JP2002536085A - Game ball ink containing aluminum trihydroxide - Google Patents

Abstract

SUMMARY Disclosed herein is a game, such as a golf ball, having a seal (14) formed from a UV curable ink containing an aluminum trihydroxide (ATH) filler. The ball (8). ATH improves the ink pad transfer. An ink composition suitable for pad printing and a method for applying a seal to a game ball are also disclosed. UV curable inks have excellent pad transfer properties and excellent durability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] This application is related to US application Ser. No. 08 / 529,361, filed Sep. 18, 1995.
No. 08 / 753,704, filed Nov. 27, 1996.

BACKGROUND OF THE INVENTION The present invention relates generally to inks, and more particularly to UV curable inks.

[0003] UV-curable inks are fast-curing inks and are therefore advantageous for use in continuous processes involving the subsequent processing of ink-printed substrates. Numerous UV curable inks are known. For example, US Pat.
No. 271,258 discloses a photopolymerizable ink composition containing an acrylate resin, a methacrylate monomer or oligomer, an acrylate monomer or oligomer, a photopolymerization initiator and a specific type of epoxy resin. US Patent 5,391,
No. 685 discloses a UV curable ink to which an isocyanate compound is added. U.S. Pat. No. 5,391,685 discloses that the inks disclosed therein are well suited for printing on slightly adherent plastic bases, such as those made of polyoxymethylene and polypropylene. Insists that.

[0004] Screen printing on a spherical surface, such as a golf ball, can be difficult. As a result, pad printing is conventionally used to make markings on golf ball surfaces. However, many of the known UV curable inks are
Transferring ink from the pad to the substrate is difficult and is not well suited for pad printing. Moreover, pad-printable UV-curable inks are not considered suitable for use on golf balls. More specifically,
When applied to golf balls, these inks do not have sufficient durability (impact resistance) to withstand multiple hits by golf clubs. Durability such that when used to print a seal on a surface, such as a curved, dimpled surface of a golf ball, it has an advantageous pad transfer characteristic and yet provides an image with good durability. It would be useful to obtain a UV curable ink with a very high UV curability.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a new and improved UV curable ink.

Another object of the present invention is to provide a UV curable ink that is particularly suitable for application by pad transfer.

[0007] It is a further object of the present invention to provide a fast-curing ink for use on game balls such as golf balls and on hard surfaces of other sports equipment, thereby enabling faster production. It is in.

It is another object of the present invention to provide a pad printable UV curable ink having excellent impact resistance.

It is still another object of the present invention to provide a game ball, such as a golf ball, having a transparent and durable ink image printed thereon.

[0010] It is a further object of the present invention to provide a method for pad printing a stamp comprising a UV curable ink on a hard surface of a game ball, golf club, bat or racket.

Yet another object of the present invention is to provide a method for applying a stain resistant and durable seal to the visible surface of a game ball.

[0012] Other objects of the invention will in part be apparent hereinafter and in part will be pointed out in more detail.

The present invention in a preferred form is a game ball with an imprint comprising one surface and a UV curable ink adhered thereto, the UV curable ink containing aluminum trihydroxide. The impact resistance of the ink and the adhesion between the seal and the surface are sufficient to make the game ball suitable for use in playing in competitions.

The seal can be applied directly to the cover of a one-piece, two-piece or multi-piece game ball. Alternatively, one or more primers may be positioned between the game ball cover and the seal. In addition, one or more finish coats are positioned on the seal. This seal shows that at least about 50%, preferably at least about 70%, and more preferably at least about 80% of the surface area of the original image after the game ball has been subjected to the wet barrel resistance test procedure described below. It has enough durability to remain on the ball.

[0015] Another preferred form of the present invention is a UV curable ink composition. The ink composition comprises a UV curable resin, an appropriate amount of aluminum trihydroxide, a colorant such as a pigment or dye to provide improved pad transfer, and a polymerization initiator for the UV curable resin. Contains a photopolymerization initiator. The ink composition forms a cured seal having adhesion properties and impact resistance that make it suitable for use in game balls to be used in competition play. A diluent containing monomers and / or solvents is also preferably included. Also, wetting agents and / or bulking agents can be added. To facilitate pad transfer, the inks should be applied at 1,000-28,
It has a viscosity of from 2,000 centipoise, preferably from 1,000 to 4,000 centipoise, more preferably from 1,000 to 2,000 centipoise.

