance, mar resistance, hardness, water 
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resistance, and dishwashing resistance. The coating compositions

are suitable for application to any suitable substrate, including glass.

BACKGROUND

[003] Polyurethanes are widely used as surface overlay coatings on a

wide variety of substrates because of their combination of desirable
properties. For example, polyurethane coatings are exible, tough,
have good water and chemical resistance, and have improved clarity
compared to other types of coatings. Polyurethane coatings are
particularly useful for providing a coating to glass surfaces for
decorative and protective purposes. Glass articles, such as bottles
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for beverages, are subjected to many environmental challenges,
such as rubbing, exposure to chemicals, exposure to harsh washing Enter your email address to
conditions, etc. Thus, coatings for glass articles must have good follow this website and receive
abrasion resistance, scratch resistance, mar resistance, solvent noti cations of new posts by
resistance, water resistance, and detergent resistance, depending on email.
the nal applications of the glassware.
Email Address
[004] Due to the increased restriction on volatile organic compounds
(VOCs) in coatings, solvent-free systems which may be supplied as a
single component are advantageous as an environmentally friendly
Subscribe
alternative. One-component coating compositions comprise pre-
mixed materials that have acceptable pot life and storage stability,
and are cured under speci c conditions (e.g. hydroxyl-functional
resins cross-linked with alkoxylated aminoplast resins or reversibly
blocked isocyanates) when applied to substrates. In contrast, multi- Follow us on Twitter
component coating compositions comprise two or more separate
and mutually reactive

components that are mixed immediately prior to application to a

substrate. The separate components respectively contain
ingredients that are reactive under ambient conditions and that
begin appreciable formation of cured resin immediately upon
mixing. Therefore, the multi-components must remain separated
until immediately before application, because pot life is limited due
to the immediate reaction and gelling upon mixing (i.e. limited pot
life).

[005] One- and two-component polyurethane coatings are generally

described in Martin, L. et. al. Waterborne polyurethane resins for
glass coatings. PCI Magazine (July 24, 2000) and Barletta, M. et. al.
Coating of glass and polycarbonate with aqueous two-component 
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polyurethane resin. J. Appl. Polym Set , 131(6), DOI:

Tweets by @P_C_Expert
10.1002/APP.40021 (2014).
Paints&Coatings Ex
[006] EP 0 519 074 describes an aqueous glass coating composition @P_C_Expert
that is applied in two coats, wherein the topcoat contains three main Boosting performance of
components: an aqueous polyurethane dispersion, an aqueous interior paint with Silres BS
333#news #business #coating
epoxy resin, and an aqueous melamine resin. The coating system is
#coatings #paint #paints
a multi-component system. #coatingstechnology
bit.ly/2OcanDx
[007] US 4,163,814 and US 4,280,944 disclose aqueous polyether-
based polyurethane dispersions containing free hydroxyl groups
and blocked isocyanate groups, which constitute a one-component
system, and can be thermally cured. However, the coatings have
inadequate pencil hardness, and do not exhibit good adhesion to
glass and resistance to alkali. Boosting performance…

[008] US 5,852,106 describes aqueous polyurethane coating Embed View on Twitter

compositions wherein the binder contains a polyol component and
a polyisocyanate component with blocked isocyanate groups. While
the coatings demonstrate good alkali resistance, it is generally
necessary to add melamine to such compositions to increase Most Read
toughness or hardness for some applications.
Hempel to announce
[009] US 2012/0201982 discloses one-component thermally-curable global price increase
aqueous polyurethane coating compositions comprising a hydroxyl-
functional polyurethane dispersion, a blocked polyisocyanate, and a
Paints and Coatings
polycarbonate-polyurethane resin, wherein the polycarbonate-
Expert
polyurethane resin is non-functional. Addition of the non-functional
polycarbonate-polyurethane resin provides improved exibility,
without any loss in adhesion or toughness. [0010] US 2013/0011590 BYK to launch two
discloses one-component thermally-curable aqueous polyurethane silicone-containing
surface additives
coating compositions comprising a hydroxyl-functional polyurethane
resin, an aminoplast, and a polycarbonate-polyurethane. The
Top 20 Most Read
polycarbonate-polyurethane resin is non-functional.
Articles of January
2020 on PCE-Paints
[0011] US 8,343,601 discloses aqueous polyurethane coating
and Coatings Expert
compositions comprising a polyol resin (e.g. acrylic resin), an
aminoplast, and a polycarbonate-polyurethane resin. The
Boosting performance
polycarbonate-polyurethane is non-functional. of interior paint with
Silres BS 333
[0012] US 6,555,231 describes an acrylic-free, waterborne coating
composition comprising a polyurethane dispersion with at least one
Top 20 Most Read
carboxyl group, and a water-soluble cross-linker (such as melamine). 
Articles of April 2020

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The coating composition provides a paint lm having improved chip on PCE-Paints and
resistance when applied to a substrate. Coatings Expert

[0013] While the compositions of the prior art have provided AkzoNobel to
aqueous coating compositions which are suitable for glass surfaces complete acquisition
exhibiting good abrasion, high impact, water, and alkali resistance, of Mauvilac and
strengthens its
such prior art coatings are generally soft, and exhibit decreased
position in Sub
hardness when compared to an uncoated glass surface. The
Saharan Africa
decreased hardness is undesirable by end users. Moreover, they all
require at least 1% coalescing agent, such as dipropylene glycol, in Climate Protection
the formulations, and are thus not truly solvent-free. Thus, there is with Energy-Saving
still a need for aqueous polyurethane coatings that exhibit increased Facades? SILRES® BS
hardness, as well as the improved resistance properties, and that 6042
are truly solvent-free.
Röhm and OQ
BRIEF SUMMARY OF THE INVENTION Chemicals to Plan US
MMA Project: 250,000
[0014] The present invention provides waterbome polyurethane tons of MMA annually
coating compositions that exhibit improved transparency and
hardness, as well as improved abrasion, high impact, water, solvent, allnex to announce
and alkali resistance. substantial strides in
2019-2023
[0015] In a particular aspect, the present invention provides a sustainability
coating composition comprising: commitments

a) a water dilutable carboxyl, or hydroxyl, or carboxyl and hydroxyl,

functional

polyurethane dispersion, in an amount of 1 wt% to 99 wt%, based

on the total weight of the coating composition; and

b) one or more cross-linking agents, in an amount of 1 wt% to 99

wt%, based on the total weight of the coating composition;

wherein the one or more cross-linking agents are selected from the
group consisting of carbodiimides, carbodiimide derivatives,
aminoplasts, blocked isocyanates, and combinations thereof; No upcoming events

wherein the polyurethane has a glass transition temperature of

-40°C to 50°C; and wherein the polyurethane has an elongation at
break of 10% to 250%.

[0016] In one embodiment, at least one cross-linker is a

carbodiimide.
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[0017] In another aspect, the present invention provides a method

of applying a coating composition on a substrate, comprising:

a) providing the coating composition of the present invention;

b) applying the coating composition to the substrate; and

c) drying and/or curing the coating composition on the substrate.

[0018] In another aspect, the present invention provides a method

of formulating a coating composition, comprising mixing:

a) a water dilutable carboxyl, or hydroxyl, or carboxyl and hydroxyl,

functional

polyurethane dispersion, in an amount of 1 wt% to 99 wt%, based

on the total weight of the coating composition; and

b) one or more cross-linking agents, in an amount of 1 wt% to 99

wt%, based on the total weight of the coating composition;

wherein the one or more cross-linking agents are selected from the
group consisting of carbodiimides, carbodiimide derivatives,
aminoplasts, blocked isocyanates, and combinations thereof;

wherein the polyurethane has a glass transition temperature of

-40°C to 50°C; and wherein the polyurethane has an elongation at
break of 10% to 250%.

[0019] In certain embodiments, the present invention provides

substrates and articles comprising the coating compositions of the
present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0020] It is to be understood that the foregoing general description

and the following detailed description are exemplary and
explanatory only, and are not restrictive of any subject matter
claimed.

[0021] Unless otherwise de ned, all technical and scienti c terms

used herein have the same meaning as is commonly understood by
one of skill in the art to which the inventions belong. All patents,
patent applications, published applications and publications,
websites and other published materials referred to throughout the

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entire disclosure herein, unless noted otherwise, are incorporated

by reference in their entirety for any purpose.

[0022] The present invention provides coating compositions which

are suitable for various substrates, including glass, and which have
high pencil hardness, in addition to outstanding optical properties,
good adhesion to the substrate, increased abrasion resistance,
scratch resistance, mar resistance, solvent resistance, water
resistance, detergent (alkali) resistance, and overprintability.

[0023] In a particular aspect, the present invention provides a

coating composition comprising:

a) a water dilutable carboxyl, or hydroxyl, or carboxyl and hydroxyl,

functional

polyurethane dispersion, in an amount of 1 wt% to 99 wt%, based

on the total weight of the coating composition; and

b) one or more cross-linking agents, in an amount of 1 wt% to 99

wt%, based on the total weight of the coating composition;

wherein the one or more cross-linking agents are selected from the
group consisting of carbodiimides, carbodiimide derivatives,
aminoplasts, blocked isocyanates, and combinations thereof;

wherein the polyurethane has a glass transition temperature of

-40°C to 50°C; and wherein the polyurethane has an elongation at
break of 10% to 250%.

De nitions

[0024] In this application, the use of the singular includes the plural
unless speci cally stated otherwise. As used herein, the singular
forms “a,” “an” and “the” are intended to include the plural forms as
well, unless the context clearly indicates otherwise.

[0025] In this application, the use of “or” means “and/or” unless

stated otherwise.

[0026] As used herein, the terms “comprises” and/or “comprising”

specify the presence of the stated features, integers, steps,
operations, elements, and/or components, but do not preclude the
presence or addition of one or more other features, integers, steps,
operations, elements, components, and/or groups thereof. 
Furthermore, to the extent that the terms “includes,” “having,” “has,”
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“with,” “composed,” “comprised” or variants thereof are used in

either the detailed description or the claims, such terms are
intended to be inclusive in a manner similar to the term “comprising.
”

[0027] As used herein, “substrate” means any surface or object to

which an ink or coating can be applied. Substrates include, but are
not limited to, paper, fabric, leather, textiles, felt, concrete, masonry,
stone, plastic, plastic or polymer lm, glass, ceramic, metal, wood,
composites, combinations thereof, and the like. Substrates may
have one or more layers of metals or metal oxides, or other
inorganic materials.

[0028] As used herein “article” or “articles” means a substrate or

product of manufacture. Examples of articles include, but are not
limited to: substrates such as paper, fabric, leather, textiles, felt,
concrete, masonry, stone, plastic, plastic or polymer lm, glass,
ceramic, metal, wood, composites, and the like; and products of
manufacture such as publications (e.g.

brochures), labels, and packaging materials (e.g. cardboard sheet or

corrugated board), containers (e.g. bottles, cans), clothing, a
polyole n (e.g. polyethylene or polypropylene), a polyester (e.g.
polyethylene terephthalate), a metalized foil (e.g. laminated
aluminum foil), metalized polyester, a metal container, and the like.

[0029] As used herein, ranges and amounts can be expressed as

“about” a particular value or range. “About” is intended to also
include the exact amount. Hence “about 5 percent” means

“about 5 percent” and also “5 percent.” “About” means within typical

experimental error for the application or purpose intended.

[0030] As used herein, a “carboxyl” functional polyurethane or

polyurethane dispersion is a polyurethane having one or more
reactive carboxyl (COOH) groups.

[0031] As used herein, a “hydroxyl” functional polyurethane or

polyurethane dispersion is a polyurethane having one or more
reactive hydroxyl (OH) groups.

[0032] As used herein, a “carboxyl and hydroxyl” functional

polyurethane or polyurethane dispersion is a polyurethane having
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one or more reactive carboxyl groups and one or more reactive

hydroxyl groups.

