USOO6455142B1

(12) United States Patent (10) Patent No.: US 6,455,142 B1

Heberger et al. (45) Date of Patent: Sep. 24, 2002

(54) ANTI-FOG COATING AND COATED FILM 5,545,713 A 8/1996 Krejci et al.
5,562.997 A 10/1996 Krejci et al.
(75) Inventors: John M. Heberger; Robin M. Donald, 5,585,186 A 12/1996 Scholz et al.
both of Greer; Jan C. Westermeier, 2
E. A2
E. S. COZ, e a

Ge. R Fulbutylors 5,753,373 A 5/1998 Scholz et al.

, lay s 5,759,696. A 6/1998 Alers ......................... 428/431
(US) 5,873.931. A 2/1999 Scholz et al.
O O O 5.997,621. A 12/1999 Scholz et al.
(73) Assignee: Mitsubishi Polyester Film, LLC, 6.228,499 B1 * 5/2001 Nakauchi et al. ........... 428/412
Greer, SC (US) FOREIGN PATENT DOCUMENTS
(*) Notice: Subject to any disclaimer, the term of this EP O 896 229 A2 2/1999
patent is extended or adjusted under 35 EP O 899 315 A2 3/1999
U.S.C. 154(b) by 0 days. JP 97/170325 6/1997
JP 97/202803 7/1997
(21) Appl. No.: 09/466,377 JP 97/206102 7/1997
JP 97/260373 9/1997
(22) Filed: Dec. 17, 1999 JP 97/279012 10/1997
WO WO 95US 15648 11/1995
(51) Int. Cl." ......................... B32B 27/06; B32B 27/08; WO WO95/32237 11/1995
B32B 27/18: B32B 27/36 WO WO 96/18918 6/1996
(52) U.S. Cl. ....................... 428/215; 428/480; 428/482;
428/213; 428/216; 106/13; 528/293; 528/294; OTHER PUBLICATIONS
528/295; 528/302; 528/308; 528/308.6; Aerosol OT NV product data sheet.
528/308.7; 427/384; 427/385.5; 427/393.5 * cited b
(58) Field of Search ................................. 428/480, 482, cited by examiner
428/212, 213, 215, 216; 528/302,308, Primary Examiner Vivian Chen
308.6, 308.7, 293,294,295. 10613 ABSTRACT
(56) References Cited The present invention provides a coated polymer film having
U.S. PATENT DOCUMENTS an essentially Streak-free coated Surface that resists the
formation of fog. The film includes a Self-Supporting poly
4,467,073. A 8/1984 Creasy mer film layer, and an anti-fog coating on the film layer. The
A 3. c s et al. anti-fog coating, which can also be applied to alternate
4944.294 A 7/1990 s Jr. substrates, consisting essentially of a copolyester binder and
4987.182 A 1/1991 Creasy OC surfactant, wherein the Surfactant contains less
5,020,533 A 6/1991 Hubbard et al. than about 0.5 weight percent of a fluoroSurfactant. A Slip
5,334,457 A * 8/1994 Wada et al. ................ 428/480 agent can also be included in the anti-fog coating.
5,496,647 A 3/1996 Krejci et al.
5,512,211 A 4/1996 McSwigan et al. 36 Claims, No Drawings
 US 6,455,142 B1
1 2
ANTI-FOG COATING AND COATED FILM copolyester as disclosed in U.S. Pat. No. 4,493,872 to
Funderburk et al., the disclosure of which is incorporated
BACKGROUND OF THE INVENTION herein by reference in its entirety. This copolyester is
disclosed as the condensation product of the following
1. Field of the Invention monomers or their polyester forming equivalents: isoph
The present invention relates generally to a method for thalic acid, a Sulfomonomer containing an alkali metal
creating a fog resistant product, typically a polymer film, by Sulfonate group attached to a dicarboxylic aromatic nucleus
means of coating the product with an anti-fog coating. The and an alkylene glycol with about 2 to about 11 carbon
anti-fog coating is also disclosed. atoms. Optionally, an aliphatic dicarboxylic acid of the
2. Description of Related Art formula HOOC(CH) COOH, where n is about 1 to about
11, can also be employed as a monomer therein. An optimal
Anti-fog coatings are desirable for many applications, copolyester is made up of about 90 mol percent isophthalic
Such as facemasks and other types of face protection, acid, about 10 mol percent of the sodium salt of
eyewear Such as goggles and glasses, car windshields, 5-sulfoisophthalic acid and about 100 mol percent ethylene
windows, bathroom mirrors, See-through packaging materi glycol.
als for moist foods and the like. Disposable and replaceable 15 It is important to note, however, that the preferred per
liners for eyewear Such as Welding goggles, ski goggles and centage of Sulfomonomer, isophthalic acid and aliphatic
the like, or for other Surfaces Subject to fogging, Such as dicarboxylic acid employed is Somewhat broader in the
windows, are also a desired end use. In many of these context of the present invention than in the Funderburk et al.
applications, it is important that the coating be Substantially patent. For example, in the context of the present invention,
transparent. However, prior art anti-fog coatings have Suf isophthalic acid is preferably about 50 to about 98 mol
fered from numerous limitations, including high cost, need percent, aliphatic dicarboxylic acid is preferably about 0 to
for frequent re-application, inadequate transparency and about 50 mol percent, and the sulfomonomer is preferably
limited anti-fog properties. There is a need for anti-fog about 2 to about 20 mol percent. In addition, the Sulfomono
coatings that address one or more of these problems. There mer group of the present invention is not limited to an alkali
is similarly a need for anti-fog coatings that are Suitable for metal Sulfonate group. Any Sulfomonomer in which a Sul
fonate group is attached to a dicarboxylic nucleus is pre
use on disposable items. Such as Single-use facemasks. A 25
ferred for use herein. In fact, any water Soluble copolyester
need also exists for anti-fog coatings that are adapted for that functions to bind the coating to the Surface of the base
application to polymer film Substrates. In addition, prior art polymer film, either alone or Synergistically in combination
anti-fog coatings are typically applied off-line. This is a leSS with other components, is preferred for use in the anti-fog
efficient and more costly alternative. Coatings adapted for coating of the present invention.
in-line application are also desirable. It is believed that films coated with an anti-fog film
containing this binder would possess the improved adhesion
BRIEF SUMMARY OF THE INVENTION to inkS and metals that have been previously disclosed in
conjunction with this class of compounds.
