CA2007314A1 - Three-dimensional self-adherent articles - Google Patents

Abstract

of the Invention The present invention provides a self-adherent, three-dimensional, article comprising one or more members, each member of the article including a radiation-cured pressure-sensitive adhesive body, each body having an top surface and a bonding surface, and a carrier film releasably adhered to the bonding surface of each member. The article may comprise one continuous member several interconnected members. Each member may likewise have a body comprising a single layer of radiation-curable adhesive or several layers of radiation-curable material. The simplest articles of the invention are single-layered continuous items, e.g., adhesive gaskets, having a pressure-sensitive adhesive body. 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-O", wherein each letter is considered a member.

Description

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, -~- 20073~4 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 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 .

- ZC~(`t73~4 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 ~

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 ~ .. ..

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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~

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.

Xoo73~4 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~

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 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.

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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 are 0 by weight unless otherwise specifically stated.
EXAMPLES

Example 1 A three-dimensional, self-adherent article of the 5 invention was prepared as follows:

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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 ~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.

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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 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.

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

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.

Claims (19)

FN: 42921CAN3A

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A self-adherent, three-dimensional, article comprising (a) one or more members, each member of the article including a radiation-cured pressure-sensitive adhesive body, each body having a top surface and a bonding surface, and (b) a carrier film releasably adhered to the bonding surface of each member.

2. The self-adherent, three-dimensional, article of claim 1 further comprising a decoration layer provided on said top surface.

3. The self-adherent, three-dimensional, article of claim 2 wherein said decoration layer comprises a clear, abrasion resistant polymeric layer.

4. The self-adherent, three-dimensional, article of claim 1 including an attachment means provided on said top surface, said means preserving the original placement and spacing during attachment of said article.

5. The self-adherent, three-dimensional, article of claim 1 wherein said article is in the shape of a gasket.

6. The self-adherent, three-dimensional, article of claim 5 wherein said gasket is one continuous member.

7. The self-adherent, three-dimensional, article of claim 1 comprising a multiplicity of members.

8. The self-adherent, three-dimensional, article of claim 1 wherein said pressure-sensitive adhesive is an acrylic pressure-sensitive adhesive.

9. The self-adherent, three-dimensional, article of claim 8 wherein said acrylic pressure-sensitive adhesive is a foam-like pressure-sensitive adhesive.

10. The self-adherent, three-dimensional, article of claim 8 comprising a) an acrylic copolymer of monomers containing:
(i) from about 60 to about 99 parts of an alkyl acrylate monomer, the alkyl groups of which have an average of 4 to 12 carbon atoms, and (ii) correspondingly, from about 40 parts to about 1 part of a monoethylenically unsaturated polar copolymerizable monomer, and (iii) from about 0.01 part to about 1 part of a photoinitiator.

11. The self-adherent, three-dimensional, article of claim 8 wherein said acrylic pressure-sensitive adhesive further comprises microbubbles.

12. The self-adherent, three-dimensional, article of claim 11 wherein said microbubbles are selected from the group comprising glass microbubbles, organic thin-film coated microbubbles, stained glass microbubbles, and polymeric microbubbles.

13. The self-adherent, three-dimensional, article of claim 1 further comprising a layer of decorative film.

14. The self-adherent, three-dimensional, article of claim 1 further comprising a layer of radiation-cured acrylate, said layer having no pressure-sensitive adhesive properties.

15. A method for producing the self-adherent, three-dimensional article of claim 1 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 cavities to the level of said surface with radiation-curable monomers, such that at least a portion of said monomers being radiation-curable to a pressure-sensitive adhesive state, said portion being added last;
c) coating a carrier film onto said surface and said radiation-curable monomers;
d) contacting said radiation-curable monomers into a pressure-sensitive adhesive with sufficient radiation to cure said monomers and to form a bond to the carrier film sufficient to releasably adhere said pressure-sensitive adhesive to the carrier film upon removal of the article member from the mold, and e) removing the contents of the mold to provide a self-adherent, three-dimensional article that comprises at least one member.

16. The method of claim 15 wherein at least one cavity is coated with a decorative layer prior to filling said cavity with said radiation-curable monomers.

17. The method of claim 16 wherein said decorative layer is vacuum-filled into a cavity of a porous mold to line said cavity prior to filling said cavity with the radiation-curable monomers.

18. The method of claim 15 wherein said decorative layer includes image means selected from the group consisting of pigments, dyes, reflective particles and metal flakes.

19. The method of claim 15 wherein after said article is removed from said mold, at least a portion of said article is subjected to a surface modification process selected from the group consisting of electroplating, sputtering, painting and evaporation.