[0033] As used herein, the term “polyisocyanate” refers to a

compound having two or more unreacted isocyanate groups.

[0034] As used herein, the term “water-dilutable” refers to solubility

as a molecular solution in water, or dispersability as a dispersion,
emulsion, suspension, colloid, and the like, in water, with or without
external dispersants, emulsi ers, surfactants, co-solvents, or the
like.

[0035] As used herein, the term “aminoplast resin” refers to resins

based on urea-formaldehyde or melamine-formaldehyde
condensation products.

[0036] As used herein, “elongation,” “percent elongation,” “%

elongation,” or “elongation (%)” is a measure that refers to the
amount that a material is elongated or stretched until it breaks,
relative to the initial length of the material. For example, if the
sample is originally 100 mm, and can be stretched to 120 mm, then
the elongation is 20%.

[0037] As used herein, the terms “coating composition(s),”

“composition(s),” “coating(s),” “formulation(s),” and the like, when
referring to the compositions of the present invention are used
interchangeably, and are intended to refer to the compositions of
the present invention.

Coating compositions

[0038] The present invention provides aqueous polyurethane

compositions which, when applied to substrates and cured, provide
the coated article with decorative and/or protective features. The
coating compositions of the present invention may provide design
freedom to manufacture transparent, pigmented, high gloss, matte,
opaque, and frosted looks on various substrates. A vast range of
colors may be selected. Dyes, pigments, etc., exhibiting the selected
colors may be included in the coating compositions, allowing the
glass or other substrate to take on a wide range of color nishes.
Color selection may be made by a customer, substrate supplier,
and/or manufacturer to provide a desired custom color nish.
Industry standard colors may also be added to the coatings. Further,
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the coatings impart superior chemical and mechanical resistance to

the coated substrates.

[0039] The coating compositions of the present invention do not

require any coalescing agent. The coating compositions contain
zero-to-low VOCs, and allow water to replace the currently used
organic solvents as cleaning liquid. VOCs, if any, derive from the
trace amounts arising from the production of the raw materials of
the composition. Unlike the coating compositions in US
2012/0201982, which still require the presence of 1% to 2% glycol,
the present invention can be free of solvent. As a result, water can
be used for cleaning. This further reduces the impact on the
environment.

[0040] The following is a non-exhaustive list, intended to be merely

exemplary, of substrates and articles that may be coated with the
coating compositions described herein: glass articles, such as
containers, windows, and mirrors; glass particles, for example glass
akes, which include, but are not limited to, platy transparent glass
or mica particles further comprising one or more inorganic layers,
such as oxide layers including titania (T1O2), silica (S1O2), iron oxide,
or combinations thereof; photonic pigments; ceramics; and metals.

[0041] One of the advantages that a coating composition of the

present invention o ers to those in the glass industry is that glass
products can be produced clear and colorless, with color being
added as needed by application of the present coatings to meet
current demand. Further, from the perspective of the recycling
industry, the need to sort based on color is greatly reduced, if not
eliminated. The coating compositions can be burned o the glass
before the glass reaches its melting temperature. Thus, recyclers
would only have clear glass to process, as opposed to working with
glass of two or more colors that would have to be sorted.

[0042] Glass particles and micas may be coated with the coatings
described herein. Such coated particles may be more robust than
those which are currently available, in which the colorants are
adsorbed onto the surface (e.g. laked colorants). With the present
coating compositions, a broader color palette may be realized and
the coated particles are not likely to bleed color. Coated particles of
the present invention may nd use in graphic arts and the coating
compositions may nd use in architectural, industrial, plastic, or
automotive coatings, and possibly cosmetic applications as well.
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[0043] The waterborne polyurethane coating compositions of the

present invention may be applied to glass substrates with or without
hot end coating and/or cold end coating; and with or without a
silane pre-treatment of the glass substrates.

[0044] The coating compositions of the present invention provide,

upon coating, high-performance environmentally-safe vehicles for
delivering a component or property to the substrate. For example,
the coatings can be used to color or protect glass, such as glass
containers and glass particles, through the delivery of a colorant or a
protectant to the glass that is included in the coating. Glass is but
one example of a substrate that may be coated with the presently
described coatings. Other suitable substrates include, but are not
limited to, wood, metal, paper, leather, textiles, felt, concrete,
masonry, ceramic, stone, plastics, combinations of the materials,
and the like.

[0045] In a preferred embodiment, the water-based coatings of the

present invention are stable as one-pot systems (i.e. single-
component or one-component systems). For example, all
components of the water-based coatings may remain in a uid,
aqueous, usable state for at least one week, or at least one month,
from the time the compositions are formulated (i.e. the components
are mixed together). The water-based coatings include a water-
dilutable polyurethane dispersion and at least one cross-linking
agent. The water-based coatings can also include at least one silane,
such as an oxysilane, as an adhesion promoter.

[0046] The water-based coatings of the present invention can be

cured after being applied to a substrate, such as a glass article. In
one embodiment, curing is e ected by the addition of heat. Heat
curing promotes a thermal cross-linking reaction involving the
water-dilutable polyurethane dispersion and the cross-linking agent.
In one embodiment, the thermal cross-linking reaction produces a
thermoset lm.

[0047] The water dilutable polyurethane dispersion is typically

present in the coating composition in an amount of about 1 wt% to
about 99 wt%, based on the total weight of the composition. For
example, the polyurethane dispersion may advantageously be
present in an amount of about 25 wt% to 95 wt%, or about 50 wt%
to about 90 wt%, based on the total weight of the composition. For
example, the polyurethane dispersion may be present in an amount
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of about 1 wt% to about 95 wt%; or about 1 wt% to about 90 wt%; or

about 1 wt% to about 85 wt%; or about 1 wt% to about 80 wt%; or
about 1 wt% to about 75 wt%; or about 1 wt% to about 70 wt%; or
about 1 wt% to about 65 wt%; or about 1 wt% to about 60 wt%; or
about 1 wt% to about 55 wt%; or about 1 wt% to about 50 wt%; or
about 1 wt% to about 45 wt%; or about 1 wt% to about 40 wt%; or
about 1 wt% to about 35 wt%; or about 1 wt% to about 30 wt%; or
about 1 wt% to about 25 wt%; or about 1 wt% to about 20 wt%; or
about 1 wt% to about 15 wt%; or about 1 wt% to about 10 wt%; or
about 1 wt% to about 5 wt%; or about 5 wt% to about 99 wt%; or
about 5 wt% to about 95 wt%; or about 5 wt% to about 90 wt%; or
about 5 wt% to about 85 wt%; or about 5 wt% to about 80 wt%; or
about 5 wt% to about 75 wt%; or about 5 wt% to about 70 wt%; or
about 5 wt% to about 65 wt%; or about 5 wt% to about 60 wt%; or
about 5 wt% to about 55 wt%; or about 5 wt% to about 50 wt%; or
about 5 wt% to about 45 wt%; or about 5 wt% to about 40 wt%; or
about 5 wt% to about 35 wt%; or about 5 wt% to about 30 wt%; or
about 5 wt% to about 25 wt%; or about 5 wt% to about 20 wt%; or
about 5 wt% to about 15 wt%; or about 5 wt% to about 10 wt%; or
about 10 wt% to about 99 wt%; or about 10 wt% to about 95 wt%; or
about 10 wt% to about 90 wt%; or about 10 wt% to about 85 wt%; or
about 10 wt% to about 80 wt%; or about 10 wt% to about 75 wt%; or
about 10 wt% to about 70 wt%; or about 10 wt% to about 65 wt%; or
about 10 wt% to about 60 wt%; or about 10 wt% to about 55 wt%; or
about 10 wt% to about 50 wt%; or about 10 wt% to about 45 wt%; or
about 10 wt% to about 40 wt%; or about 10 wt% to about 35 wt%; or
about 10 wt% to about 30 wt%; or about 10 wt% to about 25 wt%; or
about 10 wt% to about 20 wt%; or about 10 wt% to about 15 wt%; or
about 15 wt% to about 99 wt%; or about 15 wt% to about 95 wt%; or
about 15 wt% to about 90 wt%; or about 15 wt% to about 85 wt%; or
about 15 wt% to about 80 wt%; or about 15 wt% to about 75 wt%; or
about 15 wt% to about 70 wt%; or about 15 wt% to about 65 wt%; or
about 15 wt% to about 60 wt%; or about 15 wt% to about 55 wt%; or
about 15 wt% to about 50 wt%; or about 15 wt% to about 45 wt%; or
about 15 wt% to about 40 wt%; or about 15 wt% to about 35 wt%; or
about 15 wt% to about 30 wt%; or about 15 wt% to about 25 wt%; or
about 15 wt% to about 20 wt%; or about 20 wt% to about 99 wt%; or
about 20 wt% to about 95 wt%; or about 20 wt% to about 90 wt%; or
about 20 wt% to about 85 wt%; or about 20 wt% to about 80 wt%; or
about 20 wt% to about 75 wt%; or about 20 wt% to about 70 wt%; or
about 20 wt% to about 65 wt%; or about 20 wt% to about 60 wt%; or 
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about 20 wt% to about 55 wt%; or about 20 wt% to about 50 wt%; or

about 20 wt% to about 45 wt%; or about 20 wt% to about 40 wt%; or
about 20 wt% to about 35 wt%; or about 20 wt% to about 30 wt%; or
about 20 wt% to about 25 wt%; or about 25 wt% to about 99 wt%; or
about 25 wt% to about 95 wt%; or about 25 wt% to about 90 wt%; or
about 25 wt% to about 85 wt%; or about 25 wt% to about 80 wt%; or
about 25 wt% to about 75 wt%; or about 25 wt% to about 70 wt%; or
about 25 wt% to about 65 wt%; or about 25 wt% to about 60 wt%; or
about 25 wt% to about 55 wt%; or about 25 wt% to about 50 wt%; or
about 25 wt% to about 45 wt%; or about 25 wt% to about 40 wt%; or
about 25 wt% to about 35 wt%; or about 25 wt% to about 30 wt%; or
about 30 wt% to about 99 wt%; or about 30 wt% to about 95 wt%; or
about 30 wt% to about 90 wt%; or about 30 wt% to about 85 wt%; or
about 30 wt% to about 80 wt%; or about 30 wt% to about 75 wt%; or
about 30 wt% to about 70 wt%; or about 30 wt% to about 65 wt%; or
about 30 wt% to about 60 wt%; or about 30 wt% to about 55 wt%; or
about 30 wt% to about 50 wt%; or about 30 wt% to about 45 wt%; or
about 30 wt% to about 40 wt%; or about 30 wt% to about 35 wt%; or
about 35 wt% to about 99 wt%; or about 35 wt% to about 95 wt%; or
about 35 wt% to about 90 wt%; or about 35 wt% to about 85 wt%; or
about 35 wt% to about 80 wt%; or about 35 wt% to about 75 wt%; or
about 35 wt% to about 70 wt%; or about 35 wt% to about 65 wt%; or
about 35 wt% to about 60 wt%; or about 35 wt% to about 55 wt%; or
about 35 wt% to about 50 wt%; or about 35 wt% to about 45 wt%; or
about 35 wt% to about 40 wt%; or about 40 wt% to about 99 wt%; or
about 40 wt% to about 95 wt%; or about 40 wt% to about 90 wt%; or
about 40 wt% to about 85 wt%; or about 40 wt% to about 80 wt%; or
about 40 wt% to about 75 wt%; or about 40 wt% to about 70 wt%; or
about 40 wt% to about 65 wt%; or about 40 wt% to about 60 wt%; or
about 40 wt% to about 55 wt%; or about 40 wt% to about 50 wt%; or
about 40 wt% to about 45 wt%; or about 45 wt% to about 99 wt%; or
about 45 wt% to about 95 wt%; or about 45 wt% to about 90 wt%; or
about 45 wt% to about 85 wt%; or about 45 wt% to about 80 wt%; or
about 45 wt% to about 75 wt%; or about 45 wt% to about 70 wt%; or
about 45 wt% to about 65 wt%; or about 45 wt% to about 60 wt%; or
about 45 wt% to about 55 wt%; or about 45 wt% to about 50 wt%; or
about 50 wt% to about 99 wt%; or about 50 wt% to about 95 wt%; or
about 50 wt% to about 90 wt%; or about 50 wt% to about 85 wt%; or
about 50 wt% to about 80 wt%; or about 50 wt% to about 75 wt%; or
about 50 wt% to about 70 wt%; or about 50 wt% to about 65 wt%; or
about 50 wt% to about 60 wt%; or about 50 wt% to about 55 wt%; or 
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about 55 wt% to about 99 wt%; or about 55 wt% to about 95 wt%; or