Still another preferred embodiment of the present invention is a method for imprinting a game ball. This method comprises (a) a colorant such as a pigment or a dye, aluminum trihydroxide, a photopolymerization initiator and a UV-curable resin, and comprising 1,000 to 280
00, preferably obtaining a UV curable ink composition having a viscosity of 1,000 to 4,000 centipoise, (b) applying the ink composition to a game ball in the form of a seal, (c) curing. Curing the ink composition to form a coated film, and (d) applying a coating on the ink. The seal has sufficient impact resistance to make the game ball suitable for use in competition play. The ink is preferably applied by pad printing. The UV curing step preferably includes placing the seal under a UV lamp under conditions of sufficient lamp intensity, lamp distance and time to initiate curing of the ink. Curing is preferably completed substantially within about 1 second. A fully cured ink is preferably (
However, it is not always necessary that the hardness is 14 to 40 (AST).
M-D2134-66).

Accordingly, the present invention is directed to a plurality of stages, and the relationship between one or more of such stages and each of the other stages, and the features exemplified in the following detailed disclosure. Includes items that have characteristics and elemental relationships.

DETAILED DESCRIPTION OF THE INVENTION The UV curable inks of the present invention are unique in that they exhibit a combination of advantageous transfer properties and excellent durability or impact resistance. The ink is a golf ball,
Used to print seals on softball, baseball, other game balls, and other sports equipment including, but not limited to, softball and baseball bats, tennis and racquetball rackets, and golf clubs. can do. The ink can also be applied to a variety of materials, including but not limited to ionomers, polybutadienes, composites, metals, and the like.

As described above, the ink contains a UV curable resin, a colorant such as a pigment or a dye, aluminum trihydroxide, and a photopolymerization initiator. A diluent containing monomers and / or solvents can be added. If necessary, wetting agents can also be included.

The UV-curable resin preferably contains an oligomer. Non-limiting examples of oligomers include one or more epoxies, acrylics, acrylated urethanes, elastic acrylates, unsaturated polyesters and polyethers. Specific examples of suitable oligomers include methacrylates such as bisphenol A ethoxylate dimethacrylate and acrylated epoxies. Mixtures of different oligomers can be used. The oligomer must provide the ink with sufficient flexibility and impact resistance properties to withstand the conditions to which it is applied. For example, where the substrate is a golf ball and optimal durability is desired, the oligomer must impart greater flexibility to the ink than is inherent in the underlying substrate. If a finish is placed over the ink, the ink should not undergo such a high level of crosslinking that the adhesion of the finish to the ink is substantially prevented.

The uncured ink is preferably about 10-90% by weight oligomer, more preferably about 20-80% by weight oligomer, and most preferably about 50-70% by weight.
Oligomers.

The colorant can be any type of pigment, dye, etc. that is resistant to UV treatment, ie not UV-labile. Further, the colorant initiates photocrosslinking,
Any combination of transmission, reflection or refraction mechanisms must allow for sufficient passage of UV light through the ink. Both liquid and powder can be used. One preferred form of the ink is a powder dispersed in a liquid monomer. Carbon black and iron oxide black are non-limiting examples of suitable pigments for making black ink. Red lakes and quinacridones are non-limiting examples of suitable pigments for making red inks. Mixtures of different pigments and / or dyes can also be used. The uncured ink preferably contains about 2 to 60% by weight pigment, more preferably about 5 to 30% by weight, and most preferably about 5 to 10% by weight pigment.