Accordingly, it is an object of the present invention to Another preferred water-Soluble copolyester binder is a
provide an anti-fog coating Suitable for application to a base polymer having a Chemical Abstract Name of 1,3-
polymer film. 35
benzenedicarboxylic acid, 5-Sulfo-, 1,3-dimethyl ester,
It is a further object of the present invention to provide a Sodium Salt, polymer with dimethyl 1,4-
base polymer film with an anti-fog coating on one or both benzenedicarboxylate, 1,2-ethanediol and 2, 2'-oxybis
Sides. ethanol. The molecular formula of this polymer is
It is another object of the present invention to provide an 40
(CoHo O.S.C.H.O. CHO.C.H.O.Na). This
anti-fog coating that is Substantially free of Streaks and copolyester is commercially available as AJ20A polymer
Smears, particularly when applied to a base polymer film. from Palmetto Chemicals, Greenville, South Carolina, and
It is yet another object of the present invention to provide contains an antimony catalyst. A similar polymer commer
an anti-fog coating that is Substantially transparent. cially available from the same company as AJ30 polymer is
The present invention has accomplished these objectives also preferred for use herein, but it contains a titanium
by providing in a preferred embodiment a coated polymer 45 catalyst. It is believed that the antimony catalyst of the
film having an essentially Streak-free coated Surface that AJ20A polymer is preferable because it minimizes the
resists the formation of fog. The film includes a self yellowness of reclaimed Scrap film. The reclaim (no exces
Supporting polymer film layer, and an anti-fog coating on the Sive yellowing or deterioration in physical properties when
film layer. The anti-fog coating, which can also be applied coated film Scrap is mixed with fresh polymer and
to alternate Substrates, includes a binder and a Surfactant, 50 reextruded) and recycling characteristics of coated polymer
where the Surfactant preferably includes a fluoroSurfactant at film are important. The ability to reuse Scrap film, instead of
less than about 0.5 weight percent. disposing of it, reduces material and waste disposal costs
and minimizes unnecessary waste.
DETAILED DESCRIPTION OF THE Without intending to be bound by theory, it is believed
INVENTION 55 that water Soluble and water dispersible binders are pre
ferred for use in the present invention because this water
The present inventors have Surprisingly found that excel Sensitivity contributes to the positive antifog performance,
lent anti-fog properties are provided by a coating that particularly in combination with anionic Surfactants. It is
includes a copolyester binder and Specific Surfactants. The postulated that the Surfactant induces wet out of the water
Selection of binder and Surfactants, and the Specific amounts 60
droplets on the film Surface, preventing fog, and the water
used of the preferred fluorosurfactant, have been found to be Sensitive binder absorbs the water, conducting it away from
critical to the optimal anti-fog results achieved by various the surface. Water-based binders are also preferred for health
coatings of this invention. and Safety reasons, due the elimination or reduction of
The anti-fog coating of the present invention preferably potentially hazardous Solvents. In addition, is it believed that
includes a binder to anchor the anti-fog coating to the base the preferred coating layers of the present invention are
polymer film. Polymeric binders have proven to be most 65 Substantially amorphous, non-crystalline layers. They are
effective. One preferred binder is a water soluble copolyes preferably hydrophilic, water-wicking or water-dispersing
ter. Preferably, the water soluble copolyester includes a layers.
 US 6,455,142 B1
3 4
Binders containing water-dispersing agents are preferred Solvent. Alternatively, alcohols or other Suitable organic
for use in the present invention. Agents having a Sulfonated Solvents can be employed, alone or in combination with
component are particularly useful. Such water-dispersing water. The solids level is preferably up to about 50 weight
agents include 5-Sulfoisophthalic acid (also known as percent, alternatively about 0.01 to about 30 weight percent,
5-SIPA), or its 1,3-dimethyl ester sodium salt. Alternate more preferably about 1 to about 6 weight percent.
Sulfomonomers disclosed in U.S. Pat. No. 5,496,647 to In addition, a slip agent is preferably incorporated into the
Krejci et al., the disclosure of which is incorporated herein anti-fog coating of the present invention. The Slip agent is
by reference, are also preferred for use herein. believed to enhance the ability of the coated film to wind
The binder is preferably present at about 1 to about 30 Smoothly during the manufacturing process. The Slip agent
percent by weight of the coating Solution, and in an alternate is preferably inorganic. More preferably, the Slip agent
preferred embodiment, it is present at about 1 to about 6 includes colloidal SiO, most preferably the product com
percent by weight of the coating Solution. mercially available as Nalco 1060(R) colloidal SiO from the
It is also preferred that the anti-fog coating of the present Nalco Chemical Company. Other slip agents that are pre
invention include a Surfactant or mixture of Surfactants. In ferred for use in the present invention include Silica in one
one preferred embodiment, the anti-fog coating contains an 15
or more of its various morphological forms, including those
anionic Surfactant. The anionic Surfactant results in a high commercially available as Syloid (R) silica or Rapidup (R)
wetting tension on the Surface of the dried coating, and the Silica, although due to their larger particle size, they are leSS
high wetting tension prevents the formation of minute water preferred for uses in which clarity and low haZe are needed.
droplets-fog-on the film Surface. The anionic Surfactant Moreover, a combination of two or more of the foregoing
further enhances the wet-out of the water to maintain a clear, Slip agents is also preferred for use. The Slip agent is