about 55 wt% to about 90 wt%; or about 55 wt% to about 85 wt%; or
about 55 wt% to about 80 wt%; or about 55 wt% to about 75 wt%; or
about 55 wt% to about 70 wt%; or about 55 wt% to about 65 wt%; or
about 55 wt% to about 60 wt%; or about 60 wt% to about 99 wt%; or
about 60 wt% to about 95 wt%; or about 60 wt% to about 90 wt%; or
about 60 wt% to about 85 wt%; or about 60 wt% to about 80 wt%; or
about 60 wt% to about 75 wt%; or about 60 wt% to about 70 wt%; or
about 60 wt% to about 65 wt%; or about 65 wt% to about 99 wt%; or
about 65 wt% to about 95 wt%; or about 65 wt% to about 90 wt%; or
about 65 wt% to about 85 wt%; or about 65 wt% to about 80 wt%; or
about 65 wt% to about 75 wt%; or about 65 wt% to about 70 wt%; or
about 70 wt% to about 99 wt%; or about 70 wt% to about 95 wt%; or
about 70 wt% to about 90 wt%; or about 70 wt% to about 85 wt%; or
about 70 wt% to about 80 wt%; or about 70 wt% to about 75 wt%; or
about 75 wt% to about 99 wt%; or about 75 wt% to about 95 wt%; or
about 75 wt% to about 90 wt%; or about 75 wt% to about 85 wt%; or
about 75 wt% to about 80 wt%; or about 80 wt% to about 99 wt%; or
about 80 wt% to about 95 wt%; or about 80 wt% to about 90 wt%; or
about 80 wt% to about 85 wt%; or about 85 wt% to about 99 wt%; or
about 85 wt% to about 95 wt%; or about 85 wt% to about 90 wt%; or
about 90 wt% to about 99 wt%; or about 90 wt% to about 95 wt%; or
about 95 wt% to about 99 wt%.

[0048] The solids content of the polyurethane dispersion is generally

about 5 wt% to about 60 wt%, based on the total weight of the
polyurethane dispersion. For example, the solids content of the
polyurethane dispersion may be about 10 wt% to about 50 wt%, or
about 20 wt% to about 40 wt%. For example, the solids content of
the polyurethane dispersion may be about 5 wt% to about 55 wt%;
or about 5 wt% to about 50 wt%; or about 5 wt% to about 45 wt%; or
about 5 wt% to about 40 wt%; or about 5 wt% to about 35 wt%; or
about 5 wt% to about 30 wt%; or about 5 wt% to about 25 wt%; or
about 5 wt% to about 20 wt%; or about 5 wt% to about 15 wt%; or
about 5 wt% to about 10 wt%; or about 10 wt% to about 60 wt%; or
about 10 wt% to about 55 wt%; or about 10 wt% to about 50 wt%; or
about 10 wt% to about 45 wt%; or about 10 wt% to about 40 wt%; or
about 10 wt% to about 35 wt%; or about 10 wt% to about 30 wt%; or
about 10 wt% to about 25 wt%; or about 10 wt% to about 20 wt%; or
about 10 wt% to about 15 wt%; or about 15 wt% to about 60 wt%; or
about 15 wt% to about 55 wt%; or about 15 wt% to about 50 wt%; or
about 15 wt% to about 45 wt%; or about 15 wt% to about 40 wt%; or

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about 15 wt% to about 35 wt%; or about 15 wt% to about 30 wt%; or

about 15 wt% to about 25 wt%; or about 15 wt% to about 20 wt%; or
about 20 wt% to about 60 wt%; or about 20 wt% to about 55 wt%; or
about 20 wt% to about 50 wt%; or about 20 wt% to about 45 wt%; or
about 20 wt% to about 40 wt%; or about 20 wt% to about 35 wt%; or
about 20 wt% to about 30 wt%; or about 20 wt% to about 25 wt%; or
about 25 wt% to about 60 wt%; or about 25 wt% to about 55 wt%; or
about 25 wt% to about 50 wt%; or about 25 wt% to about 45 wt%; or
about 25 wt% to about 40 wt%; or about 25 wt% to about 35 wt%; or
about 25 wt% to about 30 wt%; or about 30 wt% to about 60 wt%; or
about 30 wt% to about 55 wt%; or about 30 wt% to about 50 wt%; or
about 30 wt% to about 45 wt%; or about 30 wt% to about 40 wt%; or
about 30 wt% to about 35 wt%; or about 35 wt% to about 60 wt%; or
about 35 wt% to about 55 wt%; or about 35 wt% to about 50 wt%; or
about 35 wt% to about 45 wt%; or about 35 wt% to about 40 wt%; or
about 40 wt% to about 60 wt%; or about 40 wt% to about 55 wt%; or
about 40 wt% to about 50 wt%; or about 40 wt% to about 45 wt%; or
about 45 wt% to about 60 wt%; or about 45 wt% to about 55 wt%; or
about 45 wt% to about 50 wt%; or about 50 wt% to about 60 wt% or
about 50 wt% to about 55 wt%.

[0049] Therefore, the amount of polyurethane resin in the coating

composition is generally about 0.05 wt% to about 60 wt%, based on
the total weight of the coating composition. For example, the
amount of polyurethane resin in the coating composition may be
about 0.1 wt% to about 50 wt%, or about 0.2 wt% to about 40 wt%.
One of ordinary skill in the art can easily calculate the amount of
polyurethane resin in the coating composition by multiplying the
amount of polyurethane dispersion in the coating composition by
the solids content of the polyurethane dispersion (e.g. 99 wt% of
dispersion X 60% solids content = (99)(0.6) = 59.4 wt% of
polyurethane resin).

[0050] Typically, the water dilutable polyurethane has a molecular

weight (MW) of about 5,000 to about 100,000 Daltons. For example,
the polyurethane may have a MW of about 10,000 to about 75,000
Daltons, or from about 15,000 to about 50,000 Daltons.

[0051] The glass transition temperature (Tg) of the polyurethane is

typically in the range of about -40°C to about 50°C. For example, the
Tg of the polyurethane may be in the range of about -30°C to about
50°C, or in the range of about -20°C to about 50°C. For example, the 
Tg of the polyurethane may be in the range of about -40°C to about
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40°C; or about -30°C to about 40°C; or about -30°C to about 30°C; or

about -20°C to about 30°C; or about -20°C to about 20°C.

[0052] The minimum lm forming temperature (MFFT) of the water

dilutable polyurethane is typically in the range of about -50°C to
about 50°C. For example, the MFFT of the polyurethane may be in
the range of about -40°C to about 40°C, or about -30°C to about
30°C, or about -20°C to about 20°C, or in the range of about -10°C to
about 10°C.

[0053] The acid number of the polyurethane is generally greater

than 20 mg KOH/g, or greater than 25 mg KOH/g, or greater than 30
mg KOH/g. Generally, the sum of the acid number and the hydroxyl
number of the polyurethane is greater than 20 mg KOH/g, or greater
than 25 mg KOH/g, or greater than 30 mg KOH/g, or greater than 40
mg KOH/g.

[0054] The viscosity of the polyurethane dispersion is typically about

5 cP to about 5000 cP. For example, the viscosity of the ink or
coating composition may be about 50 cP to about 4000 cP, or about
100 cP to about 2000 cP.

[0055] The elongation at break of the polyurethane is typically about

10% to about 250%. For example, the elongation of the
polyurethane can be about 20% to about 200%, or about 30% to
about 150%.

[0056] The tensile strength at break of the polyurethane is typically

about 5 MPa to about 150 MPa. For example the tensile strength of
the polyurethane may be about 10 MPa to about 100 MPa, or from
about 20 MPa to about 50 MPa.

[0057] The water dilutable polyurethane resin may comprise a

reaction product of: (A) a polyisocyanate component; (B) a polyol
component; and (C) an isocyanate-reactive component comprising
an ionic group or potentially ionic group. As used herein, the term
“polyisocyanate” refers to compounds comprising at least two
unreacted isocyanate groups. Polyisocyanates include diisocyanates
and diisocyanate reaction products comprising, for example,
urethane groups, urea groups, uretodione groups, uretonimine
groups, isocyanurate groups, iminooxadiazine dione groups,
oxadiazine trione groups, carbodiimide groups, acyl urea groups,
biuret groups, and/or allophanate groups. 
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[0058] The repeat unit in the water dilutable carboxyl or hydroxyl

functional polyurethane may comprise an aliphatic or cycloaliphatic
diisocyanate. Examples of the polyisocyanate component (A) include,
but are not limited to, 4,4′-diisocyanatocyclohexylmethane (HMDI);
hexamethylene diisocyanate (HDI); l -methyl-2,4(2,6)-
diisocyanatocyclohexane; or 1-isocyanato-3,3,5-trimethyl-5-
isocyanatomethyl-cyclohexane (IPDI); and mixtures thereof.
Preferably the polyisocyanate component is 4,4′-
diisocyanatocyclohexylmethane (HMDI). In addition to the aliphatic
or cycloaliphatic diisocyanate, the water-dilutable carboxyl or
hydroxyl functional polyurethane dispersion may also contain other
polyisocyanates, such as norbornane diisocyanate (NBDI); 2,4-
and/or 2,6-diisocyanatotoluene (TDI); l-methyl-2,4-and/or -2,6-
diisocyanatocyclohexane; and 4,4′-diisocyanatodiphenylmethane
(MDI); xylylene diisocyanate; tetramethylene diisocyanate; 1,4-
diisocyanatobutane; 1, 12-diisocyanatododecane; 2,3,3-
trimethylhexamethylene diisocyanate; 1,4-cyclohexylene
diisocyanate; 4,4′-dicyclohexylmethane diisocyanate; 4,4′-
dicyclohexyl diisocyanate;

α,α,α’,α’-tetramethyl-m- or p-xylylene diisocyanate;

triphenylmethane 4,4′,4″-triisocyanate; 4-isocyanatomethyl-l ,8-
octamethylene diisocyanate; mixtures thereof; and the like.

[0059] In various non-limiting embodiments, the polyol component

(B) may comprise an oligomeric or polymeric compound having
terminal and/or pendant hydroxyl groups.

Examples of the polyol component include, but are not limited to,
polyether polyol, polyester polyol, polyacrylic polyol, polycarbonate
polyol, or mixtures thereof, which may comprise diol, triol or tetraol
monomers. Examples of diol monomers include tetrahydrofuran;
styrene oxide; propylene oxide; ethylene oxide; butylene oxides;
epichlorohydrin; ethylene glycol; 1,2 propanediol; 1,3 -propanediol;
diethylene glycol; 1,4-butanediol; 1,5-pentanediol; 1,6- hexanediol;
1,8-octanediol; neopentyl glycol; 2-methyl-l,3-propanediol; the bis-
hydroxymethylcyclohexane isomers; and 2,2-bis-(4-
hydroxyphenyl)propane. Examples of triol monomers include
trimethylolpropane (TMP), glycerol, and triethanolamine.

Preferably, pentaerythritol or tris-(2-hydroxyethyl)isocyanurate

(THEIC) is used as a tetraol or triol monomer.
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[0060] In various non-limiting embodiments, the isocyanate-reactive

group (C) may comprise at least one ionic group or potentially ionic
group, which may be either cationic or anionic in nature. The
isocyanate-reactive component (C) may also comprise at least one
isocynanate-reactive group such as a hydroxyl group and/or an
amine group. Examples of the isocyanate-reactive group (C) include,
but are not limited to, 2,2-bis(hydroxymethyl)-alkanecarboxylic acids
(such as dimethylolacetic acid; 2,2-dimethylol-propionic acid; 2,2
dimethylolbutyric acid; or 2,2-dimethylolpentanoic acid),
dihydroxysuccinic acid, hydroxypivalic acid and mixtures thereof.

[0061] The bases necessary for at least partially neutralizing the

carboxyl groups include, but are not limited to, ammonia, N-
methylmorpholine, dimethyl-isopropanolamine,

tri ethyl amine, dimethylethanolamine, methyldiethanolamine,

triethanolamine, morpholine, tri propylamine, ethanolamine,
triisopropanolamine, 2-diethylamino-2-methyl-l-propanol and
mixtures of these and/or other neutralizing agents. Sodium
hydroxide, lithium hydroxide and potassium hydroxide are also
suitable, although less preferred, as neutralizing agents.

[0062] The cross-linking agents can react with either carboxyl

groups, or hydroxyl groups, or both. Examples of suitable cross-
linkers include, but are not limited to, blocked

polyisocyanates (e.g. API-BI795®, Advanced Polymer, Inc.), in which

the isocyanate end group is protected by a blocking group, and is
activated upon heating; aminoplast resins (e.g. Cymel® 303 LF,
Allnex); and carbodiimides and carbodiimide derivates (e.g. the

Carbodilite® series from Nisshinbo Chemical, Inc., and Picassian®

series from Stahl Polymers).

[0063] In various non-limiting embodiments, the blocked

polyisocyanates are soluble or dispersible in water and typically
have a blocked isocyanate group content (calculated as NCO,
molecular weight = 42) of about 1 to 10 wt%, or of about 2 to 8 wt%,
based on the

supply form. The solids content of the blocked polyisocyanates is

generally about 5 to 60 wt%. For example, the solids content of the
blocked polyisocyanates can be 10 to 50 wt%, or 20 to 40 wt%. The
viscosity of the blocked polyisocyanates is typically about 5 to 5000
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cP. For example, the viscosity of the blocked polyisocyanates can be

about 50 to 4000 cP, or about 100 to 2000 cP. The blocked
polyisocyanates generally have an unblocking temperature of 50 °C
to 300 °C. For example, the blocked polyisocyanates may have an
unblocking temperature of 100 – 250 °C, or 150 to 200 °C. The
boiling point of the blocking group is typically above 150 °C. For
example, the boiling pointof the blocking group can be above 200
°C. Suitable blocking agents are disclosed in “Blocked isocyanates III
Part A: Mechanism and Chemistry,” Douglas A. Wicks and Zeno W.
Wicks Jr., Progress in Organic Coatings 36 (1999) 148-172 and
“Blocked isocyanates III Part B: Uses and applications of blocked
isocyanates,” Douglas. A. Wicks and Zeno W. Wicks Jr., Progress in
Organic Coatings 41 (2001) 1-83.

[0064] In various non-limiting embodiments, aminoplast cross-

linking components disclosed herein may be selected from the
group consisting of urea-based resins and melamine-based resins
that are water-dilutable. As used herein, the term “aminoplast resin”
refers to resins based on urea-formaldehyde or melamine-
formaldehyde condensation products. Suitable aminoplast resins
are commercially available from Allnex USA Inc., under the Cymel®
trademark. Aminoplast resins comprise functional groups, such as,
for example,

alkoxymethyl groups, which are reactive with carboxyl or hydroxyl

groups at temperatures above ambient temperature. For instance,
aminoplast resins comprising alkoxymethyl groups may be used to
crosslink and cure polyol resins primarily by trans-esteri cation
reaction between the hydroxyl groups on the polyol resins and the
alkoxymethyl groups on the aminoplast resin.

[0065] In various non-limiting embodiments, the aminoplast resin of

the waterborne polyurethane coating compositions disclosed herein
may comprise a urea-based resin comprising a urea-formaldehyde
condensation product. Suitable urea-formaldehyde condensation
products include, for example, urea-formaldehyde condensates that
are non-etheri ed, partially-etheri ed, or fully-etheri ed with
monohydric alcohols comprising 1 to 20 carbon atoms.

[0066] In various non-limiting embodiments, the aminoplast resin of

the waterborne polyurethane coating compositions disclosed herein
may comprise a melamine-based resin comprising a melamine-
formaldehyde condensation product. Suitable melamine-
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formaldehyde condensation products include, for example,

melamine-formaldehyde condensates that are non-etheri ed,
partially-etheri ed, or fully-etheri ed with monohydric alcohols
comprising 1 to 20 carbon atoms. The aminoplast resins are
generally supplied in liquid form, and may have a solids content of
greater than 98%.

[0067] In various non-limiting embodiments, the aminoplast resin

may comprise monomeric, oligomeric, or polymeric melamine-
formaldehyde resins such as, for example, methylated melamines,
ethylated melamines, propylated melamines, butylated melamines,
and mixed alkylated melamines (e.g., methylated/butylated
melamines).

[0068] In various non-limiting embodiments, the aminoplast resin

may comprise methylol groups, alkoxymethyl groups, or both. An
alkoxymethyl group may be of the general formula — CH2OR, where
R is a linear, cyclic, or branched alkyl chain having from 1 to 20
carbon atoms.

[0069] In various non-limiting embodiments, the aminoplast resin

may comprise an oligomeric, methylated, and high-imino group-
containing melamine-formaldehyde condensate comprising low
methylol content. For example, the aminoplast resin may comprise
an oligomeric methylated melamine-formaldehyde condensation
product comprising imino groups, methoxymethyl groups, and
methylol groups.

[0070] In various non-limiting embodiments, the water-dilutable

carbodiimide cross-linker has a carbodiimide equivalent weight of
about 100 to 800. For example, the carbodiimide cross-linker may
have a carbodiimide equivalent weight of 200 to 600, or 300 to 400.
The ratio of moles of carbodiimide (-NCN-) groups in the cross-linker
to moles of the carboxylic groups (-COOH) in the polyurethane is
generally about 0.2: 1 to about 1.2: 1. For example, the ratio of
carbodiimide groups in the cross-linker to the carboxylic groups in
the polyurethane may be about 0.4: 1 to about 1.0: 1, or about 0.6: 1
to about 0.8: 1. The solids content of the carbodiimide cross-linker is
typically about 30 to 60 wt%. For example, the solids content of the
carbodiimide cross-linker may be 35 to 55 wt%, or 40 to 50 wt%. The
viscosity of the carbodiimide cross-linker is generally about 50 to
500 cP. For example, the viscosity of the carbodiimide may be about
100 to 400 cP, or about 150 to 300 cP. Examples of suitable

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carbodiimide cross-linkers include, but are not limited to,

CARBODILITE® E-05 (Nisshinbo Chemical Inc.) and Picassian® XL-
732 (Stahl Polymers).

[0071] The cross-linkers are generally available as liquid

formulations (e.g. as dispersions or solutions in water or another
suitable solvent). The cross-linker liquid formulation is typically
present in the coating composition in an amount of about 1 wt% to
about 99 wt%, based on the total weight of the composition. For
example, the cross-linker liquid formulation may advantageously be
present in an amount of about 5 wt% to 75 wt%, or about 10 wt% to
about 50 wt%, based on the total weight of the composition. For
example, the cross-linker liquid formulation may be present in an
amount of about 1 wt% to about 95 wt%; or about 1 wt% to about 90
wt%; or about 1 wt% to about 85 wt%; or about 1 wt% to about 80
wt%; or about 1 wt% to about 75 wt%; or about 1 wt% to about 70
wt%; or about 1 wt% to about 65 wt%; or about 1 wt% to about 60
wt%; or about 1 wt% to about 55 wt%; or about 1 wt% to about 50
wt%; or about 1 wt% to about 45 wt%; or about 1 wt% to about 40
wt%; or about 1 wt% to about 35 wt%; or about 1 wt% to about 30
wt%; or about 1 wt% to about 25 wt%; or about 1 wt% to about 20
wt%; or about 1 wt% to about 15 wt%; or about 1 wt% to about 10
wt%; or about 1 wt% to about 5 wt%; or about 5 wt% to about 99
wt%; or about 5 wt% to about 95 wt%; or about 5 wt% to about 90
wt%; or about 5 wt% to about 85 wt%; or about 5 wt% to about 80
wt%; or about 5 wt% to about 75 wt%; or about 5 wt% to about 70
wt%; or about 5 wt% to about 65 wt%; or about 5 wt% to about 60
wt%; or about 5 wt% to about 55 wt%; or about 5 wt% to about 50
wt%; or about 5 wt% to about 45 wt%; or about 5 wt% to about 40
wt%; or about 5 wt% to about 35 wt%; or about 5 wt% to about 30
wt%; or about 5 wt% to about 25 wt%; or about 5 wt% to about 20
wt%; or about 5 wt% to about 15 wt%; or about 5 wt% to about 10
wt%; or about 10 wt% to about 99 wt%; or about 10 wt% to about 95
wt%; or about 10 wt% to about 90 wt%; or about 10 wt% to about 85
wt%; or about 10 wt% to about 80 wt%; or about 10 wt% to about 75
wt%; or about 10 wt% to about 70 wt%; or about 10 wt% to about 65
wt%; or about 10 wt% to about 60 wt%; or about 10 wt% to about 55
wt%; or about 10 wt% to about 50 wt%; or about 10 wt% to about 45
wt%; or about 10 wt% to about 40 wt%; or about 10 wt% to about 35
wt%; or about 10 wt% to about 30 wt%; or about 10 wt% to about 25
wt%; or about 10 wt% to about 20 wt%; or about 10 wt% to about 15
wt%; or about 15 wt% to about 99 wt%; or about 15 wt% to about
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95 wt%; or about 15 wt% to about 90 wt%; or about 15 wt% to about

85 wt%; or about 15 wt% to about 80 wt%; or about 15 wt% to about
75 wt%; or about 15 wt% to about 70 wt%; or about 15 wt% to about
65 wt%; or about 15 wt% to about 60 wt%; or about 15 wt% to about
55 wt%; or about 15 wt% to about 50 wt%; or about 15 wt% to about
45 wt%; or about 15 wt% to about 40 wt%; or about 15 wt% to about
35 wt%; or about 15 wt% to about 30 wt%; or about 15 wt% to about
25 wt%; or about 15 wt% to about 20 wt%; or about 20 wt% to about
99 wt%; or about 20 wt% to about 95 wt%; or about 20 wt% to about
90 wt%; or about 20 wt% to about 85 wt%; or about 20 wt% to about
80 wt%; or about 20 wt% to about 75 wt%; or about 20 wt% to about
70 wt%; or about 20 wt% to about 65 wt%; or about 20 wt% to about
60 wt%; or about 20 wt% to about 55 wt%; or about 20 wt% to about
50 wt%; or about 20 wt% to about 45 wt%; or about 20 wt% to about
40 wt%; or about 20 wt% to about 35 wt%; or about 20 wt% to about
30 wt%; or about 20 wt% to about 25 wt%; or about 25 wt% to about
99 wt%; or about 25 wt% to about 95 wt%; or about 25 wt% to about
90 wt%; or about 25 wt% to about 85 wt%; or about 25 wt% to about
80 wt%; or about 25 wt% to about 75 wt%; or about 25 wt% to about
70 wt%; or about 25 wt% to about 65 wt%; or about 25 wt% to about
60 wt%; or about 25 wt% to about 55 wt%; or about 25 wt% to about
50 wt%; or about 25 wt% to about 45 wt%; or about 25 wt% to about
40 wt%; or about 25 wt% to about 35 wt%; or about 25 wt% to about
30 wt%; or about 30 wt% to about 99 wt%; or about 30 wt% to about
95 wt%; or about 30 wt% to about 90 wt%; or about 30 wt% to about
85 wt%; or about 30 wt% to about 80 wt%; or about 30 wt% to about
75 wt%; or about 30 wt% to about 70 wt%; or about 30 wt% to about
65 wt%; or about 30 wt% to about 60 wt%; or about 30 wt% to about
55 wt%; or about 30 wt% to about 50 wt%; or about 30 wt% to about
45 wt%; or about 30 wt% to about 40 wt%; or about 30 wt% to about
35 wt%; or about 35 wt% to about 99 wt%; or about 35 wt% to about
95 wt%; or about 35 wt% to about 90 wt%; or about 35 wt% to about
85 wt%; or about 35 wt% to about 80 wt%; or about 35 wt% to about
75 wt%; or about 35 wt% to about 70 wt%; or about 35 wt% to about
65 wt%; or about 35 wt% to about 60 wt%; or about 35 wt% to about
55 wt%; or about 35 wt% to about 50 wt%; or about 35 wt% to about
45 wt%; or about 35 wt% to about 40 wt%; or about 40 wt% to about
99 wt%; or about 40 wt% to about 95 wt%; or about 40 wt% to about
90 wt%; or about 40 wt% to about 85 wt%; or about 40 wt% to about
80 wt%; or about 40 wt% to about 75 wt%; or about 40 wt% to about
70 wt%; or about 40 wt% to about 65 wt%; or about 40 wt% to about 
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60 wt%; or about 40 wt% to about 55 wt%; or about 40 wt% to about