The photoinitiator is selected to be responsive to the wavelength of the UV radiation to be used for photoinitiation. As described above, since UV light needs to enter the ink composition to initiate curing, it is also important to consider the color of the ink when selecting a photopolymerization initiator. More specifically, penetration is required to cure the portion of the ink below the surface. Penetration is usually the most difficult when black or white pigments are used. Non-limiting examples of photoinitiators to be used in conjunction with black pigments include isopropylthioxanthone and sulfur-based photoinitiators such as benzophenone and its derivatives of the acetophenone type and thioxanthone. Photoactive agents can also be used in conjunction with one or more photoinitiators. Non-limiting examples of suitable photoactivators include amine photoactivators such as ethyl 4-dimethylaminobenzoate. The uncured ink preferably contains about 0.3-5% by weight, more preferably about 1-4% by weight, most preferably about 3-4% by weight of a photoinitiator. Different photoinitiators or blends of photoinitiators and photoactivators can also be used.

A diluent is added as needed to reduce the viscosity of the uncured ink composition or contribute to impact resistance or flexibility. If a monomer is used as a diluent, it must be a photopolymerizable monomer that forms a polymer structure upon irradiation. In contrast, when solvents are used as diluents, they evaporate during curing. The monomers may be mono-, di- or tri-functional acrylates. Non-limiting examples of suitable monomers include 1,6 hexanediol diacrylate, butanediol diacrylate, trimethylolpropane diacrylate, tripropylene glycol diacrylate, and tetraethylene glycol diacrylate. .

The uncured ink is preferably about 10-70% by weight, more preferably about 10-6%
It contains 0% by weight and most preferably about 10 to 55% by weight of monomer. Preferably, the combination of monomers and oligomers comprises about 45-80%, more preferably about 50-80%, and most preferably about 60-80% by weight of the uncured ink.

A non-UV curable quick-drying resin can be added to assist in transferring the ink from the pad to the ball. Non-limiting examples of such resins are vinyl resins, nitrocellulose, acrylic resins and other fast drying film forming resins. One preferred resin is Resi by Mc Worther, Inc of Carpentersville, Illinois.
Acrylic-OH functional resin sold as n975. Typically, when such resins are used, they are added in amounts up to about 30 parts by weight, based on 100 total parts by weight of the uncured ink composition.

When a solvent is used, it typically makes the ink sticky at the point of partial evaporation, thereby providing a high to medium evaporation rate that promotes transfer onto and out of the ink pad. It has a liquid. The solvent may be a medium in which the photopolymerization initiator 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 is preferably about 1-30% by weight solvent, more preferably about 5-20%.
%, Most preferably about 8 to 10% by weight of solvent.

If necessary to prevent the ink from spheroidizing when applied to the golf ball, a wetting agent can be added. Suitable wetting agents also include, but are not limited to, silicone surfactants and fluorocarbon surfactants. The uncured ink preferably contains about 0-2% by weight of a wetting agent. Other additives that do not adversely affect the pad transfer and impact resistance of the ink can also be incorporated into the ink composition.

[0029] Extender pigments such as talc, barium sulfate and the like can be added as long as sufficient durability is maintained. Such materials can be used to improve transferability. Typically, when such materials are used, they make up about 10-40%, or more preferably 20-30%, by weight of the uncured ink formulation.

Printing, curing and treating by replacing some or all of the extender pigments such as talc and barium sulfate with aluminum trihydroxide (Al ₃ O ₃ (H ₂ O) ₃ ) (ATH) filler Has been found to result in a number of significant improvements over UV inks. In addition, ATH includes:
Has little effect on the color of the ink. In addition, ATH has a low oil absorption and therefore the ink viscosity is only slightly increased. When up to 50% by weight of ATH is added, based on the total (uncured) ink weight, the transfer of ink from the pad to the substrate is improved. Significantly, ATH does not absorb UV light and therefore does not hinder the curing of the ink.

When ATH is used 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.
Preferably, ATH is present in an amount of 10 to 32% by weight, more preferably 20 to 30% by weight.
Used in the quantity. ATH additions of up to at least 50% by weight, based on the weight of the (uncured) ink, can be useful for an overall balance of properties. If low cost inks are desired and durability requirements are not critical, more ATH
Can be used. The higher the durability required, the lower the quantity of ATH is useful. ATH is preferably used in an amount suitable to impart a balance of properties such as ink pad transfer and durability to the ink. The ATH used has, for example, a narrow particle size distribution with a median particle size of about 1 micron. However, intermediate particle sizes can range from at least only 0.25 microns to at least 50
It can be as large as a micron.

