Note: Descriptions are shown in the official language in which they were submitted.
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FN 42921 CAN 3A
T~IREE--DIMENSIONAI- SELF~ ERENT ARTICLES
Technical Field
The present invention relates to radiation-
curable three-dimensional articles that may be transferred
and adhered to a substrate, particularly to article~
compri~ing at least one layer of radiation-curable
pressure-sensitive adhesive.
Background of the Invention
15 There are many applications in which a
three-dimensional article or a two-dimensional graphic is
adhered to a substrate to provide ornamentation or
identification. Such articles are attached to a myriad of
articles such as novel~ies, e.g., key chains, and coffee
mugs, appliancec, e.g., vacuum cleaners, sports equipment,
and automobiles.
These article may be formed of plastic,
plastic-met~l composites, or may be a primarlly two-
dimensional object such as a thin polymeric film, e.g.,
decals or striping. The objects may be purely ornamental or
they may identify the type or manufacturer of the item,
e.g., "PACRARD" or "TURBO."
Three-dimensional articles have been produced by
providing an indicia-bearing substrate, and providing a
transparent polymeric lens disposed over the indicia
bearing substrate. A curable liquid resin i~ typically
applied over the indicia-bearing substrate to form a clear
meniscus that becomes a clear polymeric lens when cured.
For example, see U.S. Patents No. 4,100,001, 3,391,853,
4,139,654, 4,332,074.
Previous attempts at providing ornamentation or
identification have also included individually
injection-molded or die-cast articles, made from plastic,
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zinc, aluminum~ and the like. These articles are
frequently decorated by use of metal plating, sputtering,
and/or painting. These varied separate steps render the
final articles too expensive for attachment to moderately
priced products.
Three-dimensional articles are typically adhered
to a substrate by one of two means, liquid adhesiveæ or
mechanical fasteners. When mechanical fasteners which
penetrate the substrate such as clips, screws, or pins, are
used, they have proven expensive. This is due to the cost
of the fastener~ and to the cost of the labor needed for
precision penetration of the substrate and attachment of
the mechanical fasteners to both the substrate and the
article to be attached. The action of penetrating the
substrate may also increase the susceptibility of the
substrate to damage, e.g., rust. Further, it is difficult
to use such fasteners where very thin articles are desired,
or where such articles involve fine details.
When liquid adhesives have been used on the
articles of the prior art, problems have arisen with
correct placement of the article, and oozing of the
adhesive onto the substrate area around the article and
onto the article itself. This is unsightly, masks the
decorative features of the article, and may be difficult to
remove without damage to the article and/or substrate.
Foam adhesive tapes have been used for attachment
of three-dimensional articles with somewhat more succes~;
however, they require an extra step in production to adhere
the tape to the article. Further, they may be undesirable
for applications where an integrated appearance is
desirable; the thickness of the tape (1.25-3 mm) may double
the typical thickness (1.25-5 mm) of the article.
Two-dimensional graphics are often substituted
for the three-dimensional articles described above. These
are generally provided in the form of a flat polymeric
films cut into a desired shape (decals) and applied to a
substrate with an adhesive. Such flat graphics are
2~)073~4
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suita~le for some applications, but do not provide the
three-dimensional appearance or benefits desired or many
applications, e.g., decals are easily obscured by even a
light layer of soil.
Acrylate pressure-sensitive adhesives are also
well known in the art. In U.S. Patent No. Re 24,906
(Ulrich), alkyl acrylate copolymers are described which are
predominately alkyl esters of acrylic acid having from 4 to
14 carbon atoms, and further comprise a minor amount
(3-12%, preferably 4-8%) of a polar copolymerizable monomer
~uch a~ acryl~c acid. Such adhe~ives are w~dely popular as
they are readily available, and provide a good balance of
tack, shear and peel properties on a variety of substrate~
at a relatively low cost.
U.S~ Patent No. 4,181,752 (Martens et al)
disclo6es a process for ultraviolet photopolymerization of
alkyl acrylate esters and polar copolymerizable monomers to
form the acrylate copolymer. The photopolymerization of
Marten~ i8 preferably carried out in an inert atmo~phere as
oxygen tends to inhibit the reaction. Adhesive properties
for tapes made via the Martens process are improved over
tho~e made by solution polymerization, and provide
reduction in solvent usage. Such adhesives and tapes made
therewith have high adhesion and shear and are permanently
adherent.
Additional patents disclose ultraviolet radiation
of acrylate adhesives for use in adhesive tape~. U.S.
P~tent No. 4,364,972 (Moon) discloses the use of
N-vinyl-2-pyrrolidone as the polar copolymerizable monomer
in the acrylate adhesive copolymer.
Foam tapes are disclosed in U.S. Patent No.
3,565,247 (Brochman), U.S. Patent No. 4,223,067 (Levens)
Becau~e the microbubble-containing tape of the Levens
patent has a foam-like appearance and character, it is
sometimes called a "foam-like" tape even though its
pressure- ensitive adhesive layer is substantially free of
voids except for the hollow spaces within the microbubbles.
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Pxessure-sensitive adhesive tapes are di~closed
in U.S. Patent No. 4,415,615, (Esmay et al.) wherein ~n
adhesive layer is made by frothing an acrylate monomer
mixture composition which is photopolymerizable to a
pressure-sensitive adhesive state and coating that froth
onto a backing, and photopolymerizing to a pre6sure-
sensitive adhesive having a cellular structure. The
cellular adhesive layer of the Esmay tape compriseg at
least 15% voids by volume, and recovers ~ubstantially its
original thickness after compression.
However, none of these patents disclose the u~e
of ~uch radlation-curable pressure-sensitive adhesives in
three-dimensional graphic objects. Further, such article~
would be flat acrylic foam which would need to be sub~ected
to further processing such as diecutting.
Accordingly, there is a continued need for low-
cost, attractive, easily attached three-dimensional
decorative articles for ornamentation and/or identification
of a wide variety of products. A molded three-dimensional
article comprising at least one member having a
radiation-cured pressure-sensitive adhesive body and a
carrier film will provide such an article, which may be
tailored for many applications.
Applicants have discovered that molded acrylic
foam performs significantly better than a flat acrylic
foam. There are several reasons for the significant
advantages seen with the molded articles of the invention.
First, the profile of the foam can be molded to match the
part being adhered to; i.e., there need be no ~pace between
the two at any point. This eliminates spaces in bonding
which would allow for dirt, etc., to contaminate the
bonding surface, leading to faulty adhesion of the article.
Further, in ~ome applications where there a seal is
required, the molded article can be designed to completely
eliminate any spacing, yielding the desired airtight or
watertight seal. Also, foams are difficult to diecut in
any intricate shape; however, the radiation-cured
.
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pressure-sensitive adhesives of the invention may be poured
into a mold with an intricate shape prior to cure, allowing
for detailed articles to be easily formed.
As used herein, these terms have the following
meanings.
1. The terms "member" or " article member" refer
to a ~ingle object that may be provided in a re~ognizable
or decorative shape, such as a letter, or may be a
functional ~hape, such as a gasket.
2. The terms "body" or "member body" refer t~ one
or more layers of radiation-curable pressure-sensitive
adhesive along with any decoration, additional adhesive
layers, polymeric layers, and the like compri~ing the
member.
3. The term "article" refers to a composite
consisting of one or more members.
Summary of the Invention
The present invention provides a self-adherent,
three-dimensional, radiation-cured article comprising:
(a) one or more members, each member of the
article including a pressure-sensitive adhesive body, each
body having a top surface and a bonding surface, and
(b) a carrier film releasably adhered to the
bonding gurface of each member.
The article may comprise one continuous member or
several interconnected members. Each member may likewise
have a body comprising a single layer of radiation-curable
material or may be several layers. The simplest articles
of the invention are single-layered continuous items, e.g.,
adhesive gaskets, having a pressure-sensitive adhe6ive
body. Such items have two self-adherent surfaceg capable of
bonding, and being radiation-curable, are inexpen~ive to
produce, and to use in production.
Where differential adhesion is desirable, an
additional adhesive layer may be provided on the 6econd
bonding surface, in order to provide the desired adhesive
ZOG731 ~
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properties. This additlonal adhesive layer may be coated
and radiation-cured or may be cured separately and then
laminated to the article.
Typical ornamental articles include members
having bodies containing additional materials which are
adhered to the pressure-sensitive body of one or more of
the article members, including decorative or abrasion-
re~istant polymeric films, dyes, pigments, reflective
particle~ and metal flakes. The members may also comprise
additional layers including nonpressure-sensitive
radiation-cured materials.
More complex articles may include several
members. Such articles may consist of members provided
together in a logical sequence such as a word, e.g.,
"T-U-R-B-0", wherein each letter is considered a member.
The present invention also provides a method for
producing a self-adherent, three-dimensional article
comprising the steps of
a) providing a mold having at least one cavity
and a lamination surface surrounding each cavity;
b) filling each of said cavitie~ to the level of
said surface with radiation-curable monomers, such that at
lea6t a portion of said monomers being radiation-curable to
a pre66ure-6en6itive adhesive state, 6aid portion ~eing
added last~
c) coating a carrier film onto said surface and
6aid radiation-curable monomers;
d) contacting the radiation-curable monomer~ into
a pre~sure-sen~itive adhesive with sufficient radiation to
cure the monomers and to form a bond to the carrier film
sufficient to releasably adhere the pressure-sensitive
adhe6ive to the carrier film upon removal of the article
member from the mold, and
e) removing the contents of the mold to provide a
gelf-adherent, three-dimensional article that comprise6 at
lea~t one member, adhered to the carrier film.
Brief Description of the Drawings
Fig. 1 is a ~chematic cross-sectional view
depict~ng one step of a method of the present invention.
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Fig. 2 is a schematic cross-sectional view of a
mold and article of the invention.
Fig. 3 is a schematic cross-sectional view of a
self-adherent three-dimensional article of the invention.
s Fig. 4 is a schematic cross-section of an article
of the invention showing excess material being removed from
the individual members.
Detailed Description of the Invention
Referring to Figure 1, a mold 10 having cavities,
12 and a lam~nation surface 14 surrounding the c~vities,
are shown. Each of the cavities 12 has a curable resin 16
that may al80 partially cover the lamination surface 14. A
carrier film 18 is shown being laminated to the curable
resin 16 by means of a roller 19. The roller 19 applies
pressure to the carrier film to force any trapped air from
between the carrier film 18 and the resin 16.
Referring to Figure 2, the article includes a
carrier film 18, a mold 20, having cavities 22, and a
lamination surface, 24 is shown. The cavities 22 each
include member bodies 26 comprising the radiation-cured
pre~sure-sensitive adhesive.
Referring to Figure 3, an article of the
invention is shown. The article includes a carrier film 31
having a release surface thereon. A pair of article
members 32, having bodies 33, top surfaces 34, ~onding
surfaces 35, a pigment layer 36, and a protective clear
coat 37, are shown.
Referring to Fig. 4, an article having a pair of
members 41, are shown adhered to a carrier film 42 having a
relea~e surface thereon~ The member~ 41 include a body 42,
a pigment layer 43, and a protective clear coat 44. Also
6hown is excess material 45 surrounding the members after
removal from the composite. The excess material 45 is
removed via known techniques such as kiss-cutting or CO2
laser.
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The self-adherent radiation-cured article6 of the
invention may be provided in a number of embodiments
containing one or more members. The member body include~ a
top surface, which is the surface that is meant to be
viewed when the article is adhered to a substrate, and a
bonding surface, which is the surface that is meant to be
bonded to a substrate, and is releasably adhered to a
carrier film. The bondin~ surface may consist of the
radiation-cured pressure-sensitive adhesive which compri6es
a portion of each member body, or it may con~ist of an
additional adhesive which has been laminated thereto. The
top 6urface, may also consist of such radiation-cured
pressure-sen6itive adhesive, either in its natural state or
decorated by a variety of ways to provide, e.g., coloring,
or metallization as desired for the particular application,
or it may comprise a number of decorative additional
radiation-cured layers. Additionally, a protective clear
coat may be provided over the decoration layer to protect
the decoration from wear over a period of time. Frequently,
an article including a series of members will be provided
having a transfer tape adhered to the top of each member 60
that the original spacing and alignment may be preserved
when the carrier film is removed for attachment.
Preferred pressure-sensitive adhesives for use in
the body of the article members, are acrylic pressure-
sensitive adhesives. The acrylic polymers u6eful in the
adhesive bodies of article members of the invention contain
at lea~t one alkyl acrylate monomer, preferably a
monofunctional unsaturated acrylate ester of non-tertiary
alkyl alcohol, the molecules of which have from about 4 to
about 14 carbon atoms. Such monomers include, e.g.,
isooctyl acrylate, 2-ethyl hexyl acrylate, isononyl
acrylate, decyl acrylate, dodecyl acrylate, butyl acrylate,
and hexyl acrylate. The acrylic polymers preferably
contain at least about from about 60 parts of the alkyl
~ .. ..
Z0~57~
g
acrylate monomer. The alkyl acrylate monomers may be ufied
as homopolymers or may be polymeri~ed with at least one
polar copolymerizable monomer.
The polar copolymerizable monomer is selected
from strongly polar monomers such as acrylic acid,
acrylamide, itaconic acid, hydroxyalkyl acrylates, or
substituted acrylamides or moderately polar monomers such
as N-vinyl-2-pyrrolidone, N-vinyl caprolactam, and
acrylonitrile. When one or more polar monomer are used,
they may comprise up to about 40 parts of the acrylic
copolymer.
The mixture of the polymerizable monomers also
contains a photoinitiator to induce polymerizati~n of the
monomers. Photoinitiators which are useful include the
benzoin ethers such as benzoin methyl ether or benzoin
isopropyl ether, substituted benzoin ethers such as anisole
methyl ether, substituted acetophenones such as
2,2-diethyoxyacetophenone and 2,2-dimethoxy-2-
phenylacetophenone, substituted alpha-ketols such as 2-
methyl-2-hydroxypropiophenone, aromatic sulfonyl chlorides
such as 2-naphthalene sulfonyl chloride, and photoactive
oximes such as 1-phenyl-1,1-propanedione-2-(0-
ethoxycarbonyl)-oxime. The photoinitiator is present in an
amount of about 0.01 to about 1 part per hundred parts of
the acrylic monomers (phr) of the instant removable
pre6sure-6en6itive adhesive compositions.
Where it is desirable for the article to have
increased internal strength, a crosslinking agent may also
be added to the monomer mixture. Useful acrylate
crosslinkers include 1,6-hexanediol diacrylate as well as
the multifunctional acrylates disclosed in U.S. Patent No.
4,379,201 (Heilmann et al.), e.g., trimethylolpropane
triacrylate, pentaerythritol tetracrylate, 1,2-ethylene
glycol diacrylate, and 1,2-dodecanediol diacrylate. Other
useful crosslinking agents include the substituted
2007~1~
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triazines, such as those disclo~ed in U.S. Patent Nos.
4,329,384 (Vesley et al.) and 4,330,590 (Vesley), e.g.,
2,4-bis(trichloromethyl)-6-(3,4-methoxyphenyl-s-triazine)
and other chromophore halomethyl-5-triazines. When u6ed,
the crosslinking agent is present in an amount of from
about 0.01 to about 1 phr.
In a highly preferred embodiment, the
pressure-sensitive adhesive body is a foam-like layer,
e.g., a monomer blend comprising microspheres may be u6ed.
The micro~pheres may be glass or polymeric. The micro~
~pheres ~hould have an average diameter of 10 to 200
micrometers, and comprise from about 5 to about 65 volume
percent of the core layer. The thickness of foam-like
layers in preferred articles of the invention range from
about 0.25 mm to about 3.5 mm in thickness.
Especially preferred microspheres are polymeric
micro~pheres, such as those described in u.S. Patent Nos.
3,615,972, 4,075,238, and 4,287,308. The microspheres are
avallable from xema Nord Plastics under the trade name
"Expancel" and from Matsumoto Yushi Seiyaku under the trade
name "Micropearl". In expanded form, the microspheres have
a specific density of approximately 0.02-0.036 g/cc. It is
possible to include the unexpanded microspheres in the core
layer and 6ub~equently heat them to cause expansion, but it
i~ generally preferred to mix in the expanded microsphere6.
Thi~ proces6 ensures that the hollow microsphere6 in the
final core layer are substantially surrounded by at least a
thin layer of adhe~ive.
Preferred glass microspheres have average
diameter~ of about 50 micrometers. When glass microspheres
are used, the pressure-sensitive adhesive layer should be
at least 3 times as thick as their diameter, preferably at
10ast 7 times. The thickness of layers containing such
glas~ microspheres should be at least six times, preferably
at lea~t twenty times that of each microsphere-free layer.
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Where colored articles are desired, the glass
microspheres may be coated with organic thin-film coatings
such as those disclosed in U.S. Patent Nos. 4,612,242,
(VeEley et al.), 4,618,525, (Chamberlain et al.), or by
forming the glass microbubbles from stained glass as
disclosed in U.S. Patent Nos~ 4,666,771, and 4,780,491,
(Vesley at al.) or, the articles may be made according to
U.S. Patent 4,748,061 (Vesley).
In another preferred embodiment, the
pressure-sensitive adhesive is a cellular pressure-
sensitive adhesive membrane comprising from about 15~ to
about 85% voids as disclosed in U.S. Patent 4,415,615,
(E~may et al.). Typical cellular pressure~sensitive
adhesives have good flexibility and good adhesion to rough
surfaces. Where such adhesives are used in articles of the
invention, the procedure involves the additional step of
frothing the radiation-polymerizable pressure-sensitive
adhesive compo~ition, and then coating the froth into the
cavity of the mold.
Other useful materials which can be blended into
the pressure-sensitive adhesive layer include, but are not
limited to, fillers, pigments, plasticizers, tackifiers,
fibrous reinforcing agents, foaming agents, antioxidants,
stabilizers, fire retardants, and viscosity adjusting
agents.
An especially useful filler material is
hydrophobic silica as disclosed in U.S. Patents No.
4,710,536 and 4,749,590, (Klingen, Zimmerman). In one
preferred embodiment of the present invention, the
pressure-sensitive adhesive layer further comprises from
about 2 to about 15 phr of a hydrophobic silica having a
surface area of at least 10 m2/g.
Other known radiation-curable resins may be
useful in the present invention to form portions of the
member bodies. A clear, abrasion-resistant resin may be
placed in the mold to form a secondary cavity into which
200~
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the pressure-sensitive adhesive i8 placed. Useful sy6tems
include urethane acrylates, acrylates, and epoxy acrylates.
Specific examples include isooctyl acrylate/acrylic
acid/hexanediol diacryla~e terpolymers and aromatic epoxy
and tetraethylene glycol diacrylate ( TTEGDA) systems.
When used, the radiation-curable resin portion6
of the member body may also include additives and fillers
known in the art, similar or different to tho6e included in
the pressure-sensitive adhesive layer. Any additives must
be of appropriate type and level of usage not to
6ignificantly interfere with the photopolymerization of the
member.
The top surface of the member bodies may be
decorated to provide the desired aesthetic properties for a
given application. Electroplating, evaporation,
sputtering, spray painting, screen printing, hot stamping,
vapor coating, ink composites, or any other known means for
decorating the top surface may be used. A decorative layer
may also be added first by vacuum-filling a porous mold
with such a layer, e.g., a film layer. This creates a new
"cavity", lined by the decorative layer. The radiation-
curable monomers are then filled into the cavity, and cured
as described.
The carrier film may be any flexible material
havinq a release surface permitting ready removal from the
pres6ure-gen6itive adhesive body of the article. The film
i6 pl~ced over the lamination surface and the pressure-
sensitive adhesive composition prior to the
photopolymerization of the article. The carrier film must
allow sufficient radiation to pass in order to allow cure
of the article in a reasonable time.
Suitable carrier films include silicone coated
poly(ethylene terephthalate) (PET), polypropylenes,
polyethylenes, polyimides, and the like.
The carrier film may also have a polymeric
6upport film laminated thereto to provide added inteqrity
to the article, especially where the individual members are
2007
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e~pecially numerous or weighty. The support film may
comprise such materials as PET, or polyvinyl chloride,
e.g., Scotchcal, available from 3M Company, and may be
clear or colored.
Method of Manufacture
The present invention provides a method for
manufacturing a self-adherent, three-dimen~ional article.
The first step in the method is to provide a mold having at
leaæt one cavity. The surface of the mold and the mold
cavities are preferably a low surface energy material so
that the molded articles are easily released from the mold.
Molds may be made from, e.g., aluminum, etched plastic,
euch as Cyrel~M, available from E.I. DuPont de Nemours,
polyethylene, polypropylene, TeflonSM, DeflonTM, or
Delfin~M. The cavities of the mold are in the shape of the
desired article. A single mold would include cavities for
multi-member articles, e.g., "~-U-R-B-O" could be produced
as a single article. The depth of the mold cavities i8
typically 0.25 mm to about 5 mm, preferably from about 0.5
mm to about 1.5 mm.
After the mold has been prepared, and a suitable
release coating provided therein, the cavities are filled
with radiation-curable resin, at least a portion of which
is radiation-curable to a pressure-sensitive adhesive
state, to a level equal to that of the surface surroundlng
the cavities; this surface is referred to as the lamination
~urface. If more than one radiation-curable resin is used,
the resin which is curable to a pressure-sensitive adhesive
state i6 the last to be placed into the cavity so that it
will form the bonding surface. The lamination surface and
the surface of the uncured resin may be coplanar or the
resin may run over onto the lamination surface. Any
additional resin that may have spilled onto the lamination
~urface may be scraped off with a squeegee or the like, or
may be forced out during placement of the carrier film.
20C~73~
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A decorative layer may be added first by
vacuum-filling a porous mold with such a layer, e.g., a
film layer first. This creates a new "cavity~, lined by
the decorative layer. The radiation-curable monom~rs are
then filled into the cavity, and cured as described.
The carrier film is then placed by conventional
means, e.g., roll-coated onto the lamination ~urfacs, and
the surface of the pressure-sensitive adhesive resin. If
any additional layers are laminated to the carrier film
such as a polymeric support film, this is done prior to the
film's placement on the cavities.
The mold is then contacted by sufficient
radiation to cure the pressure-sen~itive adhesive and any
other radiation-curable resin therein, and to form a bond
between the adhesive and the carrier film. While the type
and amount of radiation are dependent upon the typets) of
radiation-curable resin used, the appropriate type and
amount are easily selected by one skilled in the art from
such types as ultraviolet radiation, e.g., mercury vapor,
mercury metal halide or pulse zenon lamps, gamma radiation
or electron-beam radiation. Where acrylic
precæure-sensitive adhesive polymers are used, they
preferably polymerized according to the methods of U.S.
Patent Nos. 4,303,485 (Levens), 4,181,752 (Martens) or
4,243,500 (Glennon).
The invention may be more fully understood from
the following examples which are intended for illustrative
purpo~es only, and do not limit the scope of the invention
as claimed. All ratios, percentages, and parts herein are0 by weight unless otherwise specifically stated.
EXAMPLES
Example 1
A three-dimensional, self-adherent article of the5 invention was prepared as follows:
20C~
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An ultra-violet ~UV) photopolymerizable mixture
containing 87.5 parts isooctyl acrylate (IOA), 12.5 parts
acrylic acid (AA), and 0.04 part 2,2-dimethoxy-2-phenyl-
acetopheone, available as IrgacureTH 651 from Ciba-Geigy, was
partially polymerized in an inert atmosphere under UV to
provide a coatable syrup having a Brookfield viscosity of
about 3000 cps. To this syrup was then added 8 parts of
C-15/250 glass microbubbles available from Minnesota Mining
and Manufacturing (3M), 2 parts of a hydrophobic fumed
silica, AerosilTM R-972 from Degussa, 0.1 part Irgacure 651
and 0.05 part 1,6-hexanedioldiacrylate (HDDA).
The above composition was then poured into the
cavities o~ a urethane mold. The mold was previou~ly pre-
pared from a .03 mm thick urethane film (25 cm x 30 cm), with
cavities thermoformed as "T"-"U"-"R"-"B"-"O"in the film at a
depth of 0.5 mm. The composition was then covered with a bi-
axially - oriented 0.05 mm thick polyethylene terephthalate
(PET) film, the facing surfaces of which had a low adhesion
release coating thereon, and placed under UV lamps at a total
energy of 450 mj. After curing, the urethane mold became an
integral part of the three-dimensional article. Kiss-cutting
may be performed on the article if desired.
Examples 2-3
The~e were made similar to Example 1 except that a
polyethylene mold was used in Example 2, and a polypropylene
mold was used in Example 3 in place of the urethane mold.
These molds were coated with release ayents so that the cured
articles were easily removed from the molds by pulling.
Example 4
A three-dimensional article was made as described in
Example 1, except that a grey colored urethane film was used
for the mold and aluminum vapor-coated glass bubbles were
used rather than clear microbubbles to produce a solid grey
emblem. The glass bubbles are as described in U. S. Patent
No. 4,618,525, (Vesley, Zimmerman et al.).
ZOG7~14
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~xample 5
A three-dimensional article of the invention was
prepared as follows:
A UV curable resin composition, consisting of 76.6
parts of an aliphatic urethane acrylate oligomer, containing
25% 2-ethylhexyl acrylate available as XP-173-09 from
Cargill, Inc., 14.2 parts of N-vinyl-2-pyrrolidone, 8.9 parts
of a multiacrylate crosslinker, tetraethyleneglycol
diacrylate available from Celanese Corp., and 0.3 part of a
photoinitiator, diethoxyacetophenone, was prepared by mixing
the ingredient6 together in a polyethylene container.
The resin composition was then poured into cavitie6
in an aluminum mold. The mold was previously prepared with
cavities "D"-"O"-"D"-"G"-E" ("DODGE") machined in the plate
at a depth of 0.5 mm. A polymeric carrier film, was then
laminated to the mold containing the UV curable composition.
The carrier film was a polyethyleneterephthalate
(PET) film of about 50-125 micrometers thick, coated with a
GE solventless silicone release material using a 3-roll
off6et gravure for a controlled release sur~ace. An adhesive
(a terpolymer of 70 parts IOA, 22.5 parts methylacrylate and
7.5 parts AA was coated at a thickness of 75 micrometers onto
the silicone release coating using a knife coater, and dried.
The adhesive side of this film was facing the UV curable
composition, pressing it into the cavities of the mold,
eliminating entrapped air.
The entire structure was then placed under UV lamps
for a total exposure energy of about 450 mj. The cured three
dimensional article with the carrier film attached was then
removed from the aluminum mold by pulling.
This was then decorated by screen printing,
employing a 230 mesh polyester screen. Scotchal 3905 ink
available from 3M was printed on the emblem on a hand
screening table using a squeeæe roll of a 60 durometer (Shore
A Hardnes6) urethane rubber. The inks were then baked for
one hour at 165F prior to applying a protective polyurethane
clearcoat overcoat.
20~7$1~
-17-
The formulation of the protective coating used wa~
as follows: 17.3 parts polyester polyol, available as
DesmophenSM 670-80 from Mobay Chemical, Inc., 6-7 parts of an
aliphatic isocyanate, available as DesmodurTM N-100 from
Mobay Chemical, Inc., 0.5 part of bis(2,2, 6,6-tetramethyl-
piperidyl) sebacate, available as Tinuvin 770 from
Ciba-Geigy, 0.5 part of a flow additive, an acrylic copolymer
resin solutisn in Xylene, 50% solid, Specific gravity at 25C
of O.g25-0.941, available as MultiflowTM from Monsanto
Industrial Chemicals, and 75 parts of a solvent, xylen~.
The emblem was finally kiss-cut using a steel rule
die, to remove excess adhesive and UV cured composition, to
form the finished product.
Examples 6-7
Three-dimensional articles of the present invention
were prepared in the same manner as Example 5, except that
the mold was machined to depths of 1.0 mm and 1.5 mm,
respectively.
Example 8
A three-dimensional article was prepared as in
Example 5, except that an application tape, Transferite
#6792, commercially available from American ~iltrite, Ine.,
was applled to the article to maintain the spacing of letters
and symbol 6 ~
Example 9
A three-dimensional article of the invention was
prepared as in Example 5, except that instead of the aluminum
plate, the mold used was made of a photo etched plastic
commercially available as Cyrel, from DuPont, Inc.
Example 10
A three-dimensional article was made in the same
manner as Example 5, except that an UV curable composition
having the following formulation was used:
-18- 20~J7 3
Component Part6
Aromatic Epoxy 99.7
Diethoxyacetophenone (DEAP ~b O .
~Aromatic Epoxy Oligomer System diluted with 30~
tetraethyleneglycol diacrylate available from Cargill, Inc.
b Photoinitiator (available from Upjohn Chemical)
Example 11
A three-dimensional article of the invention was
made in 6ub~tantially the same way as Example 5, except the
mold wa6 decorated with a spray paint prior to filling with
the UV curable composition. The formulation of the spray
paint was as follows:
Component Parts
Desmophen 670-~0- 15.9
De~modur N-100 6.1
Raven 1208C 2.0
Multiflow 0.5
TinUvin 770
Xylene 75.0
^Polyester Polyol available from Mobay Chemical, Inc.
bAn aliphatic isocyanate available from Mobay Chemical, Inc.
CCarbon black available from City Services, Inc.
An acrylic copolymer resin solution in Xylene 50% 601id,
6p. gr. at 25C of 0.925-0.949 available from Monsanto
Indu6trial Chemicals.
Hindered amine stabilizer available from Ciba-Geigy, Inc.
Example 12
A three-dimensional article of the invention wa6
made in a similar manner as Example 5, except that a
different carrier film was used. The carrier film included
an additional polymeric layer to supply extra rigidity and
integrity to the film during removal from the mold. The
compo~ition of the polymeric film layer was as follow6:
2G(~ 1 4
--19--
Component Parts
Geon 178~ 36.5
Pla~toleen 9776b 11 . 7
Ferro 5444' 1.~
5 Diisobutyl ketone~ 25.0
Xylene 25.0
'Polyvinyl chloride resin available from h. F. Goodrich.
bA polyester plasticizer available from Nuodex Chemical.
'A heat stabilizer with Ba, Cd, Zn, available from Ferro
Corp.
d Solvent
The mixture was sandmilled to a finene~s of grind of
6.0 on the PC scale and then applied at a wet thicknesfi of
100 micrometers onto a polyester casting liner. The solvent
was flashed off at 200F for 120 seconds, 300F for 40
seconds, and fused at 400F for 30 seconds to produce a 50
micrometer dry PVC film which was stripped from the casting
liner and subsequently laminated to the adhe~ive coated
polyester release liner described in Example 5.
Example 13
A three-dimensional article was made aceording to
Example 5, except that the mold was shaped to produce a
transparent lens and the support film used was a pigmented
film.
Example 14
A three-dimensional article that required no
post-decoration was made using a porous mold. A 50
micrometers thick colored PVC film, ScotchalTM film from 3M,
was vacuum formed into the mold prior to filling with the UV
composition as described in Example 5, and then cured in the
same manner, except no carrier film was used. The emblem was
removed from the mold easily with the colored PVC uniformly
surrounding its surface.
-20-
Example 15
~ three-dimensional article was made using the same
mold as in Example 14 and the same 50 micrometer thick
colored PVC ScotchalTn film was vacuum formed into the mold.
The film-lined mold was filled with W curable composition
having the following composition:
10 Composition Parts
I OA
AA 10
IRG--651 0 . 14
HDDA 0 . 11
A carrier film similar to that of Example 5, except
without an adhesive coatin~, was also used.
Example 16
A three-dimensional article was made in a manner
similar to Example 15, except that a colored urethane film
wa6 vacuum formed into the mold and the UV curable
composition used was the same as in Example 1. The
composition was cured in a manner similar to Exa~ple 1 to
produce a decorated, foam-like, pressure-sensitive article.
