Classifications

• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B45/00—Apparatus or methods for manufacturing balls
  • A63B45/02—Marking of balls
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/0004—Surface depressions or protrusions
  • A63B37/0006—Arrangement or layout of dimples
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/0004—Surface depressions or protrusions
  • A63B37/0007—Non-circular dimples
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/0004—Surface depressions or protrusions
  • A63B37/0007—Non-circular dimples
  • A63B37/0008—Elliptical
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/0004—Surface depressions or protrusions
  • A63B37/0007—Non-circular dimples
  • A63B37/0009—Polygonal
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/0004—Surface depressions or protrusions
  • A63B37/0018—Specified number of dimples
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/0022—Coatings, e.g. paint films; Markings
  • A63B37/00221—Coatings, e.g. paint films; Markings characterised by the material
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/0023—Covers
  • A63B37/0024—Materials other than ionomers or polyurethane
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/0023—Covers
  • A63B37/0024—Materials other than ionomers or polyurethane
  • A63B37/0026—Balata
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/0023—Covers
  • A63B37/0029—Physical properties
  • A63B37/0031—Hardness
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/005—Cores
  • A63B37/0051—Materials other than polybutadienes; Constructional details
  • A63B37/0052—Liquid cores
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/007—Characteristics of the ball as a whole
  • A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
  • A63B37/0073—Solid, i.e. formed of a single piece
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/007—Characteristics of the ball as a whole
  • A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
  • A63B37/0074—Two piece balls, i.e. cover and core
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/007—Characteristics of the ball as a whole
  • A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
  • A63B37/0075—Three piece balls, i.e. cover, intermediate layer and core
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/007—Characteristics of the ball as a whole
  • A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
  • A63B37/0076—Multi-piece balls, i.e. having two or more intermediate layers
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B45/00—Apparatus or methods for manufacturing balls
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J3/00—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed
  • B41J3/407—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed for marking on special material
  • B41J3/4073—Printing on three-dimensional objects not being in sheet or web form, e.g. spherical or cubic objects
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
  • B41M5/0256—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet the transferable ink pattern being obtained by means of a computer driven printer, e.g. an ink jet or laser printer, or by electrographic means
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/0054—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or film forming compositions cured by thermal means, e.g. infrared radiation, heat

Definitions

• the present invention generally relates to ink jet printing on curved surfaces, and more particularly to ink jet printing on game balls.
• Inks that are used in ink jet printing commonly are water-based resins which contain dye as a coloring agent.
• Other types of inks such as solvent-based (i.e., non-aqueous) formulations and ultraviolet (“UV”) curable inks, could be useful in ink jet printing if an appropriate viscosity and surface tension of the ink could be achieved as to be compatible with both the ink jet printing system and the game ball surface.
• UV curable inks are quick-curing inks and therefore are advantageous for in continuous-type processes in which subsequent treatment of an ink-printed substrate is involved.
• a number of UV curable inks are known.
• U.S. Patent No. 4,271 ,258 discloses a photopoiymerizable ink composition containing acrylate resin, methacrylate monomer or oligomer, acrylate monomer or oligomer, photoinitiator, and a particular type of an epoxy resin.
• U.S. Patent No. 5,391 ,685 discloses a UV curable ink having an isocyanate compound added thereto.
• U.S. Patent No. 5,391 ,685 contends that the ink disclosed therein is particularly well suited for printing on slightly adhesive plastic bases, such as those made of polyoxymethylenes and polypropylenes.
• UV curable inks are not well suited for pad printing due to difficulties in transferring the ink from a pad to a substrate.
• UV curable inks that can be pad printed have not been found suitable for use on golf balls. More specifically, when applied to a golf ball, these inks are not sufficiently durable (impact resistant) to withstand multiple blows by a golf club. It would be useful to obtain a highly durable UV curable ink which has favorable pad transfer properties when used for printing indicia on surfaces such as a curved and dimpled surface of a golf ball, and which provides an image having good durability.
• Ink jet printing is commonly used to form multicolor images on paper for use in advertising materials, computer-generated photographs, etc.
• ink jet printing There are two fundamental types of ink jet printing: continuous and drop on demand.
• U.S. Patent No. 5,623,001 describes the distinction between continuous and drop on demand ink jet printing.
• continuous ink jet printing a stream of ink drops is electrically charged and then deflected by an electrical field either directly or indirectly onto the substrate.
• the ink supply is regulated by an actuator such as a piezoelectric actuator. The pressure produced by the actuation forces a droplet through a nozzle or nozzles onto the substrate.
• An object of the invention is to provide a new and improved method of forming durable images on game balls.
• Another object of the invention is to provide a method of forming multi- color images on game balls.
• a further object of the invention is to provide a method of quickly and efficiently transferring a logo or image from a computer screen to a game ball surface.
• Another object of the invention is to provide a game ball, such as a golf ball, having a clear and durable ink image printed thereon.
• Another object of the invention is to provide a method for printing indicia on a hard surface of a game ball, the indicia comprising ink jet printable ink.
• Yet another object of the invention is to provide a method for applying smudge resistant and durable indicia to a visible surface of a game ball.
• Other objects of the invention will be in part obvious and in part pointed out more in detail hereafter.
• the present invention satisfies at least one of the foregoing objects, at least in part.
• One aspect of the invention is a method of applying indicia to a game ball, comprising: (a), obtaining an ink composition suitable for use in ink jet printing, (b) . dispensing the ink composition in the form of indicia on a transfer medium using an ink jet printer, and (c). transferring the indicia from the transfer medium to the surface of a game ball.
• the transfer medium comprises at least one member selected from the group consisting of silicone, fluoropolymer, and polypropylene.
• the transfer medium can be a low surface energy material.
• the ink composition contains a polymer resin. In another form of the invention, the ink composition contains resin components.
• the game ball can be a golf ball.
• the golf ball usually has a dimpled surface.
• An alternative method further includes: (d). forming a protective coating over the indicia on the surface of the game ball.
• the protective coating can include a polyurethane.
• the method of the invention optionally includes forming a primer coating layer on at least a portion of the surface of game ball prior to (b) .
• the primer coating layer can contain a material which promotes at least one of absorption, adhesion and clarity of the indicia. Several examples of this material are talc, amorphous silica, bentonite clay, magnesium silicate, or combinations of these materials.
• the transfer medium used in the method of the invention can be a silicone-containing medium such as a sheet or a pad.
• the ink composition is an aqueous-based formulation.
• the ink composition is a non- aqueous, or solvent-based, formulation.
• the ink comprises a UV curable resin, and the method further comprises: (e). curing the indicia after the indicia have been transferred onto the game ball surface.
• Another aspect of the invention is a method of applying indicia to a game ball, comprising: (a) , obtaining an ink composition suitable for use in ink jet printing, (b) . forming an indicia receiving layer on at least a portion of the game ball surface, the indicia receiving layer containing a material which promotes absorption, adhesion or clarity of the indicia, and (c). printing indicia on the indicia receiving layer using an ink jet printer.
• the method further includes: (d). forming a protective coating over the indicia.
• the indicia may have impact resistance sufficient to render the game ball suitable for use in competitive play.
• the indicia receiving layer optionally comprises a polyurethane.
• the material which promotes absorption, adhesion or clarity of the indicia can be talc, amorphous silica, bentonite clay, magnesium silicate, or combinations thereof.
• the indicia can be printed directly on the game ball surface using the ink jet printer.
• the indicia can be printed on a transfer medium using the ink jet printer, and can be subsequently transferred to the surface of the indicia receiving layer of the game ball.
• a drop-on-demand ink jet printer can be used. It can have a piezo crystal or thermal printhead.
• the ink comprises an UV curable resin
• the method further comprises: (e) . curing the indicia after the indicia have been printed on the indicia receiving layer.
• Another aspect of the invention is a method of applying indicia to a game ball, such as a golf ball, comprising: (a), obtaining a UV curable ink composition suitable for use in ink jet printing, (b). printing indicia on a surface of the game ball using an ink jet printer, and (c) . curing the UV ink composition.
• the method can further include: (d) . forming a protective coating over the indicia.
• Another aspect of the invention is a method of applying indicia to a game ball, such as a golf ball, comprising: (a), obtaining an ink composition suitable for use in ink jet printing, (b) . printing indicia on the surface of a game ball using a drop-on-demand ink jet printer, and (c). forming a protective coating over the indicia.
• the resolution of the indicia may be at least about 300 dots per inch ("d.p.i. ") (about 1 20 dots per cm), optionally at least about 500 d.p.i. (about 200 dots per cm), optionally at least about 600 d.p.i. (about 240 dots per cm), optionally at least about 1000 d.p.i. (about 390 dots per cm).
• Figure 1 depicts a golf ball having indicia comprising ink jet printable ink in accordance with the present invention.
• Figure 2 is a flow chart depicting two methods for applying ink jet printable indicia to a game ball by indirect transfer.
• Figure 3 is a flow chart depicting a method for applying ink jet printable indicia to a game ball using a direct printing method.
• Figure 4 schematically depicts the durability test apparatus to determine the durability of the indicia of the invention on a golf ball.
• Figure 5 is a partial side view of a portion of an insert plate in the durability test apparatus which has grooves intended to simulate a golf club face.
• Figure 6 depicts differences in pad transfer of four UV curable inks.
• Figure 7 depicts a method for applying indicia to a game ball via a logo stamping machine using ink jet printed ink.
• Figure 8 depicts a golf ball with indicia imprinted by custom stamping - by pad printing using a conventional solvent-borne pad printable ink - after being subjected to the wet barrel durability test.
• Figure 9 depicts a golf ball with an indicia imprinted by an ink jet printer using solvent-based (non-aqueous) ink after being subjected to the wet barrel durability test.
• Figure 10 depicts the adaptations made to the drive system of an ink jet printer to allow for accommodation of a game ball.
• One method of the invention for forming an image on a game ball using ink jet printing is an indirect printing technique which involves printing indicia on a transfer medium using an ink jet printer and then transferring the image from the transfer medium to the game ball surface.
• Another method of the invention is to print directly on a specially treated surface of a game ball using an ink jet printer.
• a golf ball formed according to one embodiment of the present invention is shown in Figure 1 .
• the golf ball 8 has a central core 1 0, which can be solid, liquid, gas, gel, wound, or a combination of these, and a dimpled cover 1 2 surrounding the core.
• Indicia 1 4 formed from an ink jet printable ink are formed over the cover 1 2.
• an indicia receiving layer 1 5 is positioned between the indicia 1 4 and the cover 1 2.
• a protective top coat 1 6 is formed over the indicia 14. This top coat 1 6 may cover the entire ball 8, though a partial topcoat 1 6 covering only a somewhat larger area than the indicia 14 is also contemplated.
• FIG. 2 Two methods of indirectly ink jet printing on a golf ball surface are depicted in Figure 2.
• a golf ball is primed with an ink retaining primer.
• An image is ink jet printed onto a transfer sheet, as shown at 32, or transfer pad, as shown at 34. If the image is printed onto a transfer sheet, it is then transferred to a transfer pad on a stamping machine at 34' .
• the transfer pad which is configured for printing on the surface of a golf ball, subsequently stamps the image on a golf ball surface at 36.
• the surface of the ball and the indicia optionally can be coated with a suitable top coat at 38.
• a golf ball is primed with an ink retaining primer. After the coating has been applied, an image is ink jet printed directly onto the surface of the primer at 42. After the image has been applied, the surface of the ball and the indicia optionally can be coated with a suitable top coat at 44.
• the method of the invention can be used on curved surfaces of game balls such as golf balls, basketballs, baseballs, softballs, and the like, and is particularly useful on golf balls. It can be difficult to print on the curved and dimpled surface of a golf ball because the dimples tend to distort an image printed thereon and because the plastic cover of a golf ball, which typically is made of ionomer, balata, or polyurethane, has a low surface energy. The low surface energy of the ionomer cover makes adhesion difficult and also causes ink to form into beads when placed on the cover, thereby blurring the printed image.
• One way in which the present invention overcomes the beading problem is by applying a primer coat to at least the portion of the ball surface upon which the indicia are to be printed, the primer coat containing a material which promotes absorption, adhesion, and/or clarity of the indicia.
• Suitable materials of this type to use in the primer coat of a game ball such as a golf ball include talc, amorphous silica, bentonite clay, magnesium silicate, or the like, or a combination of these.
• the material which promotes absorption, adhesion, and/or clarity of the indicia is incorporated into the cover itself.
• suitable materials of this type which can be incorporated therein include talc, amorphous silica, bentonite clay, magnesium silicate, or the like, or a combination of these.
• the ink which is used in the method of the invention is one which is suitable for use in an ink jet printer.
• the ink contains a coloring agent, a carrier, and additives.
• the coloring agent usually is a dye and/or pigment and can be fluorescent.
• the ink can contain a fluorescent material as the coloring agent instead of or in addition to an ordinary dye.
• the ink can contain a selective absorber of infrared or microwave radiation.
• the carrier or vehicle for the coloring agent may be water or an organic solvent.
• the physical characteristics of the substrate and the other ink components determine the type and quantity of carrier to be used. Examples of useful additives include materials to control pH, viscosity, light fade and surface tension.
• the ink can contain a polymer resin or resin components.
• polymer resins or resin components which are used in conventional ink jet printing inks include polyurethanes, polyesters, polyketones and polyacrylates.
• the resin components could be, for example, oligomers.
• the ink composition and the composition of the ball cover or primer layer to which the indicia are to be applied may be selected such that the surface tension of the ink is appropriately related to the surface properties of the substrate to which it is to be adhered.
• Inks contemplated to be suitable for ink jet printing typically have a viscosity of from about 1 to about 20 cps measured at the temperature of application.
• UV curable inks can be used in accordance with the method of the present invention.
• Most commercially available UV inks are not suitable for ink jet printing due to the high concentration and size of the pigments and fillers in these formulations.
• a UV ink suitable for an ink jet printer should incorporate very finely divided pigments (about 0.1 micron or alternatively less than 1 00 Angstroms), dissolved dyes, or combinations of dyes and finely divided pigments. Flow additives, surface tension modifiers, extra solvent, etc. may be added to the ink formula to improve ink jet printability and prevent clogging of the ink jet printer. UV curable inks are described below in further detail in a separate section of this document.
• a primer coating layer is applied to a game ball cover
• the coating typically is a solvent-borne or water-borne polyurethane material.
• suitable coatings are described in detail in commonly assigned U.S. Patent Nos. 5,409,233, 5,459,220 and 5,494,291 , the contents of which are incorporated herein by reference.
• top coat it is useful for a top coat to be applied over the indicia to protect the indicia unless the indicia have sufficient adhesion to the surface to which they are applied, e.g., the cover or a primer layer, to render the use of a top coat unnecessary.
• the adhesion between the ink and the top coat and/or substrate is contemplated to be sufficiently strong so that the indicia remain substantially intact when the game ball is used. Standards for image retention vary depending upon the intended use of the game ball and the degree and frequency of impact that the image is required to withstand.
• the ink durability desirably is sufficient that after the ball is subjected to the wet barrel durability test procedure described below, at least about 50% of the surface area of the original image remains, optionally at least about 70%, optionally at least about 80% . Excellent durability results when more than about 85 % of the image remains.
• the indicia are printed onto a transfer medium using an ink jet printer and are subsequently transferred to the game ball surface.
• a suitable transfer medium is one which has a surface that allows for good clarity of the indicia printed thereon while providing for transfer of the image onto the game ball surface.
• One contemplated transfer medium is a silicone pad. If necessary, an absorptive filler can be added to the silicone pad to promote flow-out of the ink, and to prevent beading on the surface of the silicone pad. Additionally or alternatively, the surface of the pad can be roughened to an extent necessary to achieve the desired surface energy.
• a pad rather than a flat sheet for the transfer substrate may facilitate the application of ink inside the dimples.
• One contemplated type of silicone pad is that which is used in conventional golf ball pad printing.
• ink jet printers Two types of ink jet printers specifically contemplated for printing on game balls are continuous ink jet printers and drop on demand ink jet printers.
• a continuous ink jet printer a stream of ink drops is electrically charged and then deflected by an electronic field either directly or indirectly onto the substrate.
• the ink supply is regulated by an actuator such as a piezoelectric actuator. The pressure produced by the actuation forces a droplet through a nozzle or nozzles onto the substrate.
• the UV curable ink of the present invention can be used for printing indicia on golf balls, softballs, baseballs, other game balls, as well as other sporting goods including, but not limited to, softball and baseball bats, tennis and racquetball rackets, and golf clubs.
• the ink also can be applied to a variety of materials including, but not limited to, ionomers, polybutadiene, composite materials, metals, etc.
• the ink comprises a UV curable resin, a coloring agent, such as a pigment or a dye, one or more photoinitiators, and possibly a solvent.
• the ink may also include aluminum trihydroxide.
• a thinning agent that includes a monomer and/or a solvent can be added.
• a wetting agent also can be included.
• the UV curable resin may comprise an oligomer.
• the oligomer include one or more epoxies, acrylics, acrylate urethanes, elastomeric acrylates, unsaturated polyesters, and polyethers.
• suitable oligomers include methacrylates such as bisphenol A ethoxylate dimethacrylate and acrylated epoxies. Blends of different oligomers can be used.
• the oligomer can provide the ink with characteristics of flexibility and impact resistance that are sufficient to withstand the conditions to which the substrate is to be subjected.
• the oligomer may impart to the ink more flexibility than is inherent in the underlying substrate, which is contemplated to provide good durability.
• the ink desirably is not so highly cross-linked that adhesion of the top coat to the ink is substantially hindered.
• the uncured ink can comprise about 1 0 - 90 wt % oligomer, optionally about 20 - 80 wt % oligomer, optionally about 50 - 70 wt % oligomer.
• the coloring agent can be any type of pigment, dye or the like which will withstand UV treatment, i.e., which is not UV labile. Furthermore, the coloring agent is contemplated to permit sufficient passage of UV light through the ink, by any combination of transmission, reflection, or refraction mechanisms, to initiate photocrosslinking. Liquids or powders can be used.
• An ink is a powder which is dispersed in a liquid monomer.
• Carbon black and iron oxide black are non-limiting examples of suitable pigments for making black inks.
• Red lake and quinacrydones are non-limiting examples of suitable pigments for making red inks.
• Blends of different pigments and/or dyes can be used.
• the uncured ink can contain about 2 - 60 wt % colorant, alternatively about 5 - 30 wt % colorant, alternatively about 5 - 1 0 wt % colorant.
• the photoinitiator is selected to respond to the wavelength of UV radiation to be used for photoinitiation. It is also important to consider the color of the ink in selecting the photoinitiator because, as indicated above, it is necessary for the UV light to penetrate the ink composition to initiate the cure.
• Photoinitiators to be used in conjunction with black pigment include sulfur-type photoinitiators such as isopropyl thioxanthone, and benzophenone and its derivatives including acetophenone types and thioxanthones.
• Photoactivators can be used in conjunction with one or more photoinitiators.
• suitable photoactivators are amine-type photoactivators such as ethyl 4-dimethylamino benzoate.
• the uncured ink may contain about 0.3 - 5 wt % photoinitiator, alternatively about 1 - 4 wt % photoinitiator, alternatively about 3 - 4 wt % photoinitiator. Blends of different photoinitiators, or photoinitiators and photoactivators can be used.
• a thinning agent can be added to lower the viscosity of the uncured ink composition or to contribute to impact resistance or flexibility.
• a monomer when used as a thinning agent, it optionally can be a photopoiymerizable monomer that forms a polymeric structure upon irradiation. In contrast, when solvents are used as thinning agents, they evaporate during curing.
• the monomer can be a monofunctional, difunctional or multifunctional acrylate.
• suitable monomers include 1 ,6 hexanediol diacrylate, butanediol diacrylate, trimethylol propane diacrylate, tripropylene glycol diacrylate and tetraethylene glycol diacrylate.
• the uncured ink may contain about 1 0 - 70 wt % monomer, alternatively about 1 0 - 60 wt % monomer, alternatively about 1 0 - 55 wt % monomer.
• the combination of monomer plus oligomer may constitute about 45 - 80 wt % of the uncured ink, optionally about 50 - 80 wt %, optionally about 60 - 80 wt % of the ink.
• Non UV curable quick-drying resins which help in ink transfer from the pad to the ball can be added.
• Non-limiting examples of such resins are vinyl resins, nitrocellulose, acrylic resins, and other quick-drying, film-forming resins.
• One contemplated resin is an acrylic-OH functional resin made by McWorther, Inc. of Carpentersville, IL, sold as Resin 975.
• McWorther, Inc. of Carpentersville, IL, sold as Resin 975.
• Resin 975 Typically, if such resins are used, they are added in an amount up to about 30 parts by weight based upon 100 total parts by weight of uncured ink composition.
• a solvent When a solvent is used in the UV curable ink, it typically is a liquid with a fast to moderate evaporation rate which, upon partial evaporation causes the ink to be tacky, and thereby promotes transfer onto and off an ink pad.
• a solvent also can be the medium in which a photoinitiator is dissolved.
• suitable solvents include aromatic solvents such as toluene, xylene, and ester types such as butyl acetate.
• the uncured ink may include about 1 - 30 wt % solvent, optionally about 5 - 20 wt % solvent, optionally about 8 - 1 0 wt % solvent.
• wetting agents can be added to prevent beading of the ink upon application to the golf ball. Suitable wetting agents include, but are not limited to, silicone surfactants and fluorocarbon surfactants.
• the uncured ink may include about 0 - 2 wt % wetting agent.
• Other additives that do not adversely affect the pad transfer and impact resistance of the ink also can be incorporated into the ink composition.
• extender pigments such as talc, barium sulfate and the like can be added to improve transferability.
• the particle size of the extender pigments should be small enough to facilitate passage through the orifices of the printer. This would include finely divided (about less than 0.1 micron or alternatively less than 100 Angstroms) silicas, clays, or talcs, or combinations of these. Typically, if such materials are used, they constitute about 1 0 - 40 wt %, alternatively 20 - 30 wt %, of the uncured ink formulation.
• ATH When ATH is used in a UV curable game ball ink, it generally is included in an amount of 1 0 - 50 wt % based upon the total weight of the ink prior to curing. ATH may be employed in an amount of 1 0 - 32 wt %, alternatively 20 - 30 wt %. It is believed that ATH loadings up to at least 50 wt % based upon the weight of (uncured) ink may be useful for providing an overall balance of properties. Greater quantities of ATH can be used when a low cost ink is desired and durability requirements are not stringent. Lower quantities of ATH are useful when higher durability is needed. The ATH can be used in a quantity appropriate to impart to the ink a balance of properties such as pad transfer and durability of the ink.
• the ratio of ATH to talc, etc. may be about 1 : 1 .
• the use of ATH does not impede the curing process.
• the surface tension of the ink affects the wetability of the substrate.
• the surface tension of the ink desirably is not substantially higher than the surface tension of the substrate upon which it is printed.
• the viscosity of the ink is one factor that will affect the thickness of the indicia on the cover. If the indicia are too thick, the UV radiation may not penetrate the indicia and complete curing may become difficult.
• the indicia are too thin, the durability of the ink layer may be insufficient for conditions of play.
• the indicia have thickness of less than about 100 microns, optionally about 1 0 - 40 microns, optionally about 1 3 - 30 microns, optionally about 20 - 25 microns.
• the cured ink is contemplated to be sufficiently flexible to exhibit good impact resistance. It is advantageous for the top coat which is applied over the ink to react with the ink to hold the ink in place, or to have adhesion by hydrogen bonding and/or van der Waals forces.
• the ink can be used in conjunction with a two-component polyurethane top coat, such as a top coat based on polyester or acrylic polyols and aliphatic isocyanates such as hexamethylene diisocyanate or isophorone diisocyanate trimers.
• a two-component polyurethane top coat such as a top coat based on polyester or acrylic polyols and aliphatic isocyanates such as hexamethylene diisocyanate or isophorone diisocyanate trimers.
• a UV curable ink formulation of the invention which is used for marking golf balls can be prepared and used in the following way.
• the photoinitiator is dissolved in the thinning agent, which is then mixed with an oligomer, and a pigment.
• the mixture is placed in a dispenser for use in direct or indirect ink jet printing. A primed but unfinished golf ball is obtained.
• the ball includes, for example, a core, and a durable cover having a dimpled surface.
• the core and cover can be formed in one piece.
• Indicia formed from the UV curable ink are ink jet printed on to the golf ball cover either directly or indirectly by use of a transfer medium.
• the unfinished golf ball is then subjected to UV treatment under conditions sufficient to at least commence curing of the ink. After photoinitiation, curing of the ink is substantially complete within a time period of between less than one second and a few seconds.
• a top coat layer is placed over the indicia.
• the top coat is optionally applied at least partially, and optionally completely, after the ink is cured.
• the top coat layer assists in keeping the indicia on the golf ball surface, as indicated above, and therefore the adhesion of indicia to the golf ball does not need to be as strong as will be required if the ink constitutes the outer layer of the ball.
• the top coat typically has a thickness of 1 0 - 40 microns.
• the conditions of UV exposure which are appropriate to cure the ink can be ascertained by one having ordinary skill in the art. For example, it has been found that when a golf ball passes through a UV treatment apparatus at a rate of about 1 0 ft. /min.
• the indicia may be exposed to UV radiation for no more than a few seconds, optionally no more than about 1 second, optionally no more than about 0.7 seconds. Higher and lower UV lamp intensities, distances, and exposure times may be used as long as the cured ink meets the applicable durability requirements. Excess UV exposure is avoided to prevent degradation of the substrate.
• the ink can be UV cured prior to application of any top coat.
• the pad to be used for transfer of the UV ink according to one embodiment of the invention can contain silicone. This type of pad has good elasticity, durability and softness and an appropriate surface tension. Other types of pads also can be used.
• the ink can be applied on a non-UV-labile surface of a game ball. According to the invention, it is generally not necessary to pretreat the surface prior to application of the ink. If it is desired to apply the UV curable ink on an extremely smooth surface upon which transfer is poor, the portion of the surface to be stamped can be chemically or physically etched or abraded in order to provide an ink-receptive surface.
• the ink of the invention has a Sward hardness (ASTM-D 21 34-66) after curing of about no more than 55, alternatively about no more than 40, alternatively about no more than about 20.
• the UV curable ink of the invention provides for durability sufficient to meet stringent durability standards required for commercial grade golf balls.
• the durability of the ink can be determined by testing stamped golf balls in a variety of ways, including using the wet barrel durability test procedure.
• Durability according to the wet barrel durability test procedure is determined by firing a golf ball at 1 35 ft/sec (at 72°F) (41 m/s (at 22°Q) into 5- sided steel pentagonal container, the walls of which are steel plates.
• the container 1 1 0, which is shown schematically in Figure 4, has a 1 9 ⁇ h inch (49.5 cm) long insert plate 1 12 mounted therein, the central portion 1 14 of which has horizontally extending square grooves on it which are intended to simulate a square grooved face of a golf club.
• the grooves which are shown in an exaggerated form in Figure 5, have a width 1 30 of 0.033 inches (0.084 cm), a depth 1 32 of 0.1 00 inches (0.25 cm), and are spaced apart from one another by land areas 1 34 having a width of 0.1 30 inches (0.330 cm) .
• the five walls 1 1 6 of the pentagonal container each have a length of 1 4 1 / ⁇ inches (36.8 cm) .
• the inlet wall is vertical and the insert plate is mounted such that it inclines upward 30° relative to a horizontal plane away from opening
• the ball travels 1 5 1 / 2 - 1 5 % inches (39.4 - 40 cm) horizontally from its point of entry into the container 1 1 0 until it hits the square- grooved central portion 1 1 4 of insert plate 1 1 2.
• the angle between the line of trajectory of the ball and the insert plate 1 1 2 is 30°.
• the balls are subjected to 70 or more blows (firings) and are inspected at regular intervals for breakage (i.e., any signs of cover cracking or delamination). If a microcrack forms in a ball, its speed will change and the operator is alerted. The operator then visually inspects the ball. If the microcrack cannot yet be observed, the ball is returned to the test until a crack can be visually detected. The balls are then examined for adhesion of the ink.
• a golf ball printing ink was prepared which contains: 5 parts by weight 1 ,6 hexanediol diacrylate (sold by Sartomer, Exton, PA), 1 7.5 parts by weight black pigment paste in diacrylate monomer, sold as Carbon Black UV Dispersion 99B41 5 (Penn Color, Doylestown, PA),
• the photoinitiator and photoactivator were dissolved in the xylene/butyl acetate solvent blend.
• the ink was pad printed using a silicone pad on unprimed, dimpled ionomeric covers of several dozen golf balls.
• the ink had a viscosity of about 27,500 centipoise ("cps") at the time of application.
• the balls containing the stamped indicia were passed through a Uvex UV treatment apparatus Lab Model #1 4201 at a rate of 1 0 feet/min. (3 m/min.), using a lamp intensity of 235 watts/in 2 (36.4 watts/cm 2) and wavelength range of 200 - 400 nm with the indicia being located about 1 % inches (4.4 cm) from the UV light source.
• the ink was cured in less than about 1 second and had a Sward hardness of about 1 4 after curing was complete.
• the golf balls were then coated with a solvent-borne polyurethane top coat formed from a polyester type hexamethylene diisocyanate.
• the adhesions of the indicia on the balls were tested for durability according to the wet barrel durability test procedure described above. After wet barrel durability testing, the balls were examined and it was found that no more than about 20% of the surface area of the original ink logo was removed.
• Example 1 The procedure of Example 1 was repeated with excepting that the ink formulation that was used contained:
• EDB ethyl 4-dimethylamino benzoate
• the ink had a viscosity of about 25,000 cps.
• the ink was cured in about 1 second and produced a film having a Sward hardness of about 1 2.
• the balls were subjected to the wet barrel durability test procedure. After the wet barrel durability testing, it was found that no more than about 20% of the ink logo was removed.
• Example 3 The procedure of Example 1 was repeated excepting that the CN965 oligomer was replaced by a difunctional oligomer sold as Ebecryl 8402 (UCB RadCure, Inc., Smyrna, GA) .
• the ink had a viscosity of about 1 8,000 cps.
• the ink was cured in about 1 second and produced a film having a Sward hardness of about 14.
• the ink was found to be as nearly as durable as that of Examples 1 and 2.
• EXAMPLE 4 The procedure of Example 1 was repeated excepting that the CN965 oligomer was replaced by a difunctional oligomer sold as Ebecryl 8402 (UCB RadCure, Inc., Smyrna, GA) .
• the ink had a viscosity of about 1 8,000 cps.
• the ink was cured in about 1 second and produced a film having a Sward hardness of about 14.
• the ink was found to be
• Example 1 The procedure of Example 1 was repeated excepting that the ink formulation that was used contained: 7.3 parts by weight 1 ,6 hexanediol diacrylate (sold by Sartomer, Exton,
• isopropyl thioxanthone C 16 H 14 OS, a sulfur-type photoinitiator (ITX, distributed by Aceto Chemical, Lake Success, NY), 1 part by weight ethyl 4-dimethylamino benzoate (EDB), 1 1 .4 parts by weight talc (Vantalc 6H, Vanderbilt, Norwalk, CT), 22.9 parts by weight barium sulfate ( 1 06 Low-Micron White Barytles,
• the ink was applied directly to ionomeric covers of golf balls, and also over ionomeric covers to which a water-borne polyurethane primer layer had been applied prior to application of the ink.
• the ink was cured in about 1 second and produced a film having a Sward hardness of about 14.
• the balls were top coated and subjected to the wet barrel durability test procedure. After the wet barrel durability testing, it was found that no more than about 20% of the ink logo was removed.
• Example 1 The procedure of Example 1 was repeated with the exception that a commercially available UV curable ink was used, namely Blk #700801 (Trans Tech, Carol Stream, IL).
• the ink had a viscosity of about 6,000 cps.
• the ink was cured in about 1 second and produced a film having a Sward hardness of about 26. After the wet barrel durability test only the outline of the logo remained. Most of the ink in the dimples and on the land areas had been removed. Intercoat adhesion between the ink and top coat was poor.
• Example 2 The procedure of Example 1 was repeated on several golf balls with the exception that a commercially available UV curable ink was used, namely L-526- 1 63-B (Qure Tech, Seabrook, NH). The ink had a viscosity of about 28,500 cps. The ink was cured in about 1 second and produced a film having a Sward hardness of about 20. As a result of the wet barrel durability test, the ink on at least about 60% of the surface area of the logo had been removed. It is believed that the ink was too brittle to withstand the conditions of the wet barrel durability test.
• a commercially available UV curable ink was used, namely L-526- 1 63-B (Qure Tech, Seabrook, NH).
• the ink had a viscosity of about 28,500 cps.
• the ink was cured in about 1 second and produced a film having a Sward hardness of about 20.
• Acetate and aromatic hydrocarbon solvent blend 2 1 89.2 ATH 3 270.3
• McWorther Resin 975 McWorther, Inc., Carpentersville, IL
• 6 Summit Ink Reducer, Summit PT #910527 (Summit Screen Inks, No. Kansas City, MO)
• a mixture based upon 43.4 parts by weight butyl acetate, 28.3 parts by weight xylene and 28.3 parts by weight propylene glycol monomethyl ether acetate can be used.
• 3 ATH SpaceRite S-3 (ALCOA Industries, Bauxite, AR) .
• the ATH-containing formulation 1 was then used to form a golf ball ink which contained:
• TMPTA trimethylolpropane triacrylate
• ATH SpaceRite S-3, ALCOA Industries, Bauxite, AR
• All ingredients were mixed and dispersed on high speed mixing equipment.
• the ink was pad printed using a silicone pad on unprimed, dimpled ionomeric covers of several dozen golf balls.
• the balls containing the stamped indicia were passed through a Uvex UV lamp at a rate of 10 feet/min. (3 m/min.), using a lamp intensity of 235 watts/in. 2 (36.4 watts/cm 2 ) and a wavelength range of 200 - 400 nm with the indicia being located about 1 % inches (4.4 cm) from the UV light source.
• the ink was cured in less than one second.
• the golf balls were then coated with a two component polyester/aliphatic polyisocyanate clear coat.
• Control A The printability, jetness, detail image, pad release, and durability of the ink was evaluated and was compared with three sets of control inks, designated as Control A, Control B, and Control C.
• the formulations of the Control A and Control B inks are shown below: Control A parts by wt.
• Barium sulfate 5 1 2.89 Black dispersion in oligomer/monomer 6 6.01
• Epoxy-acrylate oligomer 1 1 9.24
• Acrylic -OH functional resin 2 27.70
• Polyester-acrylate oligomer 7 1 5.38 Isopropyl thioxanthone 8 0.77
• Ebecryl 3700 (Rad-Cure, Smyrna, GA) .
• McWorther Resin 975 McWorther, Inc., Carpentersville, IL
• Summit Ink Reducer Pt# 910527, Summit Screen Inks, No. Kansas City, MO.
• Van Talc 6H Van Talc 6H (Vanderbilt, Norwalk, CT). Barytes #22 (Whittaker, Clark & Daniels, Inc., South Plainfield, NJ).
• ICU 386 (Industrial Color Inc., Joliette, IL).
• Ebecryl 80 (Rad-Cure, Smyrna, GA).
• ITX distributed by Aceto Chemical, Lake Success, NY
• EDB (distributed by Aceto Chemical, Lake Success, NY).
• Control C was Trans Tech ink # 2P37-2 (Trans Tech, Carol Stream, IL). The ratings for the various ink formulations are shown below:
• the ink of Example 5 had a oligomer/monomer content of 22.608 wt %, an acrylic resin content of 21 .508 wt %, a black pigment content of 3.08 wt %, an ATH pigment content of 31 .63 wt %, a solvent content of 20.008 wt % and an initiator content of 1 .62 wt %.
• the density of the ink was 1 0.68 lbs. /gal. (1 .28 kg/L), the total nonvolatiles content was 80%, and the volatile organic compounds constituted 2.14 IbsJgal. (0.256 kg/L).
• the viscosity of the ink was
• Figure 6 shows a silicone pad after 1 2 golf balls have been stamped with a particular type of ink.
• Figure 6A (1 50) shows the stamp after stamping with the ink of Control A.
• Figure 6B (1 52) shows the silicone pad after stamping with the ink of Control B.
• Figure 6C (1 54) shows the pad after stamping with the ink of Example 5.
• Figure 6D ( 1 55) shows the pad after stamping with Control C.
• the best transfer i.e. the least quantity of ink remaining on the stamp, resulted from the use of the ink of Example 5.
• ATH-containing formulation 2 shown below, was prepared:
• McWorther Resin 975 (McWorther, Inc., Carpentersville, IL) .
• ICU 386 Industrial Color Inc., Joliet, IL.
• Aromatic 100 or HiSol 53 (Ashland Chemicals), 3.08 parts by weight cyclohexanone (Ashland Chemicals), 0.50 parts by weight isopropyl thioxanthone, C l 6 H 14 OS, a sulfur-type photoinitiator (ITX, distributed by Aceto Chemical, Lake Success, NY), 1 part by weight ethyl 4-dimethylamino benzoate, C l 1 H 15 NO 2 , an amine- type photoactivator (EDB, distributed by Aceto Chemical, Lake Success, NY),
• UV curable resin aliphatic urethane triacrylate
• TMPTA trimethylolpropane triacrylate
• the total parts by weight were 1 00. All ingredients were mixed and dispersed using high speed mixing equipment.
• the ink was pad printed using a silicone pad on unprimed, dimpled ionomeric covers of a large number of golf balls.
• the golf balls containing stamped indicia were passed through a Uvex UV lamp at a rate of 1 0 ft/min. (3 m/min.), using a lamp intensity of 235 watts/in. 2 (36.4 watts/cm 2 ) and a wavelength range of 200 - 400 nm with the indicia being located at about 1 % inches (4.4 cm) from the UV light source.
• the ink was cured in less than one second.
• the golf balls were then coated with a two-component polyester/aliphatic polyisocyanate clear coat and were subjected to the wet barrel durability test procedure. After the wet barrel durability testing, it was found that no more than about 20% of the ink logo was removed.
• Example 6 The procedure of Example 6 was repeated with the exception that the quantity of ATH was reduced to 1 9.20 parts by weight, and the ATH-containing formulation (ATH-containing formulation 2) included only 0.22 parts by weight of black dispersion in oligomer/monomer (CU 386, Industrial Color Inc., Joliet, IL), and further contained 8.1 6 parts of a first red dispersion in oligomer/monomer (ICU Red Lake C, Industrial Color Inc., Joliet, IL) and 2.62 parts of a second red dispersion in oligomer/monomer (ICU Lithol 388 Red, Industrial Color Inc., Joliet, IL). All ingredients were mixed and dispersed on high speed mixing equipment. The total parts by weight were 1 00.
• ATH-containing formulation 3 shown below, was prepared:
• McWorther Resin 975 (McWorther, Inc. , Carpentersville, IL) .
• TMPTA trimethylolpropane triacrylate
• the total parts by weight were 99.99. To provide for optimum printing, the viscosity of the ink was reduced to
• the ink was printed on a number of golf balls.
• the golf balls were then coated with a two-component polyester/aliphatic polyisocyanate clear coat and were subjected to the wet barrel durability test procedure. After the wet barrel durability testing, it was found that no more than about 20% of the ink logo was removed. The balls which were initially printed had a crisp image. After time, some ghosting appeared.
• ATH-containing formulation 4 as shown below, was prepared:
• McWorther Resin 975 (McWorther, Inc., Carpentersville, IL) .
• ICU Red Lake C (Industrial Color Inc., Joliet, IL).
• ICU Lithol Rubine 388 (Industrial Color Inc., Joliet, IL) .
• ICU 386 (Industrial Color Inc., Joliet, IL). After mixing, the following materials were added:
• the ink was printed on a number of golf balls.
• the image was very dark.
• the golf balls were then coated with a two-component polyester/aliphatic polyisocyanate clear coat and were subjected to the wet barrel durability test procedure. After the wet barrel durability testing, it was found that no more than about 20% of the ink logo was removed.
• an ink jet printer (Epson Stylus Color 640) 200 was used to print an image from a JPEG computer file onto a polysilicone coated sheet of paper (Dow Corning HS2) 202. This resulted in an ink jet logo 204 on the silicone coated paper 202.
• An ionomer covered golf ball 206 was obtained which had been coated with an ink retaining primer coat formed from 1 00.00 parts by weight of Witcobond 235 (Witco), which is a water borne polyurethane primer, and 7.0 parts by weight of amorphous silica (Hi-Sil 91 5, PPG, Pittsburgh, PA) . After the primer coating had dried, the image 204 on the silicone paper 202 was transferred to the surface of the golf ball 206 using a golf ball logo stamping machine 208.
• the ball logo stamping machine 208 has a horizontal arm 21 0 to which is attached a plunger 21 2 carrying a transfer pad 21 4.
• the silicone coated paper 202 holding the logo 204 was placed underneath the transfer pad 214.
• the plunger 21 2 advanced the transfer pad 21 4 against the logo 204, lifting the logo image 204 onto the transfer pad 214.
• the transfer pad 214 retracted, moving along the arm 210 to a second position beneath which a golf ball 206 was held. At this second position, the plunger 21 2 advanced the transfer pad 214 against the primed golf ball 206, stamping the newly imprinted image onto the ball 206.
• the primed golf ball 206 with the stamped image was then coated with a top coat 21 6 of the following formulation:
• UV stabilizer Tinavin 292, CibaGeigy 1 .0
• the ball was durability tested using the wet barrel test described above. About 80% of the ink logo remained. This process produced a multi-color logo with good distinction, recognition and durability on a dimpled and curved surface of a golf ball.
• An ionomer covered golf ball was obtained which had been coated with an ink retaining primer coat formed from 1 00.00 parts by weight of Witcobond 235 (CK Witco, Stamford, CT), which is a water borne polyurethane primer, 1 0.0 parts of talc (magnesium silicate), 1 .0 part by weight of amorphous silica (Hi-Sil 532EP, PPG, Pittsburgh, PA), and 5 parts by weight of polyaziridine (Zeneca Resus, Wilmington, MA).
• Witcobond 235 CK Witco, Stamford, CT
• talc magnesium silicate
• Hi-Sil 532EP PPG, Pittsburgh, PA
• polyaziridine Zeneca Resus, Wilmington, MA
• a solvent-based printing ink of the following formulation was prepared:
• BYK 346 a polyether modified polydimethyl siloxane, sold by BYK Chemie, Wallingford, Connecticut.
• the above ink formulation was ink jet printed directly onto the primed golf ball using an Epson Stylus Color 640 ink jet printer, a drop on demand piezoelectric printer.
• the drive system of the ink jet printer was physically adapted to allow for printing directly on to the golf ball as shown in Figure 10.
• the adaptation was constructed in such a manner that the game ball had the identical indexing or rotational speed as paper that is driven through the printer.
• a rotational system 305 consisting of a series of shafts connected by belts and pulleys rotated the main drive shaft 300.
• the rotational system 305 advanced the main drive shaft 300 at such a rate that the game ball 31 0 advanced at a rate identical to the index speed of a piece of paper.
• the ink jet printhead 320 advanced horizontally across the game ball 31 0, printing the desired image onto the game ball 31 0 in a series of passes.
• the ink had a viscosity of about 6 cps at the time of application.
• the resulting golf ball had a clean, durable and opaque image found thereon.
• the golf ball with the image thereon was then coated with a solvent-borne two-part aliphatic polyurethane top coat which is described in U.S. Patent No. 5,459,220.
• the opacity, clarity and color of the image did not change upon application of the top coat.
• the ball was durability tested using the wet barrel test, breaking after 1 97 blows. The results after durability testing are shown in Figure 9. After testing, the balls were examined and it was found that about 80% of the ink logo remained.
• FIG. 8 depicts a golf ball that has been subjected to wet barrel testing after an indicia was imprinted via custom stamping. The ball broke after 1 86 blows. After wet barrel durability testing, far less of the ink logo remained on the custom stamped ball in Figure 8 than the ink jet printed ball in Figure 9.
• Example 12 The procedure of Example 1 1 was repeated with the exception that a water-based printing ink of the following formulation was substituted: 50.0 parts by weight water,
• BYK 346 a polyether modified polydimethyl siloxane, sold by BYK Chemie, Wallingford, Connecticut.
• the resulting golf ball had a clear and durable image formed thereon. While the opacity of this image was slightly less than that of the image on the ball of Example 1 1 , the opacity could be improved by using a larger quantity of dye or by increasing the mixing intensity of the formula during preparation in order to better disperse the dye. COMPARATIVE EXAMPLE 3
• Example 1 1 The procedure of Example 1 1 was repeated excepting that a commercially available glycol-based ink formulation, found in conventional ink jet ink cartridges, namely Epson Ink Jet Printer ink formulation found in ink cartridges for use with the Epson Stylus Color 640 ink jet printer, was used.
• the ink had a viscosity of about 5 or 6 cps. This process did not produce an acceptable image.
• a golf ball printing ink was prepared which contained Formula C.
• Formulas A and B were first prepared:
• Polyester-acrylate oligomer 2 30.0
• Ebecryl 3700 (Rad-Cure, Smyrna, GA).
• the ingredients of Formula C were mixed and ink jet printed directly onto the golf ball primed with the primer of Example 1 1 and using the ink jet printer of Example 1 1 .
• the drive system of the ink jet printer, a piezoelectric printer, was physically adapted to allow for printing directly on to the golf ball.
• the balls containing the stamped indicia were passed through a Uvex UV treatment apparatus at a rate of about 1 0 feet/min. (3 m/min.), using a lamp intensity of about 235 watts/in 2 (36.4 watts/cm 2) and wavelength range of about 200 - 400 nm with the indicia being located about 1 % inches (4.4 cm) from the UV light source.
• the indicia on the ball were distinct and durable.
• a golf ball printing ink which contains:
• Acrylic -OH functional resin 2 30.0 Acetate and aromatic hydrocarbon solvent blend 3 15.0 Black Dye 4 1 5.0 Polyester-acrylate oligomer 5 15.0
• Ebecryl 3700 (Rad-Cure, Smyrna, GA).
• McWorther Resin 975 (McWorther, Inc., Carpentersville, IL).
• the ingredients are mixed.
• the ink is sufficiently diluted with solvent, e.g., butyl acetate, to constitute a viscosity of between about 1 to 20 cps, optionally between about 5 to 1 0 cps, optionally between about 5 to 6 cps.
• solvent e.g., butyl acetate
• the above ink formulation is ink jet printed directly onto the primed golf ball using the ink jet printer of Example 1 1 .
• the drive system of the ink jet printer, a piezoelectric printer, is physically adapted to allow for printing directly on to the golf ball.
• the balls containing the stamped indicia are passed through a Uvex UV treatment apparatus at a rate of about 1 0 feet/min. (3 m/min.), using a lamp intensity of about 235 watts/in 2 (36.4 watts/cm 2 ) and wavelength range of about 200 - 400 nm with the indicia being lcoated about 1 % inches (4.4 cm) from the UV light source.
• the golf balls are then coated with a solvent-borne polyurethane top coat formed from a polyester type hexamethylene diisocyanate.
• Example 1 2 The procedure of Example 1 2 is repeated excepting that a Hewlett Packard 693C bubble jet printer, a drop on demand printer, is substituted for the Epson Stylus Color 640 ink jet printer.
• Example 1 2 The procedure of Example 1 2 is repeated excepting that 1 0 parts by weight of black pigment, Microlith Black C-WA (CIBA Specialty Chemicals Corp.
• the pH of the composition is increased to at least 8.5 by adding an amine such as triethanol amine.

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• 1999
  • 1999-10-06 JP JP2000575066A patent/JP2002526866A/ja active Pending
  • 1999-10-06 JP JP2000573556A patent/JP2002526182A/ja active Pending
  • 1999-10-06 WO PCT/US1999/023296 patent/WO2000021014A2/en not_active Ceased
  • 1999-10-06 AU AU11019/00A patent/AU760798B2/en not_active Ceased
  • 1999-10-06 CA CA002344404A patent/CA2344404A1/en not_active Abandoned
  • 1999-10-06 AU AU64171/99A patent/AU753386B2/en not_active Ceased
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  • 1999-10-06 WO PCT/US1999/023150 patent/WO2000020219A1/en not_active Ceased
  • 1999-10-06 CA CA002346391A patent/CA2346391A1/en not_active Abandoned
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