When ATH is used in combination with talc, barium sulfate, etc., the ratio of ATH to talc is preferably 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. The surface tension of the ink must not be substantially higher than the surface tension of the substrate to be printed. The viscosity of the ink will determine the thickness of the seal on the cover. If the stamp is too thick, the UV radiation will not penetrate into the stamp and complete curing may be difficult. On the other hand, if the seal is too thin,
The durability of the ink layer may be insufficient for play conditions. The seal is 10
Less than 0 microns, preferably about 10-40 microns, more preferably 13-30
Micron, and most preferably 20-25 microns thick.

The cured ink should have sufficient flexibility to exhibit good impact resistance. It is advantageous for the finish applied over the ink to react with the ink and hold the ink in place or to have adhesion by hydrogen bonding and / or Van der Waals forces. By way of non-limiting example, it can be used in conjunction with two-component polyurethane finishes, such as those based on aliphatic isocyanates such as hexamethylene diisocyanate or isophorone diisocyanate trimer and polyester or acrylic polyols.

[0035] The finish may be applied to the seal to protect it unless the seal has sufficient adhesion to the surface to which it is applied, such as a cover or subbing layer, so that the use of the finish is not required. Is essential. The adhesion between the ink and the topcoat and / or substrate should be strong enough so that the seal remains substantially intact when the game ball is used. The criteria for image retention are governed by the intended use of the game ball and the degree and frequency of impact that the image must withstand. When applied to a golf ball, the durability of the ink should be at least 50% of the surface area of the original image after the ball has undergone the wet barrel resistance test described below.
%, More preferably at least 70%, and most preferably at least 80%
Must be enough to remain.

The UV curable ink formulation of the present invention used for marking golf balls is prepared and used as follows. The photoinitiator is dissolved in a diluent, which is then mixed with the oligomer, pigment and aluminum trihydroxide. The mixture is placed in an open or closed cup dispenser of the pad printing device. A primed but unfinished golf ball is obtained.
The ball 8 shown in finished form in FIG. 1 includes, for example, a core 10 and a durable cover layer 12 having a dimpled surface. Alternatively, the core and the cover can be formed in one piece. A seal 14 made of UV curable ink is pad-printed on the golf ball cover 12. The ink imprint may be stamped directly on the cover or may be stamped on a primer placed on the cover. Thereafter, the unfinished golf ball is subjected to UV treatment under conditions sufficient to initiate curing of the ink. After initiation of photopolymerization, curing of the ink is substantially completed within a time period of less than one second to several seconds.

After the ink has cured, a finish coat 16 is applied over the ink stamp. Finish coating layer 16
Helps maintain the seal on the golf ball surface as described above, and thus the adhesion of the seal to the golf ball is as high as would be required if the ink constituted the outer layer of the ball. No need to be strong. Finish coats are typically 10-40
It has a thickness of microns.

Conditions for UV exposure suitable for curing the ink can be ascertained by those skilled in the art. For example, if the golf ball is at a speed of 10 feet / minute,
When passing through a UV treatment instrument at a distance of about 1 1/4 to 1 3/4 inch from a UV light source having an intensity of ~ 300 watts / in ² , the seal takes less than a few seconds, preferably about 1
It should be exposed to UV radiation for less than a second, and more preferably less than about 0.7 seconds. Higher and lower UV lamp intensities can be used as long as the cured ink meets applicable durability requirements. Excess UV exposure is avoided to prevent degradation of the base. Prior to applying any finish,
UV cured.

The pad to be used for the transfer of the UV ink preferably contains silicone. This kind of pad has excellent elasticity, durability and flexibility and appropriate surface tension. Other types of pads can be used.