non-fogged Surface. A preferred anionic Surfactant for use in preferably present at about 0.25 to about 2 weight percent of
the anti-fog coatings of the present invention is Sodium the anti-fog coating. In an alternate preferred embodiment,
dodecyl benzeneSulfonate. This Surfactant is commercially the Slip agent is present at about 0.3 to about 1.0 weight
available as Rhodacal LDS-10 Surfactant from Rhone Pou percent, or in a third preferred embodiment at about 0.5
lenc. In an alternate preferred embodiment, a fluoroSurfac weight percent.
tant is included in the anti-fog coating of the present 25 Conventional additives that are known in the art can be
invention. Preferably, this fluorosurfactant contains fluoro included in the anti-fog coatings of the present invention.
aliphatic oxyethylenes of carbon chain lengths of about 4 to For example, pigments, other colorants, Stabilizers, anti
about 8, and it can also include polyethylene glycol. Such a Static agents, adhesion promoters, antioxidants, delusterants,
flurosurfactant is commercially available from 3M as Fluo fillers, plasticizers and the like can be included in the
rad FC-170C surfactant. The fluorosurfactant, among other anti-fog coatings of the present invention.
things, Serves to minimize Streaking of the coating. This The preferred Solids level of the anti-fog coating, as it is
effect is shown clearly when the coating is applied to a applied to the base polymer film, is a level Sufficient to yield
polymer film Surface. This is particularly important for a final dry coating thickness within the range of about 0.02
anti-fog coatings that are applied to clear films for applica microns to about 0.1 microns, alternatively about 0.03
tions such as window films and face shields, where visibility 35 microns to about 0.05 microns. In addition, the anti-fog
should not be limited by streaks or smears. The fluorosur coating of the present invention is Suitable for application at
factant WorkS optimally in combination with the anionic much higher levels, and for extrusion or coextrusion as a
Surfactant because it minimizes or eliminates the coating Separate Self-Supporting web.
Streaks that can be caused by the anionic Surfactant. The coating compositions of the present invention can be
Alternate Surfactants that are preferred for use in the 40
formulated by Simply combining the desired coating com
present invention include Sodium lauryl Sulfate, an anionic ponents. Agitation may be used to insure an even dispersion
Surfactant commercially available as Sipon UB, and a Sul or Solution.
foSuccinate blend, an anionic Surfactant commercially avail Base Film
able as Aerosol OTNV. While this blend is proprietary, it is For many preferred uses of the coating and method of the
indicated to be covered by U.S. Pat. No. 5,512,211, the present invention, a polymer film Substrate is most useful. It
disclosure of which is incorporated herein by reference. A 45 provides a lightweight, Substantially transparent,
Similar Surfactant, AeroSol TO, is also commercially avail inexpensive, disposable or recyclable Substrate that accom
able from Cytec Industries, and is a Sodium dioctyl Sulfos modates many of the end uses of fog resistant materials. In
luccinate. The anionic Surfactant Sodium 2-ethylhexyl addition, the coated polymer film can also easily be lami
sulfate, commercially available as Rhodapon BOS, is also nated by heat bonding or by adhesives to various other
preferred for use herein. 50 Substrates.
The Surfactant component is preferably present at about The anti-fog coatings and coating methods of the present
0.4 to about 2.0 weight percent of the anti-fog coating invention are applicable to any polymeric film capable of
composition. Higher levels can be used, however they acting as a Substrate for an anti-fog coating. For example, the
typically result in an increase in haze, which is undesirable present invention is applicable to polymeric films Such as
for many applications. In an alternate preferred embodiment, 55 those made from polyamides exemplified by nylon; poly
the Surfactant component makes up about 0.8 to about 1.5 olefins Such as polypropylene and polyethylene, polyester
weight percent of the coating. It has been Surprisingly found Such as polyethylene terephthalate; polyacetal; polycarbon
that the fluoroSurfactant provides optimal results when ate, and the like. The invention is particularly applicable to
present at no more than about 0.5 weight percent of the polyester, most preferably polyethylene terephthalate, poly
coating. A range of about 0.001 to about 0.5 weight percent 60
ethylene naphthalate or polybutylene terephthalate. The
is preferred, with a range of about 0.01 to about 0.10 being present invention is also applicable to polymeric films
alternately preferred. In an alternate embodiment, the pre including copolyesterS Such as polyethylene terephthalate
ferred content is about 0.05 weight percent fluorosurfactant isophthalate. A preferred process for forming a base film is
of the coating. At Significantly higher amounts of set forth in U.S. Pat. No. 5,350,601 to Culbertson et al.,
fluoroSurfactant, the anti-fog properties of the coating and incorporated herein by reference. Generally, any polyester
coated film Show markedly lower performance. 65 film based on a polymer resulting from polycondensation of
The ingredients of the anti-fog coating are preferably a glycol or diol with a dicarboxylic acid (or its ester
formulated as a dispersion in water or a water-containing equivalents) Such as terephthalic acid, isophthalic acid,
 US 6,455,142 B1
S 6
Sebacic acid, malonic, adipic, aZelaic, glutaric, Suberic, facturing and heat Setting the film), preferably after conven
Succinic acids and the like, of mixtures of two or more of the tional Surface modification of the polymeric Substrate has
foregoing, are preferred for use in the present invention. occurred. Thus, the coating and method of the present
Suitable glycols include ethylene glycol, diethylene glycol, invention are also intended for use where, for example, the
polyethylene glycol, and polyols Such as butanediol and the base polymer film is produced and later coated off-line with
like. Mixtures of two or more of the foregoing are also one or more coatings of the present invention. Alternatively,
Suitable.
Any of the above base polymer films can contain con one or more coatings can be applied in-line, with the
ventional additives Such as antioxidants, delusterants, remainder being applied off-line. Conventional off-line coat
pigments, fillerS Such as Silica, calcium carbonate, kaolin, ing processes include roll coating, reverse roll coating,
titanium dioxide, antistatic agents and the like, or mixtures gravure roll coating, reverse gravure roll coating, brush
thereof, all of which are well known in the art. coating, wire-wound rod (Meyer rod) coating, spray coating,
In addition, the base polymer film may be a polymer air knife coating, meniscus coating or dipping.
laminate. Such laminates include polymer-polymer lami While surface modification of the base polymer film prior
nates like polyester-polyolefin or polyester-adhesive
polyolefin, polymer-metallic laminates Such as polyester to coating is not required, it has been found that better results
aluminum, or polymer-paper or polymer-adhesive-paper 15 are obtained if the Surface or Surfaces of the base polymer
laminates. Coated polymer films or film laminates can also film are modified before application of the coatings of the
be used. Primer coatings used to enhance wet-out or coating present invention. Conventional Surface modification tech
adhesion are preferred examples of Such coatings. niques include corona treatment, which is the most common
The films may be produced by any well known technique and most preferred procedure for modifying the Surface of
in the art. For example, polyester is typically melted and the polymer base film to enhance coating adhesion. The
extruded as an amorphous sheet onto a polished revolving corona treatment or other Surface modification should be
casting drum to form a cast Sheet of the polymer. The sheet Sufficient to permit wetting out of the coating. Corona
is quickly cooled and then Stretch oriented in one or more treatment of about 1.0 watt per Square foot per minute is
directions to impart Strength and toughness to the film. The typically Sufficient to achieve the desired results. In addition,
sheet is typically stretched from about two to about four 25 primer or other intermediate layers can optionally be used
times the original cast sheet dimension, in one or both between the polymer film and the anti-fog coating
directions. Biaxial orientation is most preferred, with mono In light of the foregoing, a preferred method of controlling
axial orientation being leSS preferred. Generally, Stretching fog formation on polymer film is provided herein.
occurs in a temperature range from about the Second order Preferably, one or both faces of a base polymer film are
transition temperature of the polymer to below the tempera coated with an anti-fog coating of the present invention.
ture at which the polymer softens and melts. Where Optionally, if only one face is coated with the anti-fog
necessary, the film is heat treated after Stretching to "lock coating of the present invention, this coating can occur
in the properties by further crystallizing the film. The
crystallization imparts Stability and good tensile properties before, after or at the Same time the opposite face of the base
to the film. Such heat treatment for polyester film is gener polymer film is coated with an alternate coating. The anti
ally conducted at about 190° C. to about 240° C. 35
fog coating is preferably not overcoated with another coat
Alternate Substrates ing. Such a top coating could limit the ability of the anti-fog
AS discussed above, the coatings and methods of reducing coating to prevent fog.
fog of the present invention are not limited to use on EXAMPLES
polymer film bases. Alternate Substrates Such as metals,
glass, polymeric articles and the like can be coated accord
ing to the teachings of the present invention. Furthermore, it 40 The following Examples demonstrate various aspects of
is envisioned that polymer films coated with the coatings of certain preferred embodiments of the present invention, and
the present invention can also be applied to other Surfaces, are not to be construed as limitations thereof. The formula
including irregular Surfaces, to provide anti-fog properties to tions of the individual Samples are shown in the charts
those surfaces. The film may be heat bonded or adhered to below. In each example, the listed coating Samples were
the Surface, or can be mechanically attached via fasteners, 45 formulated and coated in-line on biaxially oriented polyester
clipS and the like. film. Specifically, heat set PET film was coated in-line
Coating Methods between draw steps on biaxially oriented polyester film with
In-line coating of the base polymer layer, in which the the following Sample coatings. AS in all of the following
coatings are applied during the film manufacturing proceSS examples, anti-fog performance was tested by placing a
and before it is heat-set, is the preferred method for use of 50 sheet of the coated film, coated Side down, over a warm air
the coatings disclosed herein. Typically, the base polymer humidifier Such as a “Holmes Air Pure Mist' humidifier at
film is coated after corona treatment and prior to the Stretch a distance of approximately 3 to 6 inches for a period of
orientation of the film as described in British Pat. No. approximately 2 Seconds. The sheets were observed for
1,411,564, or coated between drawing steps (when biaxially fogging, with a Score of 1 being completely obscured by fog
oriented film is produced) as taught by U.S. Pat. No. 55
and 5 being fog-free. The wetting tension of the film Surface
4,571,363, or coated post-draw as taught by U.S. Pat. No. is measured using the Victor Contact Angle System of AST
3,322,553. Products, Billerica, Mass.
In addition to in-line coating, one or more of the coatings
of the present invention may be off-line coated (after manu EXAMPLE SERIES A

Wetting Tension
Ex. Coating Formulation Anti-fog (dynes/cm)
A-1 12.5% AJ-3O+ 0.5% Nalco 1060 1. 51.OO
A-2 13.5% AJ-3O+ 0.5% Nalco 1060 1. 52.16
 US 6,455,142 B1

-continued
Wetting Tension
Ex. Coating Formulation Anti-fog (dynes/cm)
A-3 12.8% AJ-30 + 0.5% Nalco 1060 + 0.7% Cymel 303 1. 51.56
A-4 14.5% AJ-30 + 0.5% Nalco 1060 1. 52.31
A-5 12.5% AJ-30 + 0.5% Nalco 1060 + 1% LDS-10 5 69.97
A-6 12.5% AJ-30 + 0.5% Nalco 1060 + 1% LDS-10 5 69.71
A-7 12.5% AJ-3O+ O.5% Nalco 1060 - 1% FC-17OC 3. 5 48.25
A-8 12.5% AJ-3O+ O.5% Nalco 1060 - 1%, Arvol 107 PWOH 2 54.25

Cymel 303 is a melamine hardener/crosslinker

Airvol 107 PVOH is polyvinyl alcohol.

The first Series of examples demonstrate the improved 15 Example Series B

performance provided by the LDS-10 surfactant. As seen in
examples A-5 and A-6, the combination of copolyester and The potential negative effect of Cymel 303 crosslinker
this anionic Surfactant provide Surprisingly Superior anti-fog melamine hardener and more than 0.1% FC 170C is Sup
performance. The presence of crosslinkers and polyvinyl ported by the following examples, in which levels of AJ-30
alcohol (A-3 and A-8) do not give rise to Such performance. copolymer, LDS-10 surfactant, Nalco 1060 silica, and
Example A-7 demonstrates that the fluoroSurfactant alone FC-170C fluoroSurfactant are varied:

Anti-fog
(fresh, Wetting Tension
Ex. Coating Formulation aged) (dynes/cm)
B-1 25% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060 5/5 68.50
B-2 25% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060 5/5 66.7O
B-3 25% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060 -3 69.02
B-4 22.5% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060 5/5 69.17
B-5 22.5% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060 5/4 70.18
B-6 22.5% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060 5/5 69.95
B-7 20% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060 4/3 65.44
B-8 20% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060 4/5 66.O7
B-9 20% AJ-30 + 1% LDS-10 + 0.5% Nalco 1060 4.f4 65.13
B-1O 22.5% AJ-30 - 1% LDS-10 + 0.1% FC-17OC + 0.5% 4.5/5 66.75
Nalco 1060
B-11 22.5% AJ-30 - 1% LDS-10 + 0.25% FC-17OC + O.5% 3/5 69.22
Nalco 1060
B-12 22.5% AJ-30 - 1% LDS-10 - 0.5% FC-17OC + 0.5% 1/5 68.977
Nalco 1060
B-13 22.5% AJ-30 - 1% LDS-10 + 0.25% FC-17OC + 2.2% 1/2 58.10
Cymel 303 + 0.5% Nalco 1060
B-14 22.5% AJ-30 + 1% LDS-10 + 0.25% FC-170C + 1.1% 1/3 63.68
Cymel 303 + 0.5% Nalco 1060
B-15, 22.5% AJ-30 - 1% LDS-10 + 0.25% FC-17OC + O.5% 3/5 64.92
Cymel 303 + 0.5% Nalco 1060
B-16 10% M + 1% LDS-10 +0.5% Nalco 1060 4/3 70.71
B-17 10% M + 1% LDS-10 + O.25% FC-17OC + 0.5% 1f4.5 70.73
Nalco 1060
B-18 10% M + 1% LDS-10 + 25% FC-17OC + 1% 1f4.5 66.91
Cymel 303 + 0.5% Nalco 1060
B-19 10% M + 1% LDS-10 + O.25 FC-17OC + O.5% 3f4.5 68.78
Cymel 303 + 0.5% Nalco 1060
B-2O 10% M + 1% LDS-10 + O.25 FC-17OC + O.25% 3f4.5 69.93
Cymel 303 + 0.5% Nalco 1060
M = a copolyester of 10 mol percent sodium salt of 5-sulfoisophthalic acid, 90 mol percent
isophthalic acid and 100 mol percent ethylene glycol
Fresh = day of manufacture
Aged = 22 days after manufacture

provides acceptable but not excellent anti-fog properties, This Example demonstrates the ameliorative effect of
Suggesting a Synergistic effect of the fluoroSurfactant with Short-term aging on Some compositions according to the
Surfactants Such as LDS-10. These data also Support a direct present invention (B-11 and following, except B-16). In
correlation between wetting tension and anti-fog perfor
60 addition, it Suggests that at fluoroSurfactant levels of 0.5 or
greater (B-12), or when crosslinkers are added (B-13
mance. It is further shown that a wetting tension of about 60 through B-15 and B-18 through B-20) anti-fog performance
dyneS/cm or greater (optionally to about 72 dyneS/cm or is diminished, particularly for fresh film.
more) is preferred herein. As will be shown in the following Example Series C
examples, wetting tension of greater than 65 dyneS/cm is 65 These examples reinforce the conclusion that the use of
alternately preferred, with wetting tension of greater than 69 greater than 1% LDS-10 surfactant gives rise to improved
being an additional preferred embodiment. performance:
 US 6,455,142 B1

-continued
Wetting Trans
Tension Total mission
Ex. Coating Formulation Anti-fog (dynes/cm) Haze (%) (%)
D-16 6% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 5 69.96 1.50 91.2
0.5% Nalco 1060
D-17 7% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 5 69.67 O.78 91.4
0.5% Nalco 1060
D-188% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 5 69.41 O.75 91.O
0.5% Nalco 1060
D-199% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 5 70.30 O.66 91.8
0.5% Nalco 1060
D-20 10% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 5 69.17 O.75 91.5
0.5% Nalco 1060

These results establish that even relatively low levels of Luminous Transmittance of Transparent Plastics, using a
copolyester binder give acceptable anti-fog performance in BYK Gardner “HaZe Gard Plus' instrument. The AJ-20A
combination with low levels of surfactants, but that even provides minimum haZe at higher concentrations, whereas
better performance is achieved at higher levels of copoly- 20 the AJ-30 provides minimum haze at lower concentrations.
ester binder.
Total haze is a preferred method of measuring the clarity Example Series E
of a polyester film, which can determine its suitability for These examples establish that two different preferred
Such films as antifog faceshield film. Haze is measured copolyester binders perform better at higher levels of LDS
based on ASTM Method D1003-61, Procedure A, “Haze and 10 Surfactant.

Wetting Trans
Anti- Tension Total Haze mission
Ex. Coating Formulation fog (dynes/cm) (%) (%)
E-1 6% AJ-20A + 0.5% LDS-10 + 0.05% FC-170C + 2 66.14 0.87 90.3
0.5% Nalco 1060
E-2 6% AJ-20A + 0.75% LDS-10 + 0.05% FC-170C + 4 69.99 1.08 90.2
0.5% Nalco 1060
E-3, 6% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 5 68.82 1.21 90.4
0.5% Nalco 1060
E-4 6% AJ-20A + 1.25% LDS-10 + 0.05% FC-170C + 5 70.34 1.14 90.3
0.5% Nalco 1060
E-5 6% AJ-20A + 1.5% LDS-10 + 0.05% FC-170C + 5 68.98 1.34 90.7
0.5% Nalco 1060
E-6 6% AJ-20A + 2% LDS-10 + 0.05% FC-170C + 5 69.24 1.62 90.4
0.5% Nalco 1060
E-7 6% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 5 70.10 O.91 91.2
0.03% Cymel 303 + 0.5% Nalco 1060
E-8 6% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 5 70.32 1.08 91.O
0.03% Cymel 303 + 0.5% Nalco 1060
E-9 6% AJ-20A + 1% LDS-10 + 0.05% FC-170C + 5 70.14 1.02 90.3
0.03% Cymel 303 + 0.5% Nalco 1060
E-1O 6%. M+ O.5% LDS-10 + O.05% FC-17OC + 1. 66.13 0.59 90.7
0.5% Nalco 1060
E-11 6%. M+ O.75% LDS-10 + O.O.5% FC-17OC + 3 70.68 0.72 91.3
0.5% Nalco 1060
E-12 6%. M+ O.5% LDS-10 + O.05% FC-17OC + 4 70.96 O.74 91.3
0.5% Nalco 1060
E-13 6%. M+ 1.25% LDS-10 + O.O.5% FC-17OC + 5 71.1.8 O82 91.2
0.5% Nalco 1060
E-14 6%. M+ 1.5% LDS-10 + O.05% FC-17OC + 5 70.87 O.88 91.O
0.5% Nalco 1060
E-15 6%. M+ 2% LDS-10 + O.05% FC-17OC + 5 70.77 O.99 91.2
0.5% Nalco 1060
 US 6,455,142 B1
13 14
Coatings containing less than 0.75%, specifically 0.5%
LDS-10, show poor anti-fog performance. Even at 0.75%
LDS-10 Surfactant, the resulting anti-fog effects are not
complete. In this case, at optimized coating formulations,
the presence of the Cymel 303 crosslinker did not adversely
affect performance (see E-7 through E-9) and its presence is
believed to provide greater permanence to the coating. Total
haze increases generally for each System as the level of
LDS-10 Surfactant increases.

Example Series F

Wetting Trans
Anti Tension Total Haze SSO
Ex. Coating Formulation fog (dynes/cm) (%) (%)
F-1 6% AJ-20A + 1%. Rhodacal LDS-10 + 0.05% FC-170C + 5 70.07 1.38 90.7
0.5% Nalco 1060
6% AJ-20A + 1.5% Rhodacal LDS-10 + 0.05% FC-170C + 5 70.86 1.47 90.8
0.5% Nalco 1060
6% AJ-20A + 1% Sipon UB + 0.05% FC-170C + 70.59 O.74 90.0
0.5% Nalco 1060
6% AJ-20A + 1.5% Sipon UB + 0.05% FC-170C + 71.29 0.97 90.6
0.5% Nalco 1060
6% AJ-20A + 1% Aerosol OTNV + 0.05% FC-170C + 71.07 0.75 90.5
0.5% Nalco 1060
6% AJ-20A + 1.5% Aerosol OTNV-- 0.05% FC-170C + 69.78 1.45 90.6
0.5% Nalco 1060
6%. M+1% Rhodacal LDS-10 + 0.05% FC-170C + 7O60 O.94 89.6
0.5% Nalco 1060
F-8 6% AJ-20A + 1.5% Rhodacal LDS-10 + 0.05% FC-170C + 70.64 1.23 90.0
0.5% Nalco 1060
6% M + 1% Sipon UB + 0.05% FC-170C + 70.92 1.01 90.1
0.5% Nalco 1060
F-106% M + 1.5% Sipon UB + 0.05% FC-170C + 70.70 1.29 90.4
0.5% Nalco 1060
F-116%. M+ 1% Aerosol OTNV-- 0.05% FC-170C + 70.97 O.93 90.0
0.5% Nalco 1060
F-12 6%. M+ 1.5% Aerosol OTNV + 0.05% FC-170C + 70.64 1.33 90.1
0.5% Nalco 1060

The foregoing preferred compositions Show that optimal 40

results can be achieved with varying levels and varying
components according to the present invention. It is noted
that haze rises to a degree when the level of Surfactant is
raised.

Example Series G

Wetting Trans
Anti Tension Total Haze mission
Ex. Coating Formulation fog (dynes/cm) (%) (%)
4% AJ-20A + 0.48% Aerosol OTNV-- 0.05% FC-170C + 3 67.91 O.77 90.7
0.5% Nalco 1060
4% AJ-20A + 0.72% Aerosol OTNV-- 0.05% FC-170C + 70.35 O.80 90.3
0.5% Nalco 1060
4% AJ-20A + 0.96% Aerosol OTNV-- 0.05% FC-170C + 70.88 O.89 90.3
0.5% Nalco 1060
4% AJ-20A + 1.2% Aerosol OTNV + 0.05% FC-170C + 70.55 O.84 90.3
0.5% Nalco 1060
6% AJ-20A + 0.48% Aerosol OTNV + 0.05% FC-170C + 69.75 O.69 90.6
0.5% Nalco 1060
6% AJ-20A + 0.72% Aerosol OTNV + 0.05% FC-170C + 70.73 O.67 90.7
0.5% Nalco 1060
6% AJ-20A + 0.96% Aerosol OTNV + 0.05% FC-170C + 71.16 O.65 90.3
0.5% Nalco 1060
6% AJ-20A + 1.2% Aerosol OTNV-- 0.05% FC-170C + 5 70.88 0.75 91.2
O5% Nalco 1060
 US 6,455,142 B1
15 16
Aerosol OTNV provides excellent antifog performance tains less than about 0.5 weight percent of a
and excellent clarity. Total haze is low throughout the ranges fluoroSurfactant, and wherein Said coating has a wetting
shown. tension of greater than about 60 dyneS/cm.
2. The coated polymer film of claim 1, wherein said
Example Series H anti-fog coating is transparent.

Wetting Trans
Anti- Tension Total Haze mission
Ex. Coating Formulation fog (dynes/cm) (%) (%)
H-1 2% AJ-20A + 0.4% Aerosol OTNV-- 0.05% FC-170C + 4 69.38 O.49 90.9
0.5% Nalco 1060
H-2 2% AJ-20A + 0.6% Aerosol OTNV-- 0.05% FC-170C + 5 69.51 O.60 89.9
0.5% Nalco 1060
H-3 2% AJ-20A + 0.8% Aerosol OTNV-- 0.05% FC-170C + 5 69.67 O.56 90.1
0.5% Nalco 1060
H-4 2% AJ-20A + 1% Aerosol OTNV-- 0.05% FC-170C + 5 70.57 O.68 90.4
0.5% Nalco 1060
H-5 3% AJ-20A + 0.4% Aerosol OTNV-- 0.05% FC-170C + 4 66.51 O.73 90.2
O.5% Nalco IO60
H-6 3% AJ-20A + 0.6% Aerosol OTNV-- 0.05% FC-170C + 4 70.56 O.77 90.3
0.5% Nalco 1060
H-7 3% AJ-20A +0.8% Aerosol OTNV-- 0.05% FC-170C + 5 70.61 O.83 89.8
0.5% Nalco 1060
H-8 3% AJ-20A + 1% Aerosol OTNV-- 0.05% FC-170C + 5 69.83 O.94 90.4
0.5% Nalco 1060
H-9 4% AJ-20A + 0.4% Aerosol OTNV-- 0.05% FC-170C + 4 66.57 O.82 90.6
0.5% Nalco 1060
H-10 4% M-20A + 0.6% Aerosol OTNV-- 0.05% FC-170C + 5 70.04 O.83 90.2
0.5% Nalco 1060
H-11 4% AJ-20A + 0.8% Aerosol OTNV-- 0.05% FC-170C + 5 70.39 O.89 90.3
0.5% Nalco 1060
H-12 4% AJ-20A + 1% Aerosol OTNV-- 0.05% FC-170C + 5 70.82 O.86 91.O
0.5% Nalco 1060
H-13 2% AJ-20A + 0.4% Sipon UB + 0.05% FC-170C + 2 55.39 O.63 90.7
0.5% Nalco 1060
H-142% AJ-20A + 0.6% Sipon UB + 0.05% FC-170C + 3 62.86 O.66 90.7
0.5% Nalco 1060
H-152% AJ-20A + 0.8% Sipon UB + 0.05% FC-170C + 4 66.76 O.66 90.7
0.5% Nalco 1060
H-16 2% AJ-20A + 1% Sipon UB + 0.05% FC-170C + 4 67.67 0.71 91.1
0.5% Nalco 1060
H-17 3% AJ-20A + 0.4% Sipon UB + 0.05% FC-170C + 2 54.57 O.66 90.6
0.5% Nalco 1060
H-183% AJ-20A + 0.6% Sipon UB + 0.05% FC-170C + 3 61.96 0.71 91.O
0.5% Nalco 1060
H-193% AJ-20A + 0.8% Sipon UB + 0.05% FC-170C + 4 66.85 0.78 90.7
0.5% Nalco 1060
H-203% AJ-20A + 1% Sipon UB + 0.05% FC-170C + 4 66.82 O.76 91.3
0.5% Nalco 1060
H-21 4% AJ-20A + 0.4% Sipon UB + 0.05% FC-170C + 2 55.87 O.69 90.8
0.5% Nalco 1060
H-22 4% AJ-20A + 0.6% Sipon UB + 0.05% FC-170C + 3 61.79 0.87 90.8
0.5% Nalco 1060
H-23 4% AJ-20A + 0.8% Sipon UB + 0.05% FC-170C + 4 68.32 0.70 91.O
0.5% Nalco 1060

50
These data Suggest that Sipon UB Surfactant is preferably 3. The coated polymer film of claim 1, wherein said film
used at a somewhat higher level than Aerosol OTNV is transparent.
surfactant, with roughly 0.8% and 0.4% preferred 4. The coated polymer film of claim 1, wherein an
minimums, respectively. intermediate coating or layer is interposed between Said
The present invention having been thus described with 55 anti-fog coating and Said film layer.
particular reference to the preferred forms and embodiments 5. The coated polymer film of claim 1, wherein said
thereof, it will be obvious to one of ordinary skill in the art fluoroSurfactant comprises fluoroaliphatic oxyethylenes of
that various changes and modifications may be made therein carbon chain lengths of about 4 to about 8 and polyethylene
without departing from the Spirit and Scope of the invention glycol.
as defined in the appended claims. 60
6. The coated polymer film of claim 1, wherein said
What is claimed is: binder comprises a water-Soluble copolyester comprising,
1,3-benzenedicarboxylic acid, 5-sulfo-, 1,3-dimethyl ester
1. A coated polymer film having a coated Surface that Sodium Salt, polymer and dimethyl 1,4-
resists the formation of fog, Said film comprising benzenedicarboxylate, 1,2-ethanediol and 2,2'-oxybis
a Self-Supporting polymer film layer, and (ethanol).
an anti-fog coating on Said film layer, Said anti-fog coating 65 7. The coated polymer film of claim 1, wherein said
consisting essentially of a hydrophilic copolyester binder comprises a water-Soluble copolyester comprising
binder and a Surfactant, wherein Said Surfactant con about 50 to about 98 mol percent isophthalic acid, about 2
 US 6,455,142 B1
17 18
to about 20 mol percent of at least one Sulfomonomer 26. The polymer film of claim 1, wherein said anti-fog
containing a Sulfonate group attached to a dicarboxylic coating has a coating thickness of about 0.02 microns to
nucleus, and about 100 mol percent of at least one copoly about 0.1 microns.
merizable glycol having from about 2 to about 11 carbon 27. The polymer film of claim 1, wherein said anti-fog
atOmS. coating has a coating thickness of about 0.03 microns to
8. The polymer film of claim 1, wherein said polymer about 0.05 microns.
comprises polyester. 28. The polymer film of claim 1, wherein said coating has
9. The polymer film of claim 1, wherein said binder is a wetting tension of greater than about 65 dyneS/cm.
present at about 1 to about 30 weight percent of Said anti-fog 29. The polymer film of claim 1, wherein said coating has
coating. a wetting tension of greater than about 69 dyneS/cm.
10. The polymer film of claim 1, wherein said binder is
1O 30. The coated polymer film of claim 1, wherein said
present at about 1 to about 6 weight percent of Said anti-fog anti-fog coating contains no crosslinkers.
coating. 31. The coated polymer film of claim 1, wherein said
anti-fog coating contains no more than about 0.5 weight
11. The polymer film of claim 1, wherein said binder percent crosslinker.
comprises a Sulfomonomer. 15
32. A process for controlling the formation of fog on a
12. The polymer film of claim 11, wherein said Sul Surface, Said process comprising:
fomonomer comprises 5-Sulfoisophthalic acid. a) coating said Surface with an anti-fog coating consisting
13. The polymer film of claim 1, wherein said fluorosur essentially of a water-Soluble hydrophilic copolyester
factant is present at about 0.02 to about 0.5 weight percent binder and a Surfactant, wherein Said Surfactant con
of Said anti-fog coating. tains less than about 0.5 weight percent of a
14. The coated polymer film of claim 1, wherein said fluoroSurfactant, and wherein Said coating has a wetting
Surfactant is present at about 0.4 to about 2.0 weight percent tension of greater than about 60 dyneS/cm.
of Said anti-fog coating. 33. The process of claim 32, wherein said coating is
15. The coated polymer film of claim 1, wherein said coated on a polymer film Surface.
Surfactant comprises an anionic Surfactant. 34. The process of claim 32, wherein Said coating of Said
16. The coated polymer film of claim 1, wherein said 25 Surface is accomplished by in-line coating.
Surfactant comprises Sodium dodecyl benzeneSulfonate. 35. A coated polymer film having a coated Surface that
17. The coated polymer film of claim 1, wherein said resists the formation of fog, Said film comprising
Surfactant includles comprises Sodium lauryl Sulfate. a Self-Supporting polymer film layer, and
18. The coated polymer film of claim 1, wherein said an anti-fog coating layer on Said film layer, Said anti-fog
Surfactant comprises a SulfoSuccinate. coating consisting essentially of a hydrophilic copoly
19. The coated polymer film of claim 1, wherein said ester binder and a Surfactant, wherein Said Surfactant
Surfactant comprises Sodium 2-ethylhexylsulfate. contains less than about 0.5 weight percent of a
20. The polymer film of claim 1, further comprising a slip fluoroSurfactant, and wherein Said coating is fog-free
agent. after 2 Seconds exposure to a warm air humidifier at a
21. The polymer film of claim 20, wherein said slip agent 35 distance of 3-6 inches.
comprises at least one Silica. 36. A process for controlling the formation of fog on a
22. The polymer film of claim 20, wherein said slip agent Surface, Said process comprising:
comprises colloidal SiO2. a) coating said Surface with an anti-fog coating layer
23. The polymer film of claim 20, wherein said slip agent consisting essentially of a hydrophilic copolyester
is present at about 0.25 to about 2 weight percent of Said
anti-fog coating. 40 binder and a Surfactant, wherein Said Surfactant con
24. The polymer film of claim 20, wherein said slip agent tains less than about 0.5 weight percent of a
is present at about 0.3 to about 1 weight percent of Said fluoroSurfactant, and wherein Said coating is fog-free
anti-fog coating. after 2 Seconds exposure to a warm air humidifier at a
25. The polymer film of claim 1, wherein said anti-fog distance of 3-6 inches.
coating has a solids level of about 0.01 to about 30 weight
percent.