50 wt%; or about 40 wt% to about 45 wt%; or about 45 wt% to about
99 wt%; or about 45 wt% to about 95 wt%; or about 45 wt% to about
90 wt%; or about 45 wt% to about 85 wt%; or about 45 wt% to about
80 wt%; or about 45 wt% to about 75 wt%; or about 45 wt% to about
70 wt%; or about 45 wt% to about 65 wt%; or about 45 wt% to about
60 wt%; or about 45 wt% to about 55 wt%; or about 45 wt% to about
50 wt%; or about 50 wt% to about 99 wt%; or about 50 wt% to about
95 wt%; or about 50 wt% to about 90 wt%; or about 50 wt% to about
85 wt%; or about 50 wt% to about 80 wt%; or about 50 wt% to about
75 wt%; or about 50 wt% to about 70 wt%; or about 50 wt% to about
65 wt%; or about 50 wt% to about 60 wt%; or about 50 wt% to about
55 wt%; or about 55 wt% to about 99 wt%; or about 55 wt% to about
95 wt%; or about 55 wt% to about 90 wt%; or about 55 wt% to about
85 wt%; or about 55 wt% to about 80 wt%; or about 55 wt% to about
75 wt%; or about 55 wt% to about 70 wt%; or about 55 wt% to about
65 wt%; or about 55 wt% to about 60 wt%; or about 60 wt% to about
99 wt%; or about 60 wt% to about 95 wt%; or about 60 wt% to about
90 wt%; or about 60 wt% to about 85 wt%; or about 60 wt% to about
80 wt%; or about 60 wt% to about 75 wt%; or about 60 wt% to about
70 wt%; or about 60 wt% to about 65 wt%; or about 65 wt% to about
99 wt%; or about 65 wt% to about 95 wt%; or about 65 wt% to about
90 wt%; or about 65 wt% to about 85 wt%; or about 65 wt% to about
80 wt%; or about 65 wt% to about 75 wt%; or about 65 wt% to about
70 wt%; or about 70 wt% to about 99 wt%; or about 70 wt% to about
95 wt%; or about 70 wt% to about 90 wt%; or about 70 wt% to about
85 wt%; or about 70 wt% to about 80 wt%; or about 70 wt% to about
75 wt%; or about 75 wt% to about 99 wt%; or about 75 wt% to about
95 wt%; or about 75 wt% to about 90 wt%; or about 75 wt% to about
85 wt%; or about 75 wt% to about 80 wt%; or about 80 wt% to about
99 wt%; or about 80 wt% to about 95 wt%; or about 80 wt% to about
90 wt%; or about 80 wt% to about 85 wt%; or about 85 wt% to about
99 wt%; or about 85 wt% to about 95 wt%; or about 85 wt% to about
90 wt%; or about 90 wt% to about 99 wt%; or about 90 wt% to about
95 wt%; or about 95 wt% to about 99 wt%.

[0072] The solids content of the cross-linker liquid formulation is

typically about 5 wt% to about 99 wt%. For example, the solids
content of the cross-linker liquid formulation may be about 10 wt%
to about 50 wt%; or about 20 wt% to about 40 wt%; or about 30 wt%
to about 60 wt%; or about 35 wt% to about 55 wt%; or about 40 wt%
to about 50 wt%; or about 40 wt% to about 99 wt%. For example, the

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solids content of the cross-linker liquid formulation may be about 5

wt% to about 95 wt%; or about 5 wt% to about 90 wt%; or about 5
wt% to about 85 wt%; or about 5 wt% to about 90 wt%; or about 5
wt% to about 85 wt%; or about 5 wt% to about 80 wt%; or about 5
wt% to about 75 wt%; or about 5 wt% to about 70 wt%; or about 5
wt% to about 65 wt%; or about 5 wt% to about 60 wt%; or about 5
wt% to about 55 wt%; or about 5 wt% to about 50 wt%; or about 5
wt% to about 45 wt%; or about 5 wt% to about 40 wt%; or about 5
wt% to about 35 wt%; or about 5 wt% to about 30 wt%; or about 5
wt% to about 25 wt%; or about 5 wt% to about 20 wt%; or about 5
wt% to about 15 wt%; or about 5 wt% to about 10 wt%; or about 10
wt% to about 99 wt%; or about 10 wt% to about 95 wt%; or about 10
wt% to about 90 wt%; or about 10 wt% to about 85 wt%; or about 10
wt% to about 80 wt%; or about 10 wt% to about 75 wt%; or about 10
wt% to about 65 wt%; or about 10 wt% to about 60 wt%; or about 10
wt% to about 55 wt%; or about 10 wt% to about 50 wt%; or about 10
wt% to about 45 wt%; or about 10 wt% to about 40 wt%; or about 10
wt% to about 35 wt%; or about 10 wt% to about 30 wt%; or about 10
wt% to about 25 wt%; or about 10 wt% to about 20 wt%; or about 10
wt% to about 15 wt%; or about 15 wt% to about 99 wt%; or about 15
wt% to about 95 wt%; or about 15 wt% to about 90 wt%; or about 15
wt% to about 85 wt%; or about 15 wt% to about 80 wt%; or about 15
wt% to about 75 wt%; or about 15 wt% to about 70 wt%; or about 15
wt% to about 65 wt%; or about 15 wt% to about 60 wt%; or about 15
wt% to about 55 wt%; or about 15 wt% to about 50 wt%; or about 15
wt% to about 45 wt%; or about 15 wt% to about 40 wt%; or about 15
wt% to about 35 wt%; or about 15 wt% to about 30 wt%; or about 15
wt% to about 25 wt%; or about 15 wt% to about 20 wt%; or about 20
wt% to about 99 wt%; or about 20 wt% to about 95 wt%; or about 20
wt% to about 90 wt%; or about 20 wt% to about 85 wt%; or about 20
wt% to about 80 wt%; or about 20 wt% to about 75 wt%; or about 20
wt% to about 70 wt%; or about 20 wt% to about 65 wt%; or about 20
wt% to about 60 wt%; or about 20 wt% to about 55 wt%; or about 20
wt% to about 50 wt%; or about 20 wt% to about 45 wt%; or about 20
wt% to about 40 wt%; or about 20 wt% to about 35 wt%; or about 20
wt% to about 30 wt%; or about 20 wt% to about 25 wt%; or about 25
wt% to about 99 wt%; or about 25 wt% to about 95 wt%; or about 25
wt% to about 90 wt%; or about 25 wt% to about 85 wt%; or about 25
wt% to about 80 wt%; or about 25 wt% to about 75 wt%; or about 25
wt% to about 70 wt%; or about 25 wt% to about 65 wt%; or about 25
wt% to about 60 wt%; or about 25 wt% to about 55 wt%; or about 25 
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wt% to about 50 wt%; or about 25 wt% to about 45 wt%; or about 25

wt% to about 40 wt%; or about 25 wt% to about 35 wt%; or about 25
wt% to about 30 wt%; or about 30 wt% to about 99 wt%; or about 30
wt% to about 95 wt%; or about 30 wt% to about 90 wt%; or about 30
wt% to about 85 wt%; or about 30 wt% to about 80 wt%; or about 30
wt% to about 75 wt%; or about 30 wt% to about 70 wt%; or about 30
wt% to about 65 wt%; or about 30 wt% to about 60 wt%; or about 30
wt% to about 55 wt%; or about 30 wt% to about 50 wt%; or about 30
wt% to about 45 wt%; or about 30 wt% to about 40 wt%; or about 30
wt% to about 35 wt%; or about 35 wt% to about 99 wt%; or about 35
wt% to about 95 wt%; or about 35 wt% to about 90 wt%; or about 35
wt% to about 85 wt%; or about 35 wt% to about 80 wt%; or about 35
wt% to about 75 wt%; or about 35 wt% to about 70 wt%; or about 35
wt% to about 65 wt%; or about 35 wt% to about 60 wt%; or about 35
wt% to about 55 wt%; or about 35 wt% to about 50 wt%; or about 35
wt% to about 45 wt%; or about 35 wt% to about 40 wt%; or about 40
wt% to about 99 wt%; or about 40 wt% to about 95 wt%; or about 40
wt% to about 90 wt%; or about 40 wt% to about 85 wt%; or about 40
wt% to about 80 wt%; or about 40 wt% to about 75 wt%; or about 40
wt% to about 70 wt%; or about 40 wt% to about 65 wt%; or about 40
wt% to about 60 wt%; or about 40 wt% to about 55 wt%; or about 40
wt% to about 50 wt%; or about 40 wt% to about 45 wt%; or about 45
wt% to about 99 wt%; or about 45 wt% to about 95 wt%; or about 45
wt% to about 90 wt%; or about 45 wt% to about 85 wt%; or about 45
wt% to about 80 wt%; or about 45 wt% to about 75 wt%; or about 45
wt% to about 70 wt%; or about 45 wt% to about 65 wt%; or about 45
wt% to about 60 wt%; or about 45 wt% to about 55 wt%; or about 45
wt% to about 50 wt%; or about 50 wt% to about 99 wt%; or about 50
wt% to about 95 wt%; or about 50 wt% to about 90 wt%; or about 50
wt% to about 85 wt%; or about 50 wt% to about 80 wt%; or about 50
wt% to about 75 wt%; or about 50 wt% to about 70 wt%; or about 50
wt% to about 65 wt%; or about 50 wt% to about 60 wt%; or about 50
wt% to about 55 wt%; or about 55 wt% to about 99 wt%; or about 55
wt% to about 95 wt%; or about 55 wt% to about 90 wt%; or about 55
wt% to about 85 wt%; or about 55 wt% to about 80 wt%; or about 55
wt% to about 75 wt%; or about 55 wt% to about 70 wt%; or about 55
wt% to about 65 wt%; or about 55 wt% to about 60 wt%; or about 60
wt% to about 99 wt%; or about 60 wt% to about 95 wt%; or about 60
wt% to about 90 wt%; or about 60 wt% to about 85 wt%; or about 60
wt% to about 80 wt%; or about 60 wt% to about 75 wt%; or about 60
wt% to about 70 wt%; or about 60 wt% to about 65 wt%; or about 65 
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wt% to about 99 wt%; or about 65 wt% to about 95 wt%; or about 65

wt% to about 90 wt%; or about 65 wt% to about 85 wt%; or about 65
wt% to about 80 wt%; or about 65 wt% to about 75 wt%; or about 65
wt% to about 70 wt%; or about 70 wt% to about 99 wt%; or about 70
wt% to about 95 wt%; or about 70 wt% to about 90 wt%; or about 70
wt% to about 85 wt%; or about 70 wt% to about 80 wt%; or about 70
wt% to about 75 wt%; or about 75 wt% to about 99 wt%; or about 75
wt% to about 95 wt%; or about 75 wt% to about 90 wt%; or about 75
wt% to about 85 wt%; or about 75 wt% to about 80 wt%; or about 80
wt% to about 99 wt%; or about 80 wt% to about 95 wt%; or about 80
wt% to about 90 wt%; or about 80 wt% to about 85 wt%; or about 85
wt% to about 99 wt%; or about 85 wt% to about 95 wt%; or about 85
wt% to about 90 wt%; or about 90 wt% to about 99 wt%; or about 90
wt% to about 95 wt%; or about 95 wt% to about 99 wt%.

[0073] Therefore, the amount of cross-linker in the coating

composition is generally about 0.05 wt% to about 99 wt%, based on
the total weight of the coating composition. For example, the
amount of cross-linker in the coating composition may be about 0.1
wt% to about 50 wt%, or about 0.2 wt% to about 40 wt%. One of
ordinary skill in the art can easily calculate the amount of cross-
linker in the coating composition by multiplying the amount of cross-
linker liquid formulation in the coating composition by the solids
content of the cross-linker liquid formulation (e.g. 99 wt% of liquid
formulation X 60% solids content = (99)(0.6) = 59.4 wt% of cross-
linker).

[0074] The water-based coating compositions may optionally include

a water-dilutable acid-catalyzed silica sol-gel composition. The silica
sol-gel composition may be any silica sol-gel composition that is
compatible with the functional polyurethane and the cross-linker,
and which provides a coating composition which, upon curing,
produces a coating with the properties described herein. The
aqueous acid-catalyzed silica sol-gel composition may have a solids
content of about 1 wt% to about 50 wt%, based on the total weight
of the silica sol-gel composition. For example, the silica sol-gel
composition may have a solids content of about 10 wt% to about 50
wt%, or about 20 wt% to about 40 wt%, based on the total weight of
the silica sol-gel composition.

[0075] The water-dilutable acid-catalyzed silica sol-gels may have a

pH of about 2 to about 6. For example, the silica sol-gels may have a 
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pH of about 3 to about 5. Such sol-gels are available as commercial

products. Examples thereof include, but are not limited to,

LUDOX® HSA (GRACE), LUDOX® CL-P (GRACE) and DYNASYLAN®

SIVO 110 (Evonik). Alkalinically- and neutrally-stabilized silica sol-gel
compositions may also be used.

[0076] The waterborne polyurethane coating compositions disclosed

herein may further comprise silane-functional adhesion promoters
such as, for example, the adhesion promoters disclosed in WO
2017/074918, which is incorporated by reference into this
speci cation. Suitable adhesion promoters include, but are not
limited to, (3-mercaptopropyl)trimethoxysilane, (3-
aminopropyl)triethoxysilane, (3-glycidyloxypropyl)trimethoxysilane,
(3-glycidyloxypropyl)triethoxysilane and mixtures thereof.

[0077] Various additives can also be combined with the sol-gel

composition to adjust the pH or further improve the chemical and
water resistance. Examples of alkaline neutralization agent, hydro-
and oleophobic additives include, but are not limited to, Dynasylan
SIVO 11 1 and SIVO 113. Furthermore, silica sols used in the
composition may contain not only amorphous, aqueous S1O2
particles but also other sol-gel-forming materials such as oxides,
e.g., aluminum oxide, silicon/aluminum oxide, titanium oxide,
zirconium oxides, zinc oxide or combinations thereof. In addition to
silica-based sol gels, the sol-gel composition may optionally include
organofunctional silanes, such as 3-
glycidyloxypropyltrimethoxysilane, 3-
glycidyloxypropyltriethoxysilane, 3-
glycidyloxypropylmethyldimethoxysilane, 3-
glycidyloxypropylmethyldiethoxysilane and mixtures thereof.

[0078] In order to add color to a substrate, the water-based coating

compositions may include one or more colorants. Suitable colorants
include but are not limited to organic or inorganic pigments (in
various forms, not limited to dry pigment, but may be used as press-
cakes or dispersions) and dyes. The dyes include but are not limited
to azo dyes, anthraquinone dyes, xanthene dyes, azine dyes, etc.,
and combinations thereof. Organic pigments may be one pigment or
a combination of pigments, such as for instance Pigment Yellow
Numbers 12, 13, 14, 17, 74, 83, 1 14, 126, 127, 174, 188; Pigment Red
Numbers 2, 22, 23, 48: 1 , 48:2, 52, 52: 1, 53, 57: 1, 112, 122, 166, 170,
184, 202, 266, 269; Pigment Orange Numbers 5, 16, 34, 36; Pigment

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Blue Numbers 15, 15 :3, 15 :4; Pigment Violet Numbers 3, 23, 27;
and/or Pigment Green Number 7. Inorganic pigments may include
but are not limited to: non-limiting pigments such as iron oxides,
titanium dioxides, chromium oxides, ferric ammonium
ferrocyanides, ferric oxide blacks, Pigment Black Number 7 and/or
Pigment White Numbers 6 and 7. Other organic and inorganic
pigments and dyes may be employed. Di erent kinds of colorants
may be mixed in combination to attain the desired colors.

[0079] Suitable natural colorants include but are not limited to

organic or inorganic pigments and dyes. The natural dyes include
but are not limited to henna, madder, spurulina, combinations
thereof and the like. Natural organic pigments include but are not
limited to cochineal red, chlorophyllin green, carotene yellow,
turmeric yellow, anthocyanin blue, etc., and combinations thereof.
Natural inorganic pigments include but are not limited to
ultramarine blue, vegetable carbon black, combinations thereof and
the like. Other natural organic and inorganic pigments and dyes can
also be employed, as well as combinations that attain the desired
colors.

[0080] In one embodiment, the colorants employed in the present

invention may be any FD&C or D&C pigment. Preferred FD&C
pigments include FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow
No. 6 and FD&C Blue No. 1, FD&C Blue #1 Aluminum Lake, FD&C
Blue #2, FD&C Blue #2 Aluminum Lake on alumina, FD&C Green #3,
FD&C Red #3, FD&C Red #40 and its Aluminum Lake, FD&C Yellow
#5, FD&C Yellow #5 Aluminum Lake, FD&C Yellow #6, FD&C Lakes,
Citrus Red #2, etc. Preferred D&C pigments include D&C Red No. 6,
D&C Red No. 7, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27,
Red No. 28, D&C Red No. 30, D&C Red No. 33, D&C Red No. 34, D&C
Red No. 36, D&C Orange No. 5 and D&C Yellow No. 10.

[0081] In one embodiment, the colorant may be in the form of a

colorant dispersion that is resin free (e.g., free of water-based
acrylics or styrene acrylics). In another embodiment, the colorant
dispersion is resin-free, surfactant based, and/or free of alkyl phenyl
ethoxylate (APEO), which is environmentally friendly.

[0082] The water-based coating composition may include one or

more matting/opacifying agents. Suitable matting/opacifying agents
include but are not limited to organic or inorganic particles. The
organic particles include but are not limited to ROPAQUE® ULTRA
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Opaque Polymer (Dow), ROPAQUE® OP-96 All Purpose Pigment

(Dow), Deuteron® MK

(Deuteron GmbH), Deuteron® MK-F (Deuteron GmbH), Deuteron®

PMH C (Deuteron GmbH), Deuteron® MM 684 (Deuteron GmbH),
SOOFINE® JJ Powder® (J Color

Chemicals), SOOFINE® JMV Microsphere (J Color Chemicals),

SOOFINE® MV Micron-Beads (J Color Chemicals), combinations
thereof and the like. The inorganic particles include but are not
limited to KRONOS® 4311 (KRONOS), TiONA® 595 (Cristal),
ACEMATT®

82 (Evonik), ACEMATT® HK 440 (Evonik), ACEMATT® OK 412 (Evonik),

ACEMATT® 3600 (Evonik), Mistron® Monomix G (Imerys), Jet ne®
1H (Imerys), Syloid® 161 (Grace), Syloid® 308 (Grace), etc., and
combinations thereof. Other organic and inorganic particles can also
be employed, as well as combinations that achieve the surface e ect
desired.

[0083] Colorants, if present, may be included in the water-based

coatings in amounts of about 0.5 wt% to about 50 wt%. For example,
colorants may be included in an amount of about 1 wt% to about 40
wt%, or about 5 wt% to about 30 wt%, and may be in the form of
pigment dispersions or matting/opacifying agents. Water-dilutable
acid-catalyzed silica sol-gel compositions, if included, may be
present in the water-based coatings in amounts of about 0.1 wt% to
about 20 wt%. For example, silica sol-gel compositions may be
present in an amount of about 1 wt% to about 15 wt%, or about 2
wt% to about 10 wt%. Organic solvents, if included, may be present
in the water-based coatings in amounts of about 0.1 wt% to about
15 wt%. For example, organic solvents may be present in amounts of
about 0.5 wt% to about 10 wt%, or about 1 wt% to about 5 wt%. In
certain embodiments, there are no organic solvents in the coating
compositions of the present invention. All values are based on the
total formulation weight. In the case of clear, non-colored glass,
colorants are not needed.

[0084] Other optional additives can be included in the water-based

coating compositions, such as defoamers, wetting agents, leveling
agents, dispersants, surfactants, plasticizers, rheology modi ers,
amine stabilizers, antimicrobials, photocatalysts, ultraviolet
absorbers, antioxidants and combinations thereof. The amount of 
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each additive may independently be between about 0.05 wt% to 5

wt%, based on the weight of the total formulation of the water-
based coatings.

[0085] The present water-based coatings can be prepared by a

number of processes, resulting in stable coating compositions with
long shelf life. Upon application and curing of the present water-
based coatings, a coated substrate, e.g., a coated glass substrate, is
produced that has desirable properties. For example, a water-
dilutable carboxyl or hydroxyl functional polyurethane dispersion
and cross-linking agent (e.g. carbodiimide) can be added to a
pigment dispersion in sequence and mixed for a period of time,
resulting in a pigment-including water-based coating that has
stability over at least a month. When applied to glass and then
cured, such coating compositions color the glass while being
substantially transparent, and meet all chemical and physical
requirements for glass coatings.

[0086] The water-based coating compositions generally contain, at

most, about 15 wt% VOCs. However, as indicated, the amount of
VOCs in the compositions may be far less than that. For example,
the compositions may contain, less than about 10 wt% VOCs, or at
most about 5 wt% VOCs. In certain embodiments, the coatings may
be essentially free of VOCs (e.g., VOCs present in trace amounts).
VOCs can be environmentally harmful and present a health hazard.

[0087] The compositions of the present disclosure can be applied by

conventional methods, such as spray coating, dip coating, ow
coating, spin coating, curtain coating, roll coating, etc. to form a
continuous surface lm. Decorative coatings providing protective
properties can be obtained by heat curing at a temperature in the
range of 50 °C to 300 °C, or 100°C to 250 °C, or 150°C to 200 °C, for
from about 5 min to 12 hr. The coating thickness can be varied by
means of the application technique. Coatings having a thickness of
0.5 μιτι to 20 μιτι, and more desirably of 1 μιτι to 10 μιτι, are
generally utilized.

EXAMPLES

[0088] The following examples illustrate speci c aspects of the

present invention and are not intended to limit the scope thereof in
any respect and should not be so construed. The following examples
illustrate speci c aspects of the present water-based coating 
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compositions. The examples are merely exemplary and are not to be

construed as limiting the scope of subject matter claimed on the
basis of the present disclosure. All parts and percentages are by
weight (wt% or mass% based on the total weight).

[0089] For example, in the examples that follow, a substrate is spray-

coated with the water-based coating compositions, yet it is possible
to apply the water-based coatings by other methods. The person of
ordinary skill in the art would be able to adjust the water-based
coating compositions for viscosity, rheology, etc., to adapt them (if
necessary) for application by another method, such as dip coating,
ow coating, spin coating, curtain coating and roll coating.

[0090] Prior to spray, 2% to 3% of the adhesion promoter (Silquest®

A-187, Momentive Performance Materials, USA) was added to
certain of the examples below and well mixed. The sprayed samples
were cured by baking at 175 °F (about 80°C) for 30 min. All the
resistance properties were measured after the samples cooled
down to room temperature naturally.

[0091] All of the ensuing Examples are essentially solvent-free (0%

VOC) coatings, leaving only the possibility of trace amounts of VOC’s.

Test methods

Application of ink or coating to a substrate

[0092] The coatings were applied to glass bottles using a central

pneumatic 4 oz. adjustable detail air spray gun. Pressure was set at
30 psi, container rotation was 250-270 rpm, spray distance was 4-6
inches, and spray cycle was 4-8 seconds. Coatings were heat cured
at 175°C for 30 minutes, followed by cooling down naturally (i.e.
ambient conditions), before any testing.

Transparency

[0093] Transparency of the cured coatings was assessed by visual

inspection, and rated on a 1 to 5 scale, with 1 being very hazy, and 5
being clear. A score of 4 or higher is desirable for coatings designed
to be transparent.

Resistance and adhesion rating scale

[0094] Solvent resistance, water resistance, and adhesion were rated

on a 5 point scale (of the amount of coating removed from the 
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substrate), wherein:

1 = poor (total removal)

2 = fair/poor (signi cant removal)

3 = fair (moderate removal)

4 = good (slight removal)

5 = excellent (no removal)

[0095] For all tests, a score of 4 or higher is desirable.

Solvent resistance

[0096] Resistance to removal by solvents was tested using acetone

and cologne (Brut cologne for men). A cotton ball was soaked with
solvent (either acetone or cologne). The cotton ball was rubbed back
and forth on the surface of the coating 100 times. The color
transferred to the cotton ball qualitatively indicated the removal
amount of the coating during the test. The resistance was rated on a
scale of 1 to 5, as described above.

Bottle rub resistance

[0097] The bottle rub resistance is an indicator of resistance of the

coating to removal by friction. Bottle rub resistance was tested by
rubbing the surfaces of two coated containers together, one
container in each hand. This test was repeated several times at
various locations on the containers. Instances of scratching or
sliding resistance were recorded. Bottle rub resistance was assessed
on a scale of 1 to 5, as described above.

Adhesion

[0098] Adhesion was tested by the cross-hatch tape adhesion test,

using a BYK-Gardner 5126 Cross-Cut Tester. First, a lattice pattern of
1 mm cutting space was made on the coating (cutting to the glass
substrate). Then, 3M 616 tape was placed on the coating covering
the cut partem, and pulled back slowly on itself at about 180° angle.
The amount of coating removed from the substrate to the tape was
rated on a scale of 1 to 5, as described above.

Pencil hardness
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[0099] The pencil hardness of the coatings was measured using a

BYK-Gardner PH-9500 Pencil Hardness Tester. Pencils of di erent
hardness were moved with a xed pressure and a xed angle over
the coating. The hardness of the pencil that scratched through the
coating was recorded. The hardness of a pencil is rated on the
following scale, from the softest (6B) to the hardest (9H): 6B < 5B <
4B < 3B < 2B < B < HB < F < H < 2H < 3H < 4H < 5H < 6H < 7H < 8H <
9H.

Water resistance

[00100] The water resistance of the cured coating was tested by

immersing the coated glass bottle in 0°C water for 48 hours, and
immersing the coated glass bottle in 25°C water for 48 hours,
respectively. This was followed by the cross-hatch tape adhesion test
after each

immersion (i.e. after the 0°C immersion, then after the 25 °C

immersion), and the reported value for adhesion is the average of
the two tests. The amount of coating removed from the substrate to
the tape was rated on a scale of 1 to 5, as described above.

Dishwashing resistance

[00101] Dishwashing resistance was tested generally following

standard BS EN 12875- 1 :2005 procedures. However, because of
equipment limitations, some minor modi cations were required.
The dishwasher used in the test was Kenmore 14659 18″ Portable

Dishwasher, selecting normal wash cycle, using the high

temperature option, and Cascade Platinum Dishwasher Detergent.
Each wash cycle included two washes at approximately 140°F (60°C)
and 4 rinses. The total time for each wash cycle was about 95 min.
After each wash cycle, the coating was inspected for defects,
anomalies, and other changes in the coating. The number of
dishwashing cycles in which the coating remained intact was
recorded.

Polyurethane dispersions

[00102] Table 1 describes the repeat units and the properties of the
polyurethane dispersions used in the examples below.

Table 1. Polyurethane dispersions

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*Polyol unit:

A = polyether

B = polyester

C = polycarbonate

Polyurethane dispersions:

PUD-1 is SUN 940-1207 (Sun Chemical, US)

PUD-3 is Alberdingk® DUR 95 (Alberdingk Boley, USA)

PUD-6 is ESACOTE® PU 70 (Lamberti S.p.A., Italy)

PUD-7 is Alberdingk® UC 80 (Alberdingk Boley, USA)

PUD-8 is ESACOTE® PU 44 (Lamberti S.p.A, Italy)

Examples 1 to 3. Preparation of Examples 1 to 3

[00103] In Example 1, the water-dilutable polyurethane dispersion

PUD-1 was mixed with the carbodiimide cross-linker CARBODILITE®
V-04 (Nisshinbo Chemical Inc., Japan), followed by various additives 
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and pigment dispersion. The resulting mixture was agitated using a

mechanical mixer until a homogeneous mixture was obtained. The
mixture was deaerated and stored overnight before use.

[00104] Example 2 was prepared similarly to Example 1, except that

a di erent water- dilutable polyurethane dispersion, PUD-2, and
cross-linker, CARBODILITE® E-05 (Nisshinbo Chemical Inc., Japan)
were used.

[00105] In Example 3, the water-dilutable polyurethane dispersion

PUD-1 was rst mixed with the deaerator (Airase 8070, BYK USA Inc.,
USA), followed by the Ti02slurry

(Sunsperse White 6, Sun Chemical Corporation, USA). After the

mixture became homogeneous, the carbodiimide cross-linker
CARBODILITE® E-05 and various additives were then added under
continuous stirring. The mixture was deaerated and stored
ovemight before use.

Table 2. Formulations of Examples 1 to 3

Aging conditions: 10 days at 50 °C.

Examples 4 to 6. Preparation of Examples 4 to 6

[00106] The formulations of Examples 4 to 6 are shown in Table 3.

Examples 4 and 5 have the same polyurethane dispersion, PUD-1, as
Examples 1 and 3, but comprise a melamine cross-linker (Cymel®
303 LF, Allnex, USA), and a blocked polyisocyanate cross-linker (AP-
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BI795®, Advanced Polymer Inc., USA), respectively. Example 6 was

prepared with PUD-3, and a melamine cross-linker.

Table 3. Formulations of Examples 4 to 6

Aging conditions: 10 days at 50 °C.

[00107] Example 4 exhibited reduced stability (i.e. gelled after aging

at 50°C for 10 days), and slightly less transparency (shown in Table
9). Example 5 showed good stability, but its dishwasher resistance
(i.e. resistance to hot, alkaline washing media) was reduced (shown
in Table 9). Example 5 coating failed at the 8th cycle. Usually, greater
than 100 dishwasher cycles are needed for glass coating application.

Examples 7 to 9. Preparation of Comparative Examples 7 to 9

[00108] Comparative Examples 7 to 9 were prepared in a similar

manner to Examples 1 to 6. The formulations of Examples 7 to 9 are
shown in Table 4.

Table 4. Formulation of Examples 7 to 9

Components Description Ex. 7 Ex. 8 Ex. 9

Blocked 
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API-BI795 13.47 polyisocyanate

Rheolate 299 Rheology modi er 0.43 0.44

BYK-348 Wetting agent 0.52

BYK-378 Leveling agent 0.16 0.16

Dynasylan SIVO

Silica sol-gel 2.26 110

Dynasylan SIVO Hydrophobizing

0.03 111 additive

TBEP Surfactant 1.03 1.04

Foamex 822 Defoamer 0.78 0.78

Rhodoline 679 Defoamer 0.72

Triethanolamine Neutralization agent 1.03 1.04

DI Water Diluent 13.41

SunSperse Red

Pigment dispersion 7.73 122

TOTAL 100.00 100.00 100.00

-NCN-/-COOH 1.0 1.0 N/A

Solids content (%) 19 17 28

Fresh Viscosity (cP) 75 30 < 50

Aged Viscosity (cP)1 56 38 < 50

Aging conditions: 10 days at 50 °C.

[00109] The elongation of PUD-4 in Example 7 is about 550%, while

the elongation of PUD- 5 in Example 8 is less than 10%. The Tg of
PUD-5 is 70°C. Also, the acid number of PUD- 6 in Example 9 is only
17. As a result, Example 7 failed in the acetone rub resistance test;
Example 8 failed in both the acetone rub resistance and the water
resistance test; Example 9 failed in both the acetone and cologne
resistance tests. In addition, the pencil hardness of Example 9 is 
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signi cantly lower than other examples. Furthermore, Examples 8

and 9 showed more haziness, which is usually undesirable by the
glass industry. Thus,

Comparative Examples 7 to 9 show that to provide improved

coatings, a PUD must have all of the claimed properties.

Examples 10 to 13. Preparation of Examples 10 to 13

[00110] Additional Examples 10 to 13 were prepared in a similar

manner. The formulations of Examples 10 to 13 are shown in Tables
5 to 7.

[00111] Examples 10 and 11 are water-based coating compositions

that include colorants, and are transparent when applied to a glass
substrate.

[00112] In Example 10 (Table 5), a carboxyl-functional polyurethane

dispersion, PUD-1, was mixed with the blocked polyisocyanate (API-
BI795, Advanced Polymer, Inc., USA). The water-dilutable acid
catalyzed silica sol-gel and hydrophobizing additive were added with
continuous stirring, followed by other additives. After addition of
pigment dispersion and water, the adhesion promoter (Silquest® A-
189, Momentive Performance Materials, USA) was added in the end
while mixing. The resulting mixture was agitated using a mechanical
mixer until a homogeneous mixture was obtained.

[00113] Example 11 (Table 5) was prepared in a similar manner to

Example 10, except that a water-dilutable hydroxyl-functional
polyurethane dispersion, PUD-3, was used, and the coating
comprises no silica sol-gel, hydrophobizing additive, or adhesion
promoter. An aminoplast resin (Cymel® 303 LF, Allnex, USA) was
used as the cross-linking agent.

Table 5. Formulations of Examples 10 and 11

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[00114] In Example 12 (Table 6), the titanium dioxide slurry

(KRONOS® 4311, KRONOS, Inc., USA) was added gradually into the
water-dilutable hydroxyl functional polyurethane dispersion PUD-3
with continuous mixing. Mixing continued until the pigment was fully
dispersed. The cross-linking agent, additives, and adhesion
promoter were added and mixing continued. Deionized water was
added to adjust the viscosity. Example 12 is an opaque white
coating.

Table 6. Formulation of Example

[00115] Example 13 (Table 7) is a frost coating. The two matting

agents were gradually added into the water-dilutable hydroxyl
functional polyurethane dispersion PUD-3 while mixing, followed by
the cross-linking agent, additives, and adhesion promoter. Deionized
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water was added to adjust the viscosity to meet the spray

requirements.

Table 7. Formulation of Example 13

Components Description Ex. 13

DI Water Diluent 10.10

Mistron Monomix Matting agent 10.09

ACEMATT OK-412 Matting agent 2.04

Silquest A- 187 Silane adhesion promoter 3.00

TOTAL 100

Solids content (%) 43

Viscosity (cP) 70

[00116] Examples 10 to 13 were tested as described above. The

results are shown in Table

Example 14 to 16. Preparation of Comparative Examples 14 to 16

[00117] Comparative Examples 14 to 16 were prepared in a similar

manner to Example 10, except for containing three di erent water-
dilutable carboxyl functional polyurethane dispersions. The
formulations of Examples 14 to 16 are shown in Table 8.

Table 8. Formulations of comparative Examples 14 to 16

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[00118] The polyurethane dispersion used in Example 15, PUD-8,

has an acid number lower than 20. The polyurethane dispersion
used in Example 14 (PUD-7) and Example 16 (PUD-6) have acid
numbers lower than 20, and MFFT higher than 30°C.

Example 17. Assessment of Examples 1 to 9

[00119] The properties of Examples 1 to 6, and comparative

Examples 7 to 9 were assessed as described above. The data are
shown in Table 9.

Table 9. Test results for Examples 1 to 9

[00120] For colors except for white, black and frost, a clearer coating
is more desirable by the glass decoration industry. Example 3 is a
white coating, and therefore its transparency was not assessed.
Examples 1 to 4 and 6, all falling within the scope of the present
invention, show superior performance in all of the properties tested.
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It can also be seen that, of the cross-linkers used, carbodiimide

cross-linkers are preferred, as Example 5, using a blocked
polyisocyanate cross-linker, failed some of the tests. Moreover,
comparative Examples 7 to 9, each having at least one parameter
outside of the scope of the invention, fail on one or more of the
tests.

Example 18. Assessment of Examples 10 to 16

[00121] Examples 10 to 13 and Comparative Examples 14 to 16 were

tested as described above. The test results are shown in Table 10.

Table 10. Test results for Examples 10 to 16

[00122] The transparency of Examples 10 and 11 is superior to the

transparency of comparative Example 14. Example 12 is an opaque
coating, and Example 13 is a frost coating, and therefore their
transparency was not assessed. The properties of Examples 10 to 13
exceed or equal the properties of comparative Examples 14 to 16.
Notably, the acetone rub resistance and cologne rub resistance of
Examples 10 to 13 exceeds that of comparative Examples 15 and 16.

[00123] The present invention has been described in detail,

including the preferred embodiments thereof. However, it will be
appreciated that those skilled in the art, upon consideration of the
present disclosure, may make modi cations and/or improvements
on this invention that fall within the scope and spirit of the
invention.

CLAIMS

What is claimed is:

1. A coating composition comprising:

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a) a water dilutable carboxyl, or hydroxyl, or carboxyl and

hydroxyl, functional polyurethane dispersion, in an amount of 1
wt% to 99 wt%, based on the total weight of the coating
composition; and

b) one or more cross-linking agents, in an amount of 1 wt% to 99

wt%, based on the total weight of the coating composition;

wherein the one or more cross-linking agents are selected from

the group consisting of carbodiimides, carbodiimide derivatives,
aminoplasts, blocked isocyanates, and combinations thereof;

wherein the polyurethane dispersion has a glass transition

temperature of -40°C to 50°C; and wherein the polyurethane
dispersion has an elongation at break of 10% to 250%.

2. The coating composition of claim 1, wherein the polyurethane

dispersion is present in an amount of 25 wt% to 95 wt%, based
on the total weight of the coating

composition.

3. The coating composition of any one of claims 1 to 2, wherein

the polyurethane

dispersion is present in an amount of 50 wt% to 90 wt%, based

on the total weight of the coating composition.

4. The coating composition of any one of claims 1 to 3, wherein

the one or more cross- linking agents are present in an amount
of 5 wt% to 75 wt%, based on the total weight of the coating
composition.

5. The coating composition of any one of claims 1 to 4, wherein

the one or more cross- linking agents are present in an amount
of 10 wt% to 50 wt%, based on the total weight of the coating
composition.

6. The coating composition of any one of claims 1 to 5, wherein

the polyurethane dispersion has a solids content of 5 wt% to 60
wt%, based on the total weight of the polyurethane dispersion.

7. The coating composition of any one of claims 1 to 6, wherein

the polyurethane dispersion has a solids content of 10 wt% to 50
wt%, based on the total weight of the polyurethane dispersion. 
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8. The coating composition of any one of claims 1 to 7, wherein

the polyurethane dispersion has a solids content of 20 wt% to 40
wt%, based on the total weight of the polyurethane dispersion.

9. The coating composition of any one of claims 1 to 8, wherein

the viscosity of the polyurethane dispersion is 5 cP to 5000 cP.

10. The coating composition of any one of claims 1 to 9, wherein

the viscosity of the polyurethane dispersion is 50 cP to 4000 cP.

11. The coating composition of any one of claims 1 to 10, wherein

the viscosity of the polyurethane dispersion is 100 cP to 2000 cP.

12. The coating of any one of claims 1 to 11, wherein the glass
transition temperature of the polyurethane is -40°C to 50°C.

13. The coating composition of any one of claims 1 to 12, wherein

the glass transition temperature of the polyurethane is -30°C to
40°C.

14. The coating composition of any one of claims 1 to 13, wherein

the glass transition temperature of the polyurethane is -20°C to
30°C.

15. The coating composition of any one of claims 1 to 14, wherein

the minimum lm forming temperature of the polyurethane is
-40°C to 40°C.

16. The coating composition of any one of claims 1 to 15, wherein

the minimum lm forming temperature of the polyurethane is
-30°C to 30°C.

17. The coating composition of any one of claims 1 to 16, wherein

the minimum lm forming temperature of the polyurethane is
-20°C to 20°C.

18. The coating composition of any one of claims 1 to 17, wherein

the acid number of the polyurethane is greater than 20 mg
KOH/g.

19. The coating composition of any one of claims 1 to 18, wherein

the acid number of the polyurethane is greater than 25 mg
KOH/g.

20. The coating composition of any one of claims 1 to 19, wherein

the acid number of the polyurethane is greater than 30 mg
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KOH/g.

21. The coating composition of any one of claims 1 to 20, wherein

the sum of the acid number and hydroxyl number of the
polyurethane is greater than 20 mg KOH/g.

22. The coating composition of any one of claims 1 to 21, wherein

the sum of the acid number and the hydroxyl number of the
polyurethane is greater than 30 mg KOH/g.

23. The coating composition of any one of claims 1 to 22, wherein

the sum of the acid number and the hydroxyl number of the
polyurethane is greater than 40 mg KOH/g.

24. The coating composition of any one of claims 1 to 23, wherein

the polyurethane comprises an aliphatic or cycloaliphatic
diisocyanate repeat unit.

25. The coating composition of any one of claims 1 to 24, wherein

at least one cross- linking agent is a carbodiimide.

26. The coating composition of claim 25, wherein the ratio of

moles of carbodiimide (- NCN-) groups in the cross-linker to
moles of the carboxylic groups (-COOH) in the polyurethane is 0.2
: 1 to 1.2: 1.

27. The coating composition of any one of claims 25 to 26,

wherein the ratio of moles of carbodiimide (-NCN-) groups in the
cross-linker to moles of the carboxylic groups (- COOH) in the
polyurethane is 0.4: 1 to 1.0: 1.

28. The coating composition of any one of claims 25 to 27,

wherein the ratio of moles of carbodiimide (-NCN-) groups in the
cross-linker to moles of the carboxylic groups (- COOH) in the
polyurethane is 0.6: 1 to 0.8: 1.

29. The coating composition of any one of claims 1 to 28, further

comprising one or more silane, oxysilane, or combinations
thereof, adhesion promoters.

30. The coating composition of any one of claims 1 to 29, having

a volatile organic

compound content of less than 10 wt%, based on the total weight

of the coating composition. 
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31. The coating composition of any one of claims 1 to 30, having

a volatile organic

compound content of less than 5 wt%, based on the total weight

of the coating composition.

32. The coating composition of any one of claims 1 to 31 , having

no volatile organic compounds.

33. The coating composition of any one of claims 1 to 32, wherein

the tensile strength of the polyurethane is 5 MPa to 150 MPa.

34. The ink or coating composition of any one of claims 1 to 33,

wherein the tensile strength of the polyurethane is 10 MPa to 100
MPa.

35. The coating composition of any one of claims 1 to 34, wherein

the tensile strength of the polyurethane is 20 MPa to 50 MPa.

36. The coating composition of any one of claims 1 to 35, wherein

the molecular weight (MW) of the polyurethane is about 5,000 to
100,000.

37. The coating composition of any one of claims 1 to 36, wherein

the molecular weight (MW) of the polyurethane is about 10,000
to 75,000.

38. The coating composition of any one of claims 1 to 37, wherein

the molecular weight (MW) of the polyurethane is about 15,000
to 50,000.

39. The coating composition of any one of claims 1 to 38, wherein

the elongation of the polyurethane is 20% to 200%.

40. The coating composition of any one of claims 1 to 39, wherein

the elongation of the polyurethane is 30% to 150%.

41. A method of applying a coating composition on a substrate,

comprising:

a) providing the coating composition of any one of claims 1 to 40;

b) applying the coating composition to the substrate; and

c) drying and/or curing the composition on the substrate.

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42. The method of claim 41, wherein step b) is carried out using a
method selected from the group consisting of spray coating, dip
coating, ow coating, spin coating, curtain coating, and roll
coating.

43. The method of any one of claims 41 to 42, wherein the

substrate is selected from the group consisting of glass, wood,
metal, paper, leather, textiles, felt, concrete, masonry, ceramic,
stone, plastics, combinations of the materials, and the like.

44. A substrate comprising the coating composition of any one of

claims 1 to 40.

45. An article comprising the coating composition of any one of

claims 1 to 40.

46. An article comprising the substrate of claim 44.

47. A method of formulating a coating composition, comprising

mixing: a) a water dilutable carboxyl, or hydroxyl, or carboxyl and
hydroxyl, functional polyurethane dispersion, in an amount of 1
wt% to 99 wt%, based on the total weight of the coating
composition; and

b) one or more cross-linking agents, in an amount of 1 wt% to 99

wt%, based on the total weight of the coating composition;

wherein the one or more cross-linking agents are selected from

the group consisting of carbodiimides, carbodiimide derivatives,
aminoplasts, blocked isocyanates, and combinations thereof;

wherein the polyurethane has a glass transition temperature of

-40°C to 50°C; and wherein the polyurethane has an elongation
at break of 10% to 250%.

48. The coating composition of any one of claims 1 to 40, having

one or more of the following:

a) a transparency rating of greater than or equal to 4;

b) a pencil hardness rating of greater than or equal to 5H;

c) a rating of greater than or equal to 5 for one or more of:

i) acetone rub resistance;

ii) cologne rub resistance;

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iii) bottle rub resistance;

iv) adhesion; and/or

v) water resistance; and/or

d) a dishwashing resistance of greater than or equal to 100 wash

cycles.

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Related

(WO2017074835) (WO2017085327)
POLYURETHANE ENCAPSULATED
COATING ACCELERATORS FOR
COMPOSITION COATINGS
(WO2018118221)
Pub. No.: Pub. No.:
WATERBORNE ACRYLIC
WO/2017/074835 WO/2017/085327
DISPERSIONS WITH
International International
HIGH BIORENEWABLE
Application No.: Application No.:
CONTENT
PCT/US2016/058367 PCT/EP2016/078356

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ENCAPSULATED COATINGS of intumescent
POLYAMINES HAVING coating
 July 8, 2017  0
ADAPTABLE  July 17, 2017  0

WETTABILITY AS
WELL AS
METHODS OF
MAKING AND
USING THEREOF
 May 13, 2018  0
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2/28/2021 (WO2018136488) WATERBORNE POLYURETHANE COATINGS – Paints and Coatings Expert

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