The ink can be applied on a non-UV-unstable surface of the game ball.
According to the present 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 a very smooth surface that has poor transfer on the surface, the part of the surface to be stamped may be chemically or physically etched or abraded to remove the ink receiving surface. Can be provided.

The inks of the present invention have a post-cure hardness (ASTM-D2134-66) of 55 or less, more preferably 40 or less, and most preferably about 20 or less. The UV curable inks of the present invention provide sufficient durability to meet the stringent durability standards required for commercial grade golf balls. Ink durability can be determined by testing a stamped golf ball in a variety of ways, including using a wet barrel resistance test procedure.

Durability according to the wet barrel resistance test procedure is determined by firing a golf ball at 135 feet / second (72 ° F.) into a five-sided steel pentagonal container with steel plate walls. You. The container 110, shown schematically in FIG. 2, has a 19.5 inch long insert plate 112 mounted therein, the central portion 114 of which defines the square grooved surface of the golf club. It has a horizontally extending square groove intended to simulate. The grooves shown in exaggerated form in FIG. 3 have a width 130 of 0.033 inches, a depth 132 of 0.100 inches, and are separated from each other by land areas 134 having a width of 0.130 inches. I have.
The five walls 116 of the pentagonal container are each 14.5 inches long. The inlet wall is vertical and the insert plate is mounted in such a way that it is inclined 60 ° upward relative to a horizontal plane away from the opening 120 in the container 110. The ball travels horizontally 15 1/2 to 15 3/4 inches into the container 110 from its entry point until it hits the square grooved central portion 114 of the insert plate 112. The angle between the ball trajectory line and the insert plate 112 is 30 °. The ball is subjected to 70 or more hits (launches) and is inspected at regular intervals for breakage (ie, cracks in the cover or any signs of delamination). If a microcrack forms in the ball, its speed will change and the operator will be alerted. At this time, the operator visually inspects the ball. If microcracks are still not observable, the ball is returned to the test until cracks can be visually detected. The ball is then inspected for ink adhesion.

Although the present invention has been described generally, the following examples are included for illustrative purposes so that the present invention can be more easily understood, and these are in any form unless otherwise specified. It is not intended to limit the invention.

Example 1 A golf ball printing ink was prepared containing the following: 5 parts by weight of 1,6 hexanediol diacrylate (Sartomer, Exton, PA193)
17.5 parts by weight of Carbon Black UV Dispersion 99B415 (Penn Color,
Black pigment paste in diacrylate monomer sold as Doylestown, PA. 35 parts by weight of an aliphatic urethane acrylate oligomer (Sartomer, Exton, PA)
CN965 sold by A19341), 0.5 parts by weight of isopropylthioxanthone, a sulfur-based photopolymerization initiator,
C ₁₆ H ₁₄ OS, an IT sold by Aceto Chemical, Lake Success, NY
X), 1 part by weight of an amine photoactivator ethyl 4-dimethylaminobenzoate, C ₁₁ H ₁₅ NO ₂ (EDB sold by Aceto Chemical, Lake Success, NY), 4.4 parts by weight Xylene solvent, and 4.4 parts by weight of butyl acetate solvent.

The photoinitiator and photoactivator were dissolved in a xylene / butyl acetate solvent formulation. The ink was pad-printed with a silicone pad on an unprimed, dimpled ionomer cover of several dozen golf balls. The viscosity of the ink was about 27,500 (centipoise) cps at the time of application. The ball containing the stamped stamp was placed 10 feet using a lamp intensity of 235 watts / in ² and a wavelength range of 200-400 nm, with the stamp positioned about 13/4 inches from the UV light source. At a rate of / min into a Uvex UV processor Lab 14201. The ink cured in less than about 1 second and had a hardness of about 14 after curing was complete. The golf ball was then coated with a solvent-based polyurethane finish formed with hexamethylene diisocyanate of the polyester type. The seal adhesion on the ball was tested for durability according to the wet barrel resistance test procedure described above. After the wet barrel resistance test, the balls were inspected and found to have removed no more than about 20% of the surface area of the original ink logo.

Example 2 The procedure of Example 1 was repeated, except that the ink formulation used contained the following: 10 parts by weight of 1,6 hexanediol diacrylate (sold by Sartomer), 35 parts by weight of black pigment paste in diacrylate monomer sold as Carbon Black UV Dispersion 99B415, 70 parts by weight Bifunctional aliphatic urethane acrylate oligomer (Ebecryl 48
33 RedCure, Smyrna, GA) 1 part by weight of sulfur-based isopropylthioxanthone, C ₁₆ H ₁₄ OS (ITX)
And 2 parts by weight of ethyl 4-dimethylaminobenzoate (EDB). The ink had a viscosity of about 25,000 cps. The ink cured within about 1 second and produced a film with a sword hardness of about 12. The balls were subjected to a wet barrel resistance test procedure. After the wet barrel resistance test, it was found that less than about 20% of the ink logo was removed.

Example 3 The procedure of Example 1 was repeated except that the CN965 oligomer was replaced by a bifunctional oligomer sold as Ebecryl 8402 (Rad-Cure, Smyrna, GA). The ink had a viscosity of about 18,000 cps. The ink cured within about one second and produced a film with a sword hardness of about 14. The ink was found to be about as durable as that of Examples 1 and 2.

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

[0049] The ink was applied directly to the ionomer cover of the golf ball and was also applied to the ionomer cover with an aqueous polyurethane subbing layer prior to application of the ink. The ink cured within about one second and produced a film with a sword hardness of about 14. The balls were finish coated and subjected to a wet barrel resistance test procedure. After the wet barrel resistance test, it was found that less than about 20% of the ink logo was removed.

Comparative Example 1 A commercially available UV curable ink, ie, Blk # 700801 (Trans Tech, Caro
l Stream, IL) was used, except that the procedure of Example 1 was used. The viscosity of the ink was about 6,000 cps. The ink cured within about one second and produced a film with a sword hardness of about 26. After the wet barrel resistance test, only the logo outline remained. Most of the ink in the dimples and on the land area was removed. The adhesion between the coating layers of the ink and the finish coat was weak.

Comparative Example 2 A commercially available UV curable ink, ie, L-526-163-B (Qure Tech, Sea
brook, NH), except that the procedure of Example 1 was repeated on a plurality of golf balls. The ink had a viscosity of about 28,500 cps. The ink cured within about 1 second, producing a film with a sword hardness of about 20. At least about 60% of the surface area of the logo was removed as a result of the wet barrel resistance test. The ink appears to be very brittle to withstand the conditions of the wet barrel resistance test.

Example 5 An ATH-containing formulation 1 shown below 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 ³ 270.3 100.0 ¹ McWorther Resin 975 (McWorther, Inc., Carpentersville, IL) ² Summit Ink Reducer, Summit PT # 910527 (Summit Screen Inks, No.
Kansas City, MO) Alternatively, 43.4 parts by weight of butyl acetate, 28.3 parts by weight of xylene and 28.
Mixtures based on 3 parts by weight of propylene glycol monomethyl ether acetate can also be used. ³ ATH SpaceRite S-3 (ALCOA Industries, Bauxite, AR)

Next, using ATH-containing formulation 1, a golf ball ink containing the following was formed. 5 parts by weight of an aliphatic urethane triacrylate (BR-990, Bomar Specia
lties Co., Winsted, CT), 35 parts by weight of an ATH containing formulation 1, 5.5 parts by weight of trimethylolpropane triacrylate (TMPTA) (Sartomer
Co., West Chester, PA), 5 parts by weight black dispersion in oligomers / monomers (ICU386, Industrial Col.
or Inc., Joliette, IL), 0.3 parts by weight of isopropylthioxanthone, a sulfur-based photopolymerization initiator,
C ₁₆ H ₁₄ OS, an IT sold by Aceto Chemical, Lake Success, NY
X), 1 part by weight of an amine photoactivator, ethyl 4-dimethylaminobenzoate, C ₁₁ H ₁₅ NO ₂ (EDB sold by Aceto Chemical, Lake Success, NY), 10 parts by weight of ATH (SpaceRite S-3, ALCOA Industries, Bauxite, AR)

All components were mixed and dispersed on a high-speed mixing device.

Inks were pad-printed with a silicone pad on an unprimed, dimpled ionomer cover of several dozen golf balls. The ball containing the stamped stamp was placed on a ball with the stamp positioned at about 1 3/4 inch from the UV light source and a lamp intensity of 235 watts per square inch and 200-400.
It was passed through a Uvex UV lamp at a speed of 10 feet / min using a wavelength range of nm.
The ink cured in less than one second. Next, the golf ball was coated with a two-component polyester / aliphatic polyisocyanate clear coat. The printability, color density (jetness), detailed image, pad release and durability of the ink were evaluated. Control A, Control B
And three sets of control inks, designated Control C. The formulations of the Control A and Control B inks are shown below.

Control A Parts by Weight Aliphatic Urethane Acrylic Oligomer ¹ 6.45 Acrylic-OH Functional Resin ² 42.96 Acetate and Aromatic Hydrocarbon Solvent Formulation 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 ) ICU386 (Industrial Color Inc., Joliette, IL) ⁷ (Sartomer Co., West Chester, PA) ⁸ ITX (Distributor: Aceto Chemical, Lake Success, NY) ⁹ EDB (Distributor: Aceto Chemical, Lake Success, NY) NY)

Control B parts by weight Epoxy acrylate oligomer ¹ 19.24 Acrylic-OH functional resin ² 27.70 Acetate and aromatic hydrocarbon solvent formulation 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 ) ICU386 (Industrial Color Inc., Joliette, IL) ⁷ Ebecryl 80 (Rad-Cure, Smyrna, GA) ⁸ ITX (Distributor: Aceto Chemical, Lake Success, NY) ⁹ EDB (Distributor: Aceto Chemical, Lake Success) , NY)

Control C is Trans Tech Ink # 2P37-2 (Trans Tech, Carol Stream, IL)
)Met. The ratings for the various ink formulations are shown below.

[0060]

[Table 1]

The rating is from 1 to 5, where 1 is ideal and 5 is unacceptable. The ball of Example 5 and the balls of Controls A, B and C are all covered with 160 mg of a one-layer finish coat system, the finish coat being a clear coat of a two-component polyester / aliphatic polyisocyanate.

The ink of Example 5 has an oligomer / monomer content of 22.608%, 21.508%
Acrylic resin content, 3.08% by weight black pigment content, 31.63% by weight A
It had a TH pigment content, a solvent content of 20.008% and a polymerization initiator content of 1.62% by weight. The density of the ink was 10.68 pounds / gal, the total nonvolatile content was 80%, and the volatile organic compounds comprised 2.14 pounds / gal. The viscosity of the ink was 11,000 centipoise at the time of application. After curing,
The stain resistance of the ink was tested using a methyl ethyl ketone solvent. No spots occurred.

It has been found that the solvent content of the ink can be significantly increased without degrading the quality of the identification stamp. For example, reducing the ink by an additional 30% (by adding a solvent) will reduce the viscosity of the ink to about 1420 centipoise. Inks with this low viscosity tend to have better printability than higher viscosity inks on certain pad printing presses.

FIG. 4 shows the silicone pad 12 after twelve golf balls have been stamped with a particular type of ink. FIG. 4-A shows the stamp after stamping with the control A ink. FIG. 4-B shows the silicone pad after stamping with the control B ink. FIG. 4-C shows the pad after being stamped with the ink of Example 5.
FIG. 4-D shows the pad after stamping with Control C. As shown in the resulting stamp, the best transfer, ie, the result that the amount of ink remaining on the stamp was minimal, was obtained by using the ink of Example 5.

Example 6 An ATH containing formulation 2 shown below 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, IL) ² Dow Chemical (and others) ³ ATH SpaceRite S-3 (ALCOA Industries, Bauxite, AR) ⁴ Van Talc # 6H (Vanderbilt, Norwalk, CT) ⁵ ICU386 (Industrial Color Inc., Joliette, IL)

After mixing the formulation, the following ingredients were added: 1.31 parts by weight of butyl acetate (Eastman Chemical et al.) 6.16 parts by weight of Aromatic 100 or HiSol 53 (Ashland Chemicals), 3.08 parts by weight of cyclohexanone (Ashland Chemicals), 0.5 parts by weight of isopropylthioxanthone, a sulfur-based photopolymerization initiator,
C ₁₆ H ₁₄ OS, an IT sold by Aceto Chemical, Lake Success, NY
X), 1 parts by weight, amine ethyl 4-dimethylaminobenzoate a photoactive _{agent, C 11 H 15 NO 2 (} Aceto Chemical, Lake Success, EDB sold by NY), 5.78 parts by weight Of aliphatic urethane triacrylate (UV curable resin) (Bo
(BR-990 sold by mar Specialties Co., Winsted, CT) and 5.78 parts by weight of trimethylolpropane triacrylate (UV curable resin) (TMPTA) (Sartomer Co., West Chester, PA). Sold)
.

The total weight was 100. All components were mixed and dispersed using a high speed mixer.

[0069] Inks were pad printed with a silicone pad on an unprimed, dimpled ionomer cover of a number of golf balls. A golf ball containing the stamped stamp is placed on a golf ball with the stamp positioned at about 1 3/4 inch from the UV light source and a lamp intensity of 235 watts per square inch and 200-400.
It was passed through a Uvex UV lamp at a speed of 10 feet per minute using a wavelength range of nm.
The ink cured in less than one second. The golf ball was then coated with a two-component polyester / aliphatic polyisocyanate clearcoat and subjected to a wet barrel resistance test procedure. After the wet barrel resistance test, it was found that less than about 20% of the ink logo 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) contained only 0.22 parts by weight of black dispersion ¹ in the oligomer / monomer, Example 6 except that it also contained 8.16 parts of the first red dispersion ² in the oligomer / monomer and 2.62 parts of the second red dispersion ^{3 in} the oligomer / monomer. Procedure was repeated. All components were mixed and dispersed using a high speed mixer. The total weight was 100. ¹ ICU 386 (Industrial Color Ink, Joliette, IL) ² ICU Red Lake C (Industrial Color Ink, Joliette, IL) ³ ICU Lithol 388 Red (Industrial Color Ink, Joliette, IL)

Inks were pad-printed with a silicone pad on an unprimed, dimpled ionomer cover of a plurality of golf balls. A golf ball containing a stamped stamp is placed with a lamp intensity of 235 watts per square inch and 200 to 40 with the stamp positioned about 13/4 inches from the UV light source.
It was passed through a Uvex UV lamp at a speed of 10 feet per minute using a wavelength range of 0 nm. The ink cured in less than one second. The golf ball was then coated with a two-component polyester / aliphatic polyisocyanate clearcoat and subjected to a wet barrel resistance test procedure. After the wet barrel resistance test, it was found that less than about 20% of the ink logo was removed.

Example 8 An ATH-containing formulation 3 shown below 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 following materials were added. 5.69 parts by weight of red dispersion in oligomer / monomer (ICU Red Lake C,
Industrial Color Inc., Joliette, IL, 1.92 parts by weight of red dispersion in oligomers / monomers (ICU Lithol Rubine)
, Industrial Color Inc., Joliette, IL), 0.47 parts by weight of black dispersion in oligomer / monomer (ICU 386, Industrial)
rial Color Inc., Joliette, IL), 0.49 parts by weight of a sulfur-based photoinitiator, isopropylthioxanthone, C ₁₆ H ₁₄ OS, (I sold by Aceto Chemical, Lake Success, NY)
TX), 1.14 parts by weight, amine photoactive agent a is ethyl 4-dimethylamino _{benzoate, C 11 H 14 NO 2 (} Aceto Chemical, Lake Success, EDB sold by NY), 8.14 Parts by weight of an aliphatic urethane triacrylate (BR-990) (Boma
r Specialties Co., Winsