JP2002526182A - Method of forming identification mark on game ball surface using ink jet printer - Google Patents

Abstract

(57) Abstract: The method of the present invention comprises: (a) obtaining an ink composition containing a colorant and a resin, which is suitable for use in inkjet printing; and (b) using an inkjet printer to transfer a transfer medium. Delivering the ink composition in the form of an identification mark thereon, and (c) transferring the identification mark from a transfer medium to a surface of the game ball. The method of forming an identification mark on a game ball includes (a) obtaining an ink composition suitable for use in inkjet printing, and (b) forming an identification mark receiving layer on at least a part of the surface of the game ball. Wherein the identification mark receiving layer contains a substance that enhances at least one of the absorption, adhesion and clarity of the identification mark, and (c) printing the identification mark on the identification mark receiving layer using an inkjet printer. Including.

Description

DETAILED DESCRIPTION OF THE INVENTION

RELATED APPLICATIONS [0001] This application is a pending application Ser. No. 09 / 166,970, filed Oct. 6, 1998.
Which is a continuation-in-part of US patent application Ser. No. 08 / 877,938 (filed Jun. 18, 1997), which is now US Pat. No. 5,885,173.
Is a continuation of U.S. Patent Application 08 / 529,361, now U.S. Patent 5,770,325.
It is a wish. US patent application Ser. No. 09 / 166,970 is also a continuation-in-part of US patent application Ser. No. 08 / 753,704, filed Nov. 27, 1996, now US Pat. No. 5,827,134. Each of the aforementioned applications and patents is incorporated herein by reference.

BACKGROUND OF THE INVENTION The present invention relates generally to ink jet printing on curved surfaces, and more particularly to ink jet printing on game balls. The inks used for ink jet printing are typically water-based resins that contain dyes as colorants. Solvent-based (ie, non-aqueous) formulations and ultraviolet (“UV”) curing, provided that the proper viscosity and surface tension of the ink is obtained, as compatible with both ink jet printing systems and game ball surfaces Other types of inks, such as hydrophobic inks, are also useful in ink jet printing.

[0003] UV-curable inks are fast-curing inks, and are therefore advantageous in continuous processes where subsequent processing of the substrate on which the ink is printed is involved. Numerous UV-curable inks are known. For example, US Pat. No. 4,271,258 discloses a photopolymerizable ink composition containing an acrylate resin, a methacrylate monomer or oligomer, an acrylate monomer or oligomer, a photoinitiator, and a particular type of epoxy resin. U.S. Pat. No. 5,391,685 discloses a UV curable ink containing an isocyanate compound. U.S. Pat.No. 5,391,685 argues that the inks disclosed therein are particularly well suited for printing on poorly adherent plastic substrates such as those made of polyoxymethylene and polypropylene. .

Screen printing on spherical surfaces such as golf balls tends to be difficult. As a result, pad printing is typically used to mark the golf ball surface. However, many known UV curable inks are not well suited for pad printing because of the difficulty in transferring the ink from the pad to the substrate. Furthermore, no pad-printable UV-curable ink suitable for use in golf balls has been found. More specifically, when applied to golf balls, these inks do not have sufficient durability (impact resistance) to withstand multiple hits by a golf club. Has suitable pad transfer properties when used to print indicia on surfaces such as curved and concave surfaces of golf balls;
And it would be useful to obtain highly durable UV curable inks that provide images with good durability.

[0005] Ink jet printing is commonly used to form multicolor images on paper for use in advertising materials, computer-generated photographs, and the like. There are two basic types of inkjet printing, continuous and drop-on-demand. U.S. Pat. No. 5,623,001 describes the difference between continuous and drop-on-demand inkjet printing. In continuous inkjet printing, a stream of ink droplets is charged and then deflected directly or indirectly onto a substrate by an electric field. In drop-on-demand inkjet printing, the supply of ink is controlled by an actuator, such as a piezoelectric actuator. The pressure created by the actuation force forces a droplet from the nozzle or nozzles onto the substrate.

It is known to print directly on a game ball surface using a continuous jet printer that relies on charging to deliver droplets of ink to the game ball surface (
Japanese Patent Application Publication No. 8322967, published December 10, 1996 (Bridgestone) and
Japanese Patent Application Publication No. 2128774, published May 17, 1990 (Bridgestone).

[0007] One of the objects of the Summary of the Invention The present invention is to provide an improved method in novel for forming a durable image on a game ball.

Another object of the present invention is to provide a method for forming a multicolor image on a game ball.

It is yet another object of the present invention to provide a method for quickly and efficiently transferring a logo or image from a computer screen to a game ball surface.

[0010] It is another object of the present invention to provide a game ball, such as a golf ball, having a clear durable ink image printed on its surface.

Another object of the present invention is to provide a method for printing indicia on a hard surface of a game ball, wherein the indicia comprises ink jet printable ink.

It is yet another object of the present invention to provide a method for forming a stain resistant and durable identification mark on a visible surface of a game ball.

[0013] Other objects of the invention will in part be obvious hereinafter and in part will be pointed out in more detail. The present invention at least partially satisfies at least one of the above objects.

One aspect of the invention is (a) obtaining an ink composition suitable for use in ink jet printing, and (b) using an ink jet printer to form an ink in the form of an identification mark on a transfer medium. A method of forming an identification mark on a game ball, comprising delivering the composition and (c) transferring the identification mark from a transfer medium to a surface of the game ball.

[0015] The transfer medium includes at least one substance selected from the group consisting of silicone, fluoropolymer, and polypropylene. The transfer medium can be a low surface energy material.

In one embodiment of the present invention, the ink composition contains a polymer resin. In another embodiment of the present invention, the ink composition includes a resin component.

A golf ball can be used as the game ball. Golf balls usually have a concave surface.

Alternatively, the method further includes (d) forming a protective coat on the identification mark on the surface of the game ball. The protective coat may include a polyurethane.

[0019] The method of the present invention optionally comprises, prior to (b), forming a primer coat layer on at least a portion of the surface of the game ball. The primer coat layer may contain a substance that enhances at least one of the absorption, adhesion, and clarity of the identification mark. Some examples of this material are talc, amorphous silica, bentonite clay, magnesium silicate or a combination of these materials.

[0020] The transfer medium used in the method of the present invention can be a silicone-containing medium such as a sheet or pad.

In one embodiment of the present invention, the ink composition is an aqueous-based formulation. In another aspect of the invention, the ink composition is a non-aqueous or solvent-based formulation. In another aspect of the invention, the ink comprises a UV curable resin and the method comprises (e)
After the identification mark is transferred to the surface of the game ball, the method further includes curing the identification mark.

Another aspect of the present invention is to provide (a) an ink composition suitable for use in ink jet printing, and (b) forming an identification mark receiving layer on at least a portion of a game ball surface. The identification mark receiving layer contains a substance that enhances at least one of the absorption, adhesion and clarity of the identification mark, and (c) printing the identification mark on the identification mark receiving layer using an inkjet printer And a method of forming an identification mark on a game ball. Optionally, the method further comprises (d)
Forming a protective coat on the identification mark. The identification mark may have sufficient shock resistance to make the game ball suitable for use in competitive play.

One example of a suitable game ball is a golf ball. The identification mark receiving layer optionally includes polyurethane.

[0024] The substance that enhances the absorbency, adhesion or clarity of the identification mark can be talc, amorphous silica, bentonite clay, magnesium silicate, or a combination thereof.

An identification mark can be printed directly on the surface of the game ball using an inkjet printer. Alternatively, the identification mark can be printed on a transfer medium using an inkjet printer and then transferred to the surface of the identification mark receiving layer of the game ball, and a drop-on-demand inkjet printer can be used. Those with piezoelectric crystals or thermal printheads are possible.

In another optional aspect of the present invention, the ink comprises a UV curable resin and the method comprises (e
And) curing the identification mark after printing the identification mark on the identification mark receptor layer.

Another aspect of the present invention is that (a) obtaining a UV curable ink composition suitable for use in ink jet printing, and (b) using an ink jet printer to place an identification mark on the surface of the game ball. A method of forming an identification mark on a game ball, such as a golf ball, comprising printing and (c) curing the UV ink composition. The method may further include (d) a step of forming a protective coat on the identification mark.

Another aspect of the invention is to provide (a) an ink composition suitable for use in inkjet printing, and (b) using a drop-on-demand inkjet printer to place an identification mark on the surface of the game ball. A method of forming an identification mark on a game ball such as a golf ball, comprising printing and (c) forming a protective coat on the identification mark. The resolution of the identification mark is at least about 300 dots / inch ("d.
pi ") (about 120 dots / cm), in some cases at least about 500 dpi (about 200 dots / cm)
Dots / cm), in some cases at least about 600 dpi (about 240 dots / cm)
In some cases, it can be at least about 1000 dpi (about 390 dots / cm).

[0029] One of the methods of the present invention for forming an image on the game ball using detailed description inkjet printing of the present invention uses an inkjet printer to print an identification mark on the transfer medium, then An indirect printing technique that involves transferring this image from a transfer medium to the surface of a game ball. Another method of the present invention uses an inkjet printer to print directly on the surface of a specially treated game ball.

FIG. 1 shows a golf ball formed according to one embodiment of the present invention. Golf ball 8 has a central core 10, which may be solid, liquid, gas, gel, wound, or a combination thereof, and a cover 12 having a recess surrounds the core. Identification mark 14 made of ink that can be printed by inkjet
Is formed on the cover 12. In some cases, the identification mark receiving layer 15 is
It is placed between 14 and cover 12. A protective topcoat 16 is formed over the identification mark 14. This top coat 16 may cover the entire ball 8. However, a partial top coat 16 that covers only a slightly larger area than the identification mark 14 is also assumed.

Two methods of indirect inkjet printing of a golf ball surface are shown in FIG. As shown at 30, the golf ball is undercoated with an ink retaining primer. An image is inkjet printed on a transfer sheet shown at 32 or a transfer pad shown at 34. If the image is to be printed on a transfer sheet, it is then transferred at 34 'to a transfer pad on a stamping machine. Next, the transfer pad is positioned to print on the surface of the golf ball, and an image is stamped at 36 on the surface of the golf ball. After forming the image, the surface of the ball and the identification mark can be applied with a suitable topcoat, if necessary.

A method for direct ink jet printing on a golf ball is shown in FIG. As shown at 40, the golf ball is undercoated with an ink retaining primer. After applying this coating, an image is inkjet printed directly on the surface of the primer at 42. After the image has been applied, the surface of the ball and identification mark can optionally be coated at 44 with a suitable topcoat.

The method of the present invention can be used on curved surfaces of game balls, such as golf balls, basketballs, baseballs, softballs, and is particularly useful for golf balls. Printing on curved, concave surfaces of golf balls can be difficult. Because the indentation tends to distort the image printed on it, and because the plastic cover of golf balls is typically made of ionomer, balata or polyurethane, the surface energy is low. It is. If the surface energy of the ionomer cover is low, adhesion becomes difficult,
Also, the formation of beads when the ink is placed on the cover also causes the printed image to be blurred. One of the ways in which the present invention overcomes this beading problem is by applying a primer coat to at least the portion of the ball surface where the identification mark is to be printed, the primer coat being able to absorb the identification mark. Contains substances that enhance adhesion and / or clarity. Materials of this type suitable for use in the primer coat of game balls, such as golf balls, include talc, amorphous silica, bentonite clay, magnesium silicate, and the like, or combinations thereof.

In another aspect of the invention, a material that enhances the absorption, adhesion and / or clarity of the identification mark is incorporated into the cover itself. For example, cover the ionomer,
When formed from polyurethane or balata, suitable materials of this type that can be incorporated therein include talc, amorphous silica, bentonite clay, magnesium silicate, and the like, or combinations thereof.

The ink used in the method of the present invention is suitable for use in an ink jet printer. Typically, the ink contains a colorant, a carrier, and additives. Colorants are usually dyes and / or pigments and may be fluorescent. Alternatively, the ink may include a fluorescent material as a colorant instead of or in addition to a conventional dye. As another variation, the ink may include a selective absorber of infrared or microwave radiation. The colorant carrier or vehicle can be either water or an organic solvent. The physical properties of the substrate and other ink components determine the type and amount of carrier used. Examples of useful additives include substances for adjusting pH, viscosity, photobleaching and surface tension. Further, a polymer resin or a resin component can be included in the ink. Examples of polymer resins or resin components used in conventional ink-jet printing inks include polyurethane, polyester, polyketone and polyacrylate. In the case of a UV curable ink, the resin component can be, for example, an oligomer. The composition of the ink and the composition of the ball cover or primer layer forming the identification mark can be selected such that the surface tension of the ink appropriately matches the surface properties of the substrate to which it is attached. Inks that are considered suitable for ink jet printing typically have a viscosity of about 1 to about 20 cps, measured at the temperature of application.

As indicated above, UV curable inks can be used according to the method of the present invention. Most commercial UV inks are not suitable for inkjet printing due to the high concentration and size of dyes and fillers in such formulations. Suitable for inkjet printer to promote flow in inkjet printer
UV inks incorporate very finely divided dyes (about 0.1 micron, or even less than 100 angstroms), dissolved dyes, or a combination of dyes and finely divided dyes. Flowability additives, surface tension modifiers, additional solvents and the like can be added to the ink formulation to improve ink jet printing performance and prevent clogging of the ink jet printer. UV curable inks are described in more detail in another section herein below.

When applying a primer coat layer to a game ball cover, the coating is typically a solvent-based or water-based polyurethane material. Non-limiting examples of 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.

To protect the identification mark, unless the identification mark has sufficient adhesion to the surface forming the identification mark, for example a cover or primer layer, and the use of a top coat is not necessary. It is useful to apply a top coat on the identification mark. It is assumed that the adhesion between the ink and the topcoat and / or substrate is strong enough that the identification mark remains substantially intact when the game ball is used. The criteria for image retention vary depending on the intended use of the game ball, and the degree and frequency of impact that the image is required to hold. When applied to a golf ball, the durability of the ink is desirably at least about 50%, and in some cases at least about 70%, of the original image surface area after subjecting the ball to the wet barrel durability test operation described below. In some cases, at least about 80% is sufficient to remain. If about 85% or more of the image remains, it means excellent durability.

As described above, in one embodiment of the present invention, the identification mark is transferred to a transfer medium using an inkjet printer, and then transferred to the surface of the game ball. Suitable transfer media are those that have a surface that allows the transfer of the image to the surface of the game ball, while providing good clarity of the identification marks printed thereon. One of the envisioned transfer media is a silicone pad. If necessary, an absorbent filler can be added to the silicone pad to facilitate ink spillage and prevent repelling on the surface of the silicone pad. Additionally or alternatively, the surface of the pad can be roughened to the extent necessary to achieve the desired surface energy. If an image is to be printed on a curved, concave surface of a golf ball, it is easier for the transfer substrate to apply the ink to the inside of the recess using a pad than a flat sheet. One type of silicone pad envisioned is that used in conventional golf ball pad printing.

Although any inkjet printer can be used, two types of inkjet printers specifically contemplated for printing on game balls are continuous inkjet printers and drop-on-demand inkjet printers. In continuous ink jet printers, a stream of ink droplets is charged and then deflected directly or indirectly onto a substrate by an electric field. In a drop-on-demand inkjet printer, the supply of ink is controlled by an actuator such as a piezoelectric actuator. The pressure generated by actuation forces the droplets from the nozzle or nozzles into the substrate.

UV curable inks Golf balls, softballs, baseball balls, other game balls, and other sports including but not limited to softball and baseball bats, tennis and racquetball rackets, and golf clubs The UV curable inks of the present invention can be used to print identification marks on articles. The ink can also be applied to a variety of materials including, but not limited to, ionomers, polybutadienes, composites, metals and the like.

As indicated above, the ink comprises a UV curable resin, a colorant such as a pigment or dye,
It contains the above photoinitiator, and optionally a solvent. The ink may also include aluminum trihydroxide. Diluents containing monomers and / or solvents can also be added. A wetting agent may be included.

The UV-curable resin may include an oligomer. Non-limiting examples of oligomers include one or more of epoxy, acrylic, acrylate urethane, elastic acrylate, unsaturated polyester, and polyether. Particular examples of suitable oligomers include methacrylates such as bisphenol A ethoxylate dimethacrylate and acrylated epoxies. Blends of various oligomers can also be used. Oligomers can provide the ink with sufficient flexibility and impact resistance to withstand the conditions experienced by the substrate. For example, if the substrate is a golf ball, the oligomer can provide the ink with more flexibility than is inherent in the underlying substrate with the intention of providing good durability. When the topcoat is placed over the ink, it is desirable that the ink not be too crosslinked so that adhesion of the topcoat to the ink is substantially hindered.

The uncured ink can include about 10-90% by weight of the oligomer, optionally about 20-80% by weight of the oligomer, optionally about 50-70% by weight of the oligomer.

The colorant may be any type of pigment that is resistant to UV treatment, ie not UV-labile,
Dyes and the like are possible. Further, it is envisioned that the colorant allows UV light to sufficiently pass through the ink by any combination of transmission, reflection or refraction mechanisms to initiate the photocrosslinking reaction. Liquids or powders can be used. One non-limiting example of an ink is a powder dispersed in a liquid monomer. Non-limiting examples of suitable pigments for producing black ink are carbon black and iron oxide black. Red lake and quinacridone are non-limiting examples of suitable pigments for producing red ink. Blends of various pigments and / or dyes can also be used. The uncured ink can include about 2-60% by weight of the colorant, or about 5-30% by weight of the colorant, or about 5-10% by weight of the colorant.

The photoinitiator is selected to be responsive to the wavelength of UV radiation used to initiate photopolymerization. In selecting a photoinitiator, it is also important to consider the color of the ink. This is because, as indicated above, UV light must be transmitted through the ink composition to initiate curing. More specifically, transmission may be required to cure the portion of the ink below the surface. Transmission is typically the most difficult when using black or white pigments. Non-limiting examples of photoinitiators used in combination with the black pigment include sulfur-type photoinitiators such as isopropylthioxanthone, and benzophenone, and derivatives thereof including acetophenone type and thioxanthone. A photoactivator can be used in combination with one or more photoinitiators. Non-limiting example of a suitable photoactivator is ethyl.
It is an amine type photoactivator such as 4-dimethylaminobenzoate. The uncured ink can include about 0.3-5% by weight of a photoinitiator, or about 1-4% by weight of a photoinitiator, or about 3-4% by weight of a photoinitiator. Other types of photoinitiators or blends of photoinitiators and photoactivators can be used.

A diluent can be added to reduce the viscosity of the uncured ink composition or to contribute to impact resistance or flexibility. When a monomer is used as a diluent, it can optionally be a photopolymerizable monomer that forms a polymer structure upon irradiation. In contrast, when using a solvent as a diluent,
These evaporate during curing. The monomers can be monofunctional, difunctional or multifunctional acrylates. Non-limiting examples of suitable monomers include 1,6 hexanediol diacrylate, butanediol diacrylate, trimethylolpropane diacrylate, tripropylene glycol diacrylate, and tetraethylene glycol diacrylate.

[0048] The uncured ink can include about 10-70% by weight of the monomer, or about 10-60% by weight of the monomer, or about 10-55% by weight of the monomer. The combination of monomers and oligomers may constitute about 45-80% by weight of the uncured ink, optionally about 50-80% by weight of the ink, and optionally about 60-80% by weight. A non-UV curable quick-drying resin that promotes transfer of the ink from the pad to the ball may be added. Non-limiting examples of such resins are vinyl resins, nitrocellulose, acrylics, and other fast-drying, film-forming resins. One envisioned resin is McWorther, Inc., Carpentersville, IL, sold as Resin975.
Acrylic-OH functional resin. Typically, when such resins are used, they are added in amounts up to about 30 parts by weight, based on a total of 100 parts by weight of the uncured ink composition.

When a solvent is used in the UV-curable ink, it is typically a liquid containing a fixing agent for controlling the evaporation rate. This, when partially evaporated, causes the ink to become sticky, thereby facilitating transfer onto or from the ink pad. The solvent can be a medium in which the photoinitiator is dissolved. Non-limiting examples of suitable solvents include aromatic solvents such as toluene, xylene, and ester types such as butyl acetate. The uncured ink can include about 1 to 30% by weight solvent, optionally about 5 to 20% by weight solvent, and optionally about 8 to 10% by weight solvent.

In order to prevent the repelling of the ink when applied to a golf ball, a wetting agent can be added. Suitable wetting agents include, but are not limited to, silicone surfactants and fluorocarbon surfactants. About 0 ~ 2 for uncured ink
Contains wt% humectant. Other additives that do not adversely affect the transfer of the ink to the pad and the impact resistance can also be incorporated into the ink composition.

As long as sufficient durability is maintained, extender pigments such as talc and barium sulfate can be added to improve transfer performance. For use in ink jet printers, the particle size of the extender pigment must be small enough to facilitate passage through the orifice of the printer. This includes finely divided (
Silica (less than about 0.1 micron, or less than 100 angstroms), clay or talc, or combinations thereof. Typically, when such materials are used, they make up about 10-40%, or about 20-30%, by weight of the uncured ink formulation.

By replacing some or all of the extender pigments such as talc and barium sulfate with aluminum trihydroxide (Al (OH) ₃ .3H ₂ O) (ATH) filler, the printing, curing and operating aspects are It has been found that a number of significant improvements in UV ink results are obtained. In addition, the inclusion of ATH has minimal effect on ink color.
Further, since ATH has low oil absorption, the viscosity of the ink hardly increases.
Addition of up to 50% by weight, based on the total (uncured) weight of the ink, improves the transfer of the ink from the pad to the substrate. Significantly, the curing of the ink is not hindered because ATH does not absorb UV light. For use in ink jet printing, the particle size of the ATH must be small enough to facilitate passage through the ink jet orifice.

When using ATH in a UV curable game ball ink, it is generally included in an amount of 10 to 50% by weight, based on the total weight of the ink before curing. ATH is preferably used in an amount of 10 to 32% by weight, or alternatively 20 to 30% by weight. Addition of ATH to at least 50% by weight based on the amount of (uncured) ink provides an overall balance of properties
It is believed to be useful to provide. If low cost inks are desired and durability requirements are not stringent, ATH can be used in larger quantities. If high durability is required, a smaller amount of ATH is useful. ATH can be used in an appropriate amount to balance the ink with properties such as pad transfer and ink durability.

When ATH is used in combination with talc, barium sulfate, etc., the ratio of ATH to talc, etc. can be about 1: 1.

The use of ATH does not interfere with the curing process. The surface tension of the ink affects the wettability of the substrate. Desirably, the surface tension of the ink is not substantially higher than the surface tension of the substrate on which it is printed. The viscosity of the ink is one of the factors affecting the thickness of the identification mark on the cover. If the identification mark is too thick, the UV radiation may not penetrate the identification mark, making complete curing difficult. On the other hand, if the identification mark is too thin, the durability of the ink layer may be insufficient for play conditions. The thickness of the identification mark is less than about 100 microns, sometimes about 10-40 microns, sometimes about 10
~ 30 microns, and sometimes about 20-25 microns.

The cured ink is intended to be sufficiently flexible to exhibit good impact resistance.
The topcoat applied over the ink is advantageously one that reacts with the ink to hold the ink in place, or that is adherent by hydrogen bonding and / or Van der Waals forces. As a non-limiting example, the ink can be used in combination with a two-component polyurethane topcoat, such as a topcoat based on a polyester or acrylic polyol and an aliphatic isocyanate such as hexamethylene diisocyanate or isophorone diisocyanate trimer. .

As one non-limiting example, the present invention may be used to mark golf balls.
A UV curable ink formulation can be prepared and used as follows. The photoinitiator is dissolved in the diluent and then mixed with the oligomer and pigment. The mixture is placed in a dispenser used in direct or indirect inkjet printing. Obtain an unfinished golf ball that has been pretreated. The ball includes, for example, a core and a durable cover having a concave surface. Alternatively, the core and cover can be one-piece molded. An identification mark formed of a UV curable ink is inkjet printed on a golf ball cover, either directly or indirectly using a transfer medium. The unfinished golf ball is then subjected to a UV treatment at least under conditions sufficient to initiate curing of the ink. After the start of light, curing of the ink is 1
Substantially complete in less than a few seconds to a few seconds.

A top coat layer is applied on the identification mark. The topcoat is applied at least partially and optionally completely after curing of the ink. Since the topcoat layer helps retain the identification marks on the golf ball surface as described above, adhesion of the identification marks to the golf ball is required when the ink constitutes the outer layer of the ball It doesn't have to be as powerful. Topcoats are typically 10-40 microns in thickness.

Those skilled in the art can ascertain the conditions of UV exposure suitable for curing the ink. By way of example, about 10 feet from a UV light source having an intensity of, for example, 200-300 watts / in ² (31-47 watts / cm ² ) at a distance of about 11 / 4-13 / 4 inches. / Minute (about 3
When the golf ball passes through the UV treatment device at a speed of (m / min), the identification mark is exposed to UV radiation for no more than a few seconds, sometimes no more than about 1 second, and sometimes no more than about 0.7 seconds. I understood. As long as the cured ink meets the required durability requirements,
Greater or smaller UV light source intensities, distances and exposure times may be used. Avoid excessive UV exposure to prevent substrate degradation. The ink can be UV cured before applying any topcoat.

The pad used for the transfer of the UV ink according to one embodiment of the present invention may include silicone. This type of pad has good elasticity, durability and flexibility, and adequate surface tension. Other types of pads can also be used.

The ink can be applied to the non-UV-unstable surface of the game ball. In the present invention, it is generally not necessary to pretreat the surface before applying the ink. If UV curable ink is required to be applied to a very smooth surface with poor transfer, chemically or physically etch portions of the surface to be stamped to provide an ink receptive surface Can be ground.

After curing, the ink of the present invention has a Sw of about 55 or less, or about 40 or less, or about 20 or less.
ard hardness (ASTM-D 2134-66). The UV curable inks of the present invention have sufficient durability to meet the stringent durability standards required for commercial grade golf balls. The durability of the ink can be determined by testing the stamped golf ball in various ways, including using a wet barrel durability test procedure.

The durability according to the wet barrel durability test operation was 135 feet / second (72 ° F.) (41 m / s (22 ° C.) in a pentagonal steel container with five sides made of steel plate.
The judgment is made by throwing the golf ball in the step ()). The container 110 shown schematically in FIG. 4 has a 191/2 inch (49.5 cm) long insert plate 112 erected therein.
Its central portion 114 has a rectangular groove extending in a horizontal plane, intended to simulate a rectangular grooved face of a golf club. The grooves shown enlarged in FIG. 5 have a width 130 of 0.033 inches (0.084 cm), a depth 132 of 0.100 inches (0.25 cm), and are separated from each other by inter-groove flats 134 having a width of 0.130 inches (0.330 cm). Have been. The five walls 116 of the pentagonal container are each 141/2 inches (36.8 cm) in length. As shown in FIG. 4, the entrance wall is vertical, and the insertion plate is set up at an angle of 30 ° above the horizontal plane and away from the opening 120 of the container 110. The ball moves horizontally from the entrance point to the container 110 until it hits the center of the insertion plate 112 having a square groove.
Go 153/4 inch (39.4-40 cm). The angle between the ball trajectory and the insert plate 112 is 30 °. The ball is hit or thrown 70 times or more and destroyed at regular intervals (
(I.e., any signs of cracking or delamination of the cover). If a minute crack is formed in the ball, the speed is changed and the operator is warned. The operator then visually inspects the ball. If the microcracks cannot be observed yet, return the ball to the test until cracks are visually detected. The ball is then tested for ink adhesion.

The following examples serve to further describe the invention. Example 1 A golf ball printing ink containing the following substances was prepared. 5 parts by weight of 1,6 hexanediol diacrylate (purchased from Sartomer, Exton, PA), purchased as Carbon Black UV Dispersion 99B415 (Penn Color, Doylestown, PA)
17.5 parts by weight of black pigment paste in diacrylate monomer, 35 parts by weight of aliphatic urethane acrylate oligomer (purchased from CN965, Sartomer, Exton, PA), isopropylthioxanthone, C ₁₆ H ₁₄ OS, sulfur type photoinitiator (IT
X, commercially available from Aceto Chemical, Lake Success, NY) 0.5 parts by weight, ethyl 4-dimethylaminobenzoate, C ₁₁ H ₁₅ NO ₂ , amine type photoactivator (EDB, commercially available from Aceto Chemical, Lake Success, NY) 1 part by weight, 4.4 parts by weight of xylene solvent, and 4.4 parts by weight of butyl acetate solvent.

The photoinitiator and photoactivator were dissolved in a xylene / butyl acetate solvent blend.
Ionomer cover with a few dozen golf balls with cavities not to be applied under,
The ink was pad printed using a silicone pad. The ink had a viscosity of about 27,500 centipoise ("cps") upon application. At a light source intensity of 235 watts / in ² (36.4 watts / cm ² ) and a wavelength of 200-400 nm, the identification mark is placed approximately 13/4 inch (4.4 cm) from the UV light source and the ball containing the stamped identification mark is placed. At a speed of 10 feet / min (3 m / min), it passed through a Labex # 14201 UVex processor. The ink cured in less than about 1 second and had a Sward hardness of about 14 after curing was complete.

The golf ball was then coated with a solvent based polyurethane topcoat formed from polyester type hexamethylene diisocyanate. According to the wet barrel durability test operation described above, the adhesion of the identification mark on the ball was tested for durability. After the wet barrel durability test, the balls were inspected and found to remove less than about 20% of the original ink logo surface area.

Example 2 The procedure of Example 1 was repeated, except that the ink formulation used contained the following composition: 10 parts by weight of 1,6 hexanediol diacrylate (purchased from Sartomer), 35 parts by weight of black pigment paste in diacrylate monomer, purchased as Carbon Black UV Dispersion 99B415, bifunctional aliphatic urethane acrylate oligomer (Ebecryl 4833, UCB , RadCure
, Inc., Smyrna, GA) 70 parts by weight, isopropylthioxanthone, 1 part by weight of C ₁₆ H ₁₄ OS (ITX), and 2 parts by weight of ethyl 4-dimethylaminobenzoate (EDB).

This ink had a viscosity of about 25,000 cps. The ink cures in about 1 second, and Sward
A film having a hardness of about 12 was formed. The ball was subjected to a wet barrel durability test operation. After the wet barrel durability test, the balls were inspected and found to remove less than about 20% of the original ink logo surface area.

Example 3 The procedure of Example 1 was repeated except that the CN965 oligomer was replaced by a bifunctional oligomer commercially available as Ebecryl 8402 (UCB, RadCure, Inc., Smyrna, GA).
This ink had a viscosity of about 18,000 cps. The ink cures in about 1 second, and Sward
A film having a hardness of about 14 was formed. The ink was found to be nearly as durable as those of Examples 1 and 2.

Example 4 The procedure of Example 1 was repeated, except that the ink formulation used contained the following composition: 7.3 parts by weight of 1,6 hexanediol diacrylate (purchased from Sartomer, Exton, PA), 19.2 parts by weight of black pigment paste in diacrylate monomer, purchased as ICU 386 (Industrial Color Inc., Joliet, IL), aliphatic Polyether urethane oligomer (BR-571, Bomar Specialties Company
, Winsted, CT) 21.0 parts by weight, isopropylthioxanthone, C ₁₆ H ₁₄ OS, sulfur type photoinitiator (ITX
0.5 parts by weight, Aceto Chemical, Lake Success, NY), 1 part by weight of ethyl 4-dimethylaminobenzoate (EDB), 11.4 parts by weight of talc (Vantalc 6H, Vanderbilt, Norwalk, CT), 11.4 parts by weight of barium sulfate (106 Low-Micron White Barytles, Whittaker, Clark & Daniels,
Inc., South Plainfield, NJ) 22.9 parts by weight, butyl acetate solvent 12.1 parts by weight, and propylene glycol monomethyl ether acetate solvent 4.6 parts by weight.

This ink was applied directly to the ionomer cover of a golf ball, and also applied to an ionomer cover to which a water-based polyurethane primer layer had been applied before the application of the ink. The ink cured in about 1 second, forming a film with a Sward hardness of about 14.
The balls were top coated and subjected to a wet barrel durability test operation. After the wet barrel durability test, it was found that less than about 20% of the original ink logo surface area was removed.

Comparative Test Example 1 A commercially available UV curable ink, ie, Blk # 700801 (Trans Tech, Carol Stream, IL)
The procedure of Example 1 was repeated, except that) was used. This ink is about 6,000 cps
It had a viscosity of The ink cured in about 1 second, forming a film with a Sward hardness of about 26. After the wet barrel durability test, only the outer shell of the logo remained. Most of the ink inside and outside the depression was removed. The adhesion between the ink and the top coat was poor.

Comparative Test Example 2 A commercial UV-curable ink, ie, L-526-163-B, was prepared for several golf balls.
The procedure of Example 1 was repeated except that (Qure Tech, Seabrook, NH) was used.
This ink had a viscosity of about 28,500 cps. The ink cures in about 1 second, and Sward
A film having a hardness of about 20 was formed. Wet barrel durability testing showed that at least about 60% of the surface area of the logo had been removed. The ink was considered too brittle to withstand the conditions of this wet barrel durability test.

Example 5 The following ATH-containing formulation 1 was prepared. ATH-containing formulation 1 part by weight Acrylic-OH functional resin ¹ 540.5 Acetate and aromatic hydrocarbon solvent blend ² 189.2 ATH ³ 270.3 1000.0 ¹ McWorther Resin 975 (McWorther, Inc., Carpentersville, IL) ² Summit Ink Reducer, Summit PT # 910527 (Summit Screen Inks, No. Kansas
City, MO). Alternatively, a mixture based on 43.4 parts by weight of butyl acetate, 28.3 parts by weight of xylene and 28.3 parts by weight of propylene glycol monomethyl ether acetate can be used ³ ATH SpaceRite S-3 (ALCOA Industries, Bauxite, AR).

Next, using the ATH-containing composition 1, a golf ball ink containing the following was prepared. Aliphatic urethane triacrylate (BR-990, Bomar Specialties Co., Winsted, C
T) 5 parts by weight, ATH-containing composition 1 35 parts by weight, trimethylolpropane triacrylate (TMPTA) (Sartomer Co., West Che
ster, PA) 5.5 parts by weight, black dispersion in oligomer / monomer (ICU 386, Industrial Color Inc.,
Joliet, IL) 5 parts by weight, isopropylthioxanthone, C ₁₆ H ₁₄ OS, sulfur type photopolymerization initiator (
ITX, commercially available from Aceto Chemical, Lake Success, NY) 0.3 parts by weight, ethyl 4-dimethylaminobenzoate, C ₁₁ H ₁₅ NO ₂ , amine type photoactivator (EDB, commercially available from Aceto Chemical, Lake Success, NY) 1 part by weight and 10 parts by weight of ATH (SpaceRite S-3, ALCOA Industries, Bauxite, AR).

All components were mixed and dispersed by a high-speed mixing device. The ink was pad-printed using a silicone pad on an ionomer cover with a few dozen golf balls without undercoating.

At a light source intensity of 235 watts / inch ² (36.4 watts / cm ² ) and a wavelength of 200-400 nm, the identification mark was stamped with the identification mark positioned about 13/4 inch (4.4 cm) from the UV light source. Was passed through a Uvex UV lamp at a speed of 10 feet / min (3 m / min). The ink cured in less than about 1 second.

Next, the golf ball was coated with a two-component polyester / aliphatic polyisocyanate clear coat.

Ink printing performance, jetness, detail image, pad release
, And durability were compared to three control inks, designated Control A, Control B and Control C. The formulations of Control A and Control B are shown below. Control A parts by weight aliphatic urethane-acrylic oligomer ¹ 6.45 acryl-OH functional resin ² 42.96 acetate and aromatic hydrocarbon solvent blend ³ 8.85 talc ⁴ 5.59 barium sulfate ⁵ 12.89 black dispersion in oligomer / monomer ⁶ 6.01 TMPTA ⁷ 15.18 Isopropylthioxanthone ⁸ 0.69 Ethyl 4-dimethylaminobenzoate ⁹ 1.38 100.00 ¹ BR-571 (Bomar Specialties Co., Winsted, CT) ² McWorther Resin 975 (McWorther, Inc., Carpentersville, IL) ³ Summit Ink Reducer (Pt # 910527, Summit Screen Inks, No. Kansas City, MO) ⁴ Van Talc # 6H (Vanderbilt, Norwalk, CT) ⁵ Barytes # 22 (Whittaker, Clark & Daniels, Inc., South Plainfield, NJ) ⁶ ICU 386 (Industrial Color Inc.) , Joliet, IL) ⁷ (Sartomer Co., West Chester, PA) ⁸ ITX (commercially available from Aceto Chemical, Lake Success, NY) ⁹ EDB (commercially available from Aceto Chemical, Lake Success, NY).

Control B parts by weight epoxy-acrylate oligomer ¹ 19.24 acrylic-OH functional resin ² 27.70 acetate and aromatic hydrocarbon solvent blend ³ 13.84 talc ⁴ 7.69 barium sulfate ⁵ 7.69 oligomer / black dispersion in monomer ⁶ 6.15 polyester Acrylate oligomer ⁷ 15.38 Isopropylthioxanthone ⁸ 0.77 Ethyl 4-dimethylaminobenzoate ⁹ 1.54 100.00 ¹ Ebecryl 3700 (Rad-Cure, Smyrna, GA) ² McWorther Resin 975 (McWorther, Inc., Carpentersville, IL) ³ Summit Ink Reducer (Pt #) 910527, Summit Screen Inks, No. Kansas City, MO) ⁴ Van Talc 6H (Vanderbilt, Norwalk, CT) ⁵ Barytes # 22 (Whittaker, Clark & Daniels, Inc., South Plainfield, NJ) ⁶ ICU 386 (Industrial Color Inc) , Joliette, IL) ⁷ Ebecryl 80 (Rad-Cure, Smyrna, GA) ⁸ ITX (commercially available from Aceto Chemical, Lake Success, NY) ⁹ EDB (commercially available from Aceto Chemical, Lake Success, NY).

Control C was Trans Tech ink # 2P37-2 (Trans Tech, Carol Stream, IL). The evaluation points of various ink formulations are shown below.

The evaluation points were 1-5 from 1 which is ideal to 5 which was not acceptable. The ball of Example 5 and all of the balls of Controls A, B and C were coated with a 160 mg one coat top coating system. The topcoat is a two-component polyester / aliphatic polyisocyanate clearcoat.

The ink of Example 5 has an oligomer / monomer content of 22.608% by weight, an acrylic resin content of 21.508% by weight, a black pigment content of 3.08% by weight, an ATH pigment content of 31.63% by weight, a solvent content of 20.008% by weight and The initiator content is 1.62% by weight. The density of the ink was 10.68 lbs./gal. (1.28 kg / L), the total nonvolatile content was 80%, and the volatile organic compounds comprised 2.14 lbs./gal. (0.256 kg / L). The viscosity of the ink was 11,000 cps at the time of application. After curing, the inks were tested for bleeding resistance using a methyl ethyl ketone solvent. No bleeding occurred.

It has been found that the solvent content of the ink can be significantly increased without reducing the quality of the identification stamp. For example, if the ink is further reduced to 30% (by adding solvent), the viscosity of the ink should drop to about 1420 cps.
This low viscosity ink tends to have better printing performance on some pad printing machines than more viscous inks.

FIG. 6 shows the silicone pad after stamping 12 golf balls with a particular type of ink. FIG. 6A (150) shows the stamp after stamping with the control A ink. FIG. 6B (152) shows the silicone pad after stamping with Control B ink. FIG. 6C (154) shows the pad after stamping with the ink of the fifth embodiment. FIG. 6D (155) shows the pad after stamping with Control C. As shown from the resulting stamp, the best transfer, ie, the result with the least amount of ink remaining on the stamp, was obtained from using the ink of Example 5.

Example 6 The following ATH-containing formulation 2 was prepared. ATH-containing formulation 2 parts by weight Acrylic-OH functional resin ¹ 21.84 Propylene glycol monomethyl ether acetate Solvent ² 4.85 ATH ³ 20.70 Talc ⁴ 19.50 Black dispersion in oligomer / monomer ⁵ 9.50 76.39 ¹ McWorther Resin 975 (McWorther, Inc., Carpentersville) ² Dow Chemical (and others) ³ ATH SpaceRite S-3 (ALCOA Industries, Bauxite, AR) ⁴ Van Talc # 6H (Vanderbilt, Norwalk, CT) ⁶ ICU 386 (Industrial Color Inc., Joliet, IL).

After mixing the formulations, the following materials were added: 1.31 parts by weight butyl acetate (Eastman Chemical and others), 6.16 parts by weight Aromatic 100 or HiSol 53 (Ashland Chemicals), 3.08 parts by weight cyclohexanone (Ashland Chemicals), Isopropylthioxanthone, C ₁₆ H ₁₄ OS, sulfur type photopolymerization initiator (
ITX, commercially available from Aceto Chemical, Lake Success, NY) 0.50 parts by weight, ethyl 4-dimethylaminobenzoate, C ₁₁ H ₁₅ NO ₂ , amine type photoactivator (EDB, commercially available from Aceto Chemical, Lake Success, NY) 1 part by weight, aliphatic urethane triacrylate (UV curable resin) (BR-990, Bomar Specialti
es Co., Winsted, CT) 5.78 parts by weight, and trimethylolpropane triacrylate (UV curable resin) (TMPTA) (Sarto
mer Co., West Chester, PA) 5.78 parts by weight. The total weight is 100. All components were mixed and dispersed in a high-speed mixing device.

An ink was pad-printed using a silicone pad on an ionomer cover having a number of unprimed wells of a golf ball. In the light source intensity 235 watts / inch ^{2 (36.4} watts / cm ²⁾ and the wavelength 200-400 nm, at an identification mark to the position of approximately 13/4 inches from the UV light source (4.4 cm), the ball including the identification marks stamped Was passed through a Uvex UV lamp at a speed of 10 feet / minute (3 m / minute). The ink cured in less than about 1 second.

Next, this golf ball was coated with a two-component polyester / aliphatic polyisocyanate clear coat and subjected to a wet barrel durability test operation. After the wet barrel durability test, it was found that only about 20% of the original ink logo surface area was removed.

Example 7 The amount of ATH was reduced to 19.20 parts by weight and the ATH containing formulation (ATH containing formulation 2) was added to a black dispersion in oligomer / monomer (CU 386, Industrial Color Inc., Joliet, IL).
0.22 parts by weight only, and the first red dispersion in oligomer / monomer (
8.16 parts by weight of ICU Red Lake C, Industrial Color Inc., Joliet, IL and a second red dispersion in oligomers / monomers (ICU Lithol 388 Red, Industrial Color Inc.)
, Joliet, IL), except that 2.62 parts by weight were included. All components were mixed and dispersed in a high-speed mixing device. The total weight is 100.

After the wet barrel durability test, it was found that only about 20% of the original ink logo surface area was removed.

Example 8 The following ATH-containing formulation 3 was prepared. ATH-containing formulation 3 parts by weight Acrylic-OH functional resin ¹ 30.78 Butyl acetate solvent 4.67 Xylene solvent ² 3.04 Propylene glycol monomethyl ether acetate solvent 3.04 ATH ³ 31.66 73.19 ¹ McWorther Resin 975 (McWorther, Inc., Carpentersville, IL) ² Shell ³ ATH SpaceRite S-3 (ALCOA Industries, Bauxite, AR).

After mixing the formulations, the following substances were added: Red dispersion in oligomer / monomer (ICU Red Lake C, Industrial Color
Inc., Joliet, IL) 5.69 parts by weight, Red dispersion in oligomer / monomer (ICU Lithol Rubine, Industrial Col.)
or Inc., Joliet, IL) 1.92 parts by weight, Black dispersion in oligomer / monomer (ICU 386, Industrial Color Inc.,
Joliet, IL) 0.47 parts by weight, isopropylthioxanthone, C ₁₆ H ₁₄ OS, sulfur type photopolymerization initiator (
ITX, commercially available from Aceto Chemical, Lake Success, NY) 0.49 parts by weight, ethyl 4-dimethylaminobenzoate, C ₁₁ H ₁₄ NO ₂ , amine type photoactivator (EDB, commercially available from Aceto Chemical, Lake Success, NY) 1.14 parts by weight, aliphatic urethane triacrylate (BR-990; Bomar Specialties Co., Winsted,
CT) 8.14 parts by weight, and trimethylolpropane triacrylate (TMPTA) (Sartomer Co., West Che
ster, PA) 8.95 parts by weight. The total weight is 99.99.

To provide optimum printability, a solvent prepared by mixing 43.4 parts by weight of butyl acetate, 28.3 parts by weight of xylene, and 28.3 parts by weight of propylene glycol monomethyl ether acetate was used (based on the weight of the ink before reduction). By adding wt%, the viscosity of the ink was reduced to 1200 cps.

The ink was printed on a number of golf balls. The golf ball was then coated with a two-component polyester / aliphatic polyisocyanate clear coat and subjected to a wet barrel durability test procedure. After the wet barrel durability test, it was found that less than about 20% of the original ink logo surface area was removed. The initially printed ball was a clear image. After some time, some ghosts appeared.

Example 9 The following ATH-containing formulation 4 was prepared. ATH-containing formulation 4 parts by weight Acrylic-OH functional resin ¹ 21.63 Butyl acetate 7.57 ATH ² 21.34 Talc ³ 19.35 First red dispersion in oligomer / monomer ⁴ 7.04 Second red dispersion in oligomer / monomer ⁵ 2.26 In oligomer / monomer Black dispersion ⁶ 0.61 Xylene solvent 3.80 83.60 ¹ McWorther Resin 975 (McWorther, Inc., Carpentersville, IL) ² ATH SpaceRite S-3 (ALCOA Industries, Bauxite, AR) ³ Van Talc # 6H (Vanderbilt, Norwalk, CT) ⁴ ICU Red Lake C, (Industrial Color Inc., Joliet, IL) ⁵ ICU Lithol Rubine 388 (Industrial Color Inc., Joliet, IL) ⁶ ICU 386 (Industrial Color Inc., Joliet, IL).

After mixing the formulation, the following substances were added: propylene glycol monomethyl ether acetate solvent 3.80 parts by weight, isopropylthioxanthone, C ₁₆ H ₁₄ OS, sulfur type photoinitiator (
ITX, commercially available from Aceto Chemical, Lake Success, NY) 0.38 parts by weight, ethyl 4-dimethylaminobenzoate, C ₁₁ H ₁₄ NO ₂ , amino-type photopolymerization initiator (EDB, commercially available from Aceto Chemical, Lake Success, NY) 0.86 parts by weight, aliphatic urethane triacrylate (BR-990, Bomar Specialties Co., Winsted, C
T) 5.69 parts by weight, and trimethylolpropane triacrylate (TMPTA) (Sartomer Co., West Che
ster, PA) 5.69 parts by weight. The total weight is 100.02.

The ink was printed on a number of golf balls. The image was very dark. The use of lower levels of the black dispersion probably resulted in satisfactory images. The golf ball was then coated with a two-component polyester / aliphatic polyisocyanate clear coat and subjected to a wet barrel durability test procedure. After the wet barrel durability test, it was found that only about 20% of the original ink logo surface area was removed.

Example 10 In FIG. 7, an image was printed from a JPEG computer file on a polysilicon coated paper sheet (Dow Corning HS2) 202 using an inkjet printer (Epson Stylus Color 640) 200. This resulted in an inkjet logo 204 on the silicone coated paper 202.

Golf with an ionomer cover coated with an ink-retaining primer coat formed of 100.00 parts by weight of a water-based polyurethane primer, Witcobond 235 (Witco) and 7.0 parts by weight of amorphous silica (HiSil 915, PPG, Pittsburgh, PA) You got the ball 206. After the primer coat dried, the image 204 on the silicone paper 202 was transferred to the surface of the golf ball 206 using a golf ball logo stamp machine 208.

More specifically, the ball logo stamping machine 208 has a horizontal arm 210 to which a plunger 212 for carrying a transfer pad 214 is connected. A silicone coated paper 202 holding a logo 204 was placed under the transfer pad 214. Plunger212
Moved the transfer pad 214 against the logo 204, and took out the logo image 204 onto the transfer pad 214. The transfer pad 214 was pulled back and moved along the arm 210 to a second location where the golf ball 206 was held below. At this second location, the plunger 212 moved the transfer pad 214 against the primed golf ball 206 and stamped the image just printed on the ball 206.

After the ink dries, the undercoated golf ball 206 with the stamped image is
Next, it was coated with a top coat 216 having the following composition. Parts by weight Polyol (Desmophen 670-80, Bayer Corp.) 100.0 Isocyanate (Desmodur N-3200, Bayer Corp.) 30.0 Methyl amyl ketone solvent 50.0 Butyl acetate solvent 25.0 Methyl isobutyl ketone solvent 25.0 UV absorber (Sandoz 3206) 2.0 UV stable (Tinavin 292, CibaGeigy) 1.0 233.0

After increasing the temperature to cure the topcoat as shown at 218, the balls were tested for durability using the wet barrel test described above. About 80% of the ink logo remained. In this way, good sharpness, on the curved surface with the depression of the golf ball,
A distinctive and durable multicolor logo was formed.

Example 11 A water-based polyurethane primer, Witcobond 235 (CK Witco, Stamford, C
T) 100.00 parts by weight, talc (magnesium silicate) 10.0 parts by weight, amorphous silica (HiSil 532EP, PPG, Pittsburgh, PA) 1.0 part by weight and polyaziridine (Zene
(Ca Resus, Wilmington, Mass.) A golf ball with an ionomer cover coated with a primer coat for ink retention generated from 5 parts by weight was obtained. The primer coat was dried.

A solvent-based printing ink having the following formulation was prepared: 50.0 parts by weight of isopropanol, 2.0 parts by weight of ethylene glycol monobutyl ether, 15.0 parts by weight of methyl isobutyl ketone (MIBK), solvent-soluble metal complex dye, Savinyl Dyes (Clariant) 6.0 parts by weight from Corp., Coventry, RI) and polyether-modified polydimethylsiloxane, BYK 346 (BYK Chemie, Wallingfor
d, Connecticut, purchased from) 3.0 drops.

The above ink formulation was inkjet printed directly onto the primed golf ball using an Epson Stylus Color 640 inkjet printer, a drop-on-demand piezoelectric printer. As shown in FIG. 10, the drive system of the inkjet printer was mechanically modified so that printing could be performed directly on the golf ball. The remodeling was such that the paper and game ball driven to pass through the printer had the same slide or rotational speed. Referring to FIG. 10, a rotation system 305, consisting of a series of shafts connected by belts and pulleys, rotates main drive shaft 300. Game ball 310 is held by two blow-up units 315 that rotate with main drive shaft 300. The rotation system 305 advances the main drive shaft 300 at such a speed that the game ball 310 moves at the same speed as the sliding speed of a piece of paper. The ink jet print head 320 moves horizontally across the game ball 310 and prints the desired image on the game ball 310 during a series of passes.

This ink had a viscosity of about 6 cps at the time of application. A clear, durable, and shielding image was observed on the obtained golf ball.

After the ink dries, the golf ball with the image on the outer surface is then replaced with US Pat. No. 5,459,
No. 220 was coated with a solvent-based two-component aliphatic polyurethane topcoat. Upon application of the top coat, the shielding properties, clarity and coloration of the image did not change.

When the ball was subjected to a durability test using a wet barrel test, the ball was broken after 197 blows. FIG. 9 shows the results after the durability test. After the test, the ball was inspected and found to have about 80% of the ink logo remaining. In this way, a multicolored logo with good definition, distinctiveness and durability was formed on the concave curved surface of the golf ball.

The results can be compared to the results after a durability test of a conventionally stamped golf ball by pad printing using conventional solvent-based pad printable inks. FIG. 8 illustrates a golf ball that has been subjected to a wet barrel test after the identification mark has been printed with a conventional stamp. This ball was destroyed after 186 hits. After the wet barrel durability test, the ink logo remaining on the custom stamped ball of FIG. 8 was much less than the ink jet printed ball of FIG.

Example 12 The procedure of Example 11 was repeated, except that the water-based printing ink of the following formulation was replaced: water 50.0 parts by weight, isopropanol 5.0 parts by weight, Sandovac-L Dyes (Clariant Corp., 6.0 parts by weight from Coventry, RI) and polyether-modified polydimethylsiloxane, BYK 346 (BYK Chemie, Wallingfor
d, Connecticut, purchased from) 3.0 drops.

The resulting golf ball had a clear and durable image formed thereon. Although the occlusion of this image was slightly inferior to that of the image on the ball of Example 11, the use of large amounts of dye or better dispersing of the dye required Increasing the mixing intensity can improve shielding.

Comparative Test Example 3 A commercially available glycol-based ink formulation in a conventional ink-jet ink cartridge, ie, an ink formulation for an Epson Ink Jet Printer in an ink cartridge for use with an Epson Stylus Color 640 inkjet printer. The procedure of Example 11 was repeated except that the product was used. The viscosity of this ink was about 5 or 6 cps. This method did not produce acceptable images.

Example 13 A golf ball printing ink containing Formulation C was prepared. To prepare Formulation C, Formulations A and B were first prepared. Formulation A parts by weight of the epoxy - acrylate oligomer ¹ 70.0 Polyester - acrylate oligomer ² 30.0 butyl acetate 100.0 methyl isobutyl ketone (MIBK) 100.0 isopropylthioxanthone ⁸ 0.7 ethyl 4-dimethylaminobenzoate ^{9 1.5 302.2 1 Ebecryl 3700 (Rad} -Cure, Smyrna, GA) ² Ebecryl 80 (Rad-Cure, Smyrna, GA) ⁸ ITX (commercially available from Aceto Chemical, Lake Success, NY) ⁹ EDB (commercially available from Aceto Chemical, Lake Success, NY).

Formulation B parts by weight Formulation A 40.0 Savinyl dye ^* 1.0 41.0 ^* For example, one of the following: Savinyl Blue GLS, Savinyl Yello RLS, Savi
nyl Black RLSN or Savinyl Pink 6BLS (Clariant Corp., Coventry, RI)
.

Formulation C parts by weight Formulation A 20.0 Formulation B 20.0 MIBK 10.0 50.0

The ingredients of Formulation C were mixed and inkjet printed directly on the golf ball primed with the primer of Example 11 using the inkjet printer of Example 11. The drive system of the ink jet printer and the piezoelectric printer was mechanically modified so that printing could be performed directly on a golf ball.

Light source intensity about 235 watts / inch ² (36.4 watts / cm ² ) and wavelength 200-400 nm
With the identification mark placed approximately 13/4 inch (4.4 cm) from the UV light source, the ball containing the stamped identification mark is placed at a speed of 10 feet / minute (3 m / minute) at Uvex UV.
Passed through the processing equipment. The identification mark on the ball was clear and durable.

Scheduled Example 14 A golf ball printing ink containing the following was prepared. Parts by weight epoxy-acrylate oligomer ¹ 20.0 acryl-OH functional resin ² 30.0 acetate and aromatic hydrocarbon solvent blend ³ 15.0 black dye ⁴ 15.0 polyester-acrylate oligomer ⁵ 15.0 isopropylthioxanthone ⁶ 1.0 ethyl 4-dimethylaminobenzoate ⁷ 1.5 ¹ Ebecryl 3700 (Rad-Cure, Smyrna, GA) ² McWorther Resin 975 (McWorther, Inc., Carpentersville, IL) ³ Summit Ink Reducer (Pt # 910527, Summit Screen Inks, No. Kansas City, MO) ⁴ For example, Savinyl Black RLS (Clariant Corp., Coventry, RI) ⁵ Ebecryl 80 (Rad-Cure, Smyrna, GA) ⁶ ITX (commercially available from Aceto Chemical, Lake Success, NY) ⁷ EDB (commercially available from Aceto Chemical, Lake Success, NY).

Mix the components. The ink is sufficiently diluted with a solvent, such as butyl acetate, to make up a viscosity of about 1-20 cps, optionally about 5-10 cps, optionally about 5-6 cps.

The above ink formulation is inkjet printed directly on the primed golf ball using the inkjet printer of Example 11. The drive system of the ink jet printer or the piezoelectric printer is mechanically modified so that it can be directly printed on a golf ball.

Light source intensity about 235 watts / inch ² (36.4 watts / cm ² ) and wavelength 200-400 nm
With the identification mark placed about 13/4 inch (4.4 cm) from the UV light source, the ball containing the stamped identification mark is placed at a speed of 10 feet / minute (3 m / minute) by Uvex U.
Pass through V processing unit.

Next, it is coated with a solvent-based polyurethane top coat formed from polyester type hexamethylene diisocyanate.

Scheduled Example 15 The procedure of Example 12 is repeated, except that the Epson Stylus Color 640 inkjet printer is replaced with a Hewlett Packard 693C Bubble Jet (registered trademark) printer, one of the drop-on-demand printers.

Scheduled Example 16 Sandovac-L dye was used as a black pigment, Microlith Black C-WA (CIBA Specialty Ch.
emicals Corp. USA, Newport, DE) The procedure of Example 12 is repeated except that the weight is changed to 10 parts by weight. The pH of the composition is increased to at least 8.5 by adding an amine such as triethanolamine.

As will be apparent to those skilled in the art, various modifications and variations of the above-described configuration will be readily apparent without departing from the spirit and scope of the invention and the scope defined in the appended claims. Will be.

[Brief description of the drawings]

FIG. 1 shows a golf ball with an identification mark including ink jet printable ink according to the present invention.

FIG. 2 is a flowchart illustrating two methods for forming an ink jet printable identification mark on a game ball by indirect transfer.

FIG. 3 is a flowchart illustrating a method for forming an ink jet printable identification mark on a game ball using a direct printing method.

FIG. 4 schematically shows a durability test apparatus for determining the durability of the identification mark of the present invention on a golf ball.

FIG. 5 is a partial side view of a portion of an insert plate in a durability test apparatus having a groove intended to simulate a golf club surface.

FIG. 6 shows the differences in pad transfer of four UV curable inks.

FIG. 7 illustrates a method for forming identification marks on a game ball via a logo stamp machine using inks for ink jet printing.

FIG. 8 shows a golf ball after a wet barrel durability test with an identification mark printed by a conventional stamp, ie, pad printing using a conventional solvent derived pad printable ink. Show.

FIG. 9 shows a golf ball with an identification mark printed by an inkjet printer using a solvent-based (non-aqueous) ink after being subjected to a wet barrel durability test.

FIG. 10 shows a modification made to the drive system of the ink jet printer to allow adaptation to a game ball.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B41M 5/00 B41M 5/00 E B44C 1/165 D B44C 1/165 C09D 11/00 C09D 11/00 B41J 3/04 101Z (72) Inventor Green, Stephen, M. Drumlin's Terrace, Syracuse, 13224, New York, USA No. 1 F term (reference) 2C056 FB01 FB09 FD13 2H086 BA01 BA02 BA15 BA36 BA41 BA59 3B005 EA01 EB05 EC01 FA05 FA17 FB13 FB30 4J039 AD09 AD10 AD21 AE04 AE05 AE06 AE07 BA04 BA13 BA37 BE01 BE02 BE27 CA06 CA07 EA06 FA01 FA02 GA05 GA24

Claims (45)

[Claims] (A) obtaining an ink composition suitable for use in ink jet printing; (b) using an ink jet printer to deliver the ink composition in the form of an identification mark on a transfer medium; (C) transferring an identification mark from the transfer medium to a surface of the game ball, the method including forming an identification mark on the game ball. 2. The transfer medium is silicone, fluoropolymer, polypropylene,
The method according to claim 1, comprising at least one substance selected from the group consisting of: and a combination thereof. 3. The method according to claim 1, wherein the transfer medium comprises a low surface energy material. 4. The method according to claim 1, wherein the transfer medium comprises silicone. 5. The method of claim 1, wherein the transfer medium comprises a fluoropolymer. 6. The method according to claim 1, wherein the transfer medium comprises polypropylene. 7. The method of claim 1, wherein the ink composition comprises a polymer resin. 8. The method according to claim 1, wherein the ink composition comprises a resin component. 9. The method of claim 1, wherein the game ball is a golf ball. 10. The method of claim 1, further comprising: (d) forming a protective coat on the identification mark on the surface of the game ball. 11. The method of claim 10, wherein the coat comprises a polyurethane. 12. The ink composition according to claim 1, wherein the ink composition contains a UV-curable resin, and further comprising: (e) curing the identification mark after transferring the identification mark to the game ball surface. Method. 13. The method of claim 1, further comprising: (f) forming a primer coat layer on at least a portion of the surface of the game ball prior to step (b). 14. The method of claim 13, wherein the primer coat layer contains a substance that enhances at least one of the absorbency, adhesion, and clarity of the identification mark. 15. At least one of absorption, adhesion and clarity of the identification mark.
Talc, amorphous silica, bentonite clay,
15. The method according to claim 14, comprising at least one of a substance selected from the group consisting of: and magnesium silicate. 16. The method according to claim 1, wherein the transfer medium is a silicone-containing pad. 17. The method according to claim 1, wherein the transfer medium is a sheet coated with silicone. 18. An ink composition suitable for use in ink-jet printing (a) is obtained, and (b) an identification mark receiving layer is formed on at least a part of a game ball surface.
The identification mark receiving layer then contains a substance that enhances at least one of the absorption, adhesion and clarity of the identification mark, and (c) printing the identification mark on the identification mark receiving layer using an inkjet printer A method of forming an identification mark on a game ball, comprising: 19. The method according to claim 18, wherein the game ball is a golf ball. 20. The method of claim 18, wherein the identification mark receiving layer comprises polyurethane. 21. The method of claim 18, wherein the substance enhances the absorbency, adhesion, and clarity of the identification mark. 22. At least one of absorption, adhesion, and clarity of the identification mark.
Talc, amorphous silica, bentonite clay,
22. The method of claim 21, wherein the method comprises at least one material selected from the group consisting of: and magnesium silicate. 23. The method of claim 22, wherein the game ball is a golf ball. 24. The method of claim 18, further comprising: (d) forming a protective coat on the identification mark on the surface of the game ball. 25. The method of claim 18, wherein the identification marks are printed directly on the surface of the identification mark receiving layer using an inkjet printer. 26. The method of claim 18, wherein the identification mark is printed on a transfer medium using an inkjet printer, and then the identification mark is transferred to the surface of the identification mark receiving layer. 27. The identification mark receiving layer is a primer coat layer.
9. The method according to 8. 28. The method according to claim 18, wherein the identification mark receiving layer is a cover. 29. The method according to claim 18, wherein the ink composition comprises a UV-curable resin, and further comprising: (e) curing the identification mark after transferring the identification mark to the identification mark receiving layer. The described method. 30. The method of claim 18, wherein the ink composition comprises a polymer resin. 31. Obtaining a UV curable ink composition suitable for use in inkjet printing; (b) printing an identification mark on the surface of the game ball using an inkjet printer; and (c) A) curing the UV ink composition; 32. The method according to claim 31, wherein the game ball is a golf ball. 33. An identification mark is printed on a transfer medium using an ink jet printer, and then the identification mark is transferred to a surface of the game ball.
The method described in. 34. obtaining an ink composition suitable for use in inkjet printing; (b) printing an identification mark on the surface of the game ball using a drop-on-demand inkjet printer; and (c) A method of forming an identification mark on a game ball, comprising: forming a protective coat on the identification mark. 35. The method according to claim 34, wherein the drop-on-demand printer does not have electronic deflection of the ink particles. 36. The method of claim 34, wherein the resolution of the identification mark is at least about 300 dpi (about 120 dots / cm). 37. The method of claim 34, wherein the resolution of the identification mark is at least about 500 dpi (about 200 dots / cm). 38. The method of claim 34, wherein the resolution of the identification mark is at least about 600 dpi (about 240 dots / cm). 39. The method of claim 34, wherein the resolution of the identification mark is at least about 1000 dpi (about 390 dots / cm). 40. The method of claim 1, wherein the ink composition is an aqueous-based formulation. 41. The method of claim 1, wherein the ink composition is a non-aqueous based formulation. 42. The method of claim 18, wherein the ink composition is an aqueous-based formulation. 43. The ink composition according to claim 18, wherein the ink composition is a non-aqueous based formulation.
The method described in. 44. The method of claim 34, wherein the ink composition is an aqueous-based formulation. 45. The ink composition of claim 34, wherein the ink composition is a non-aqueous based formulation.
The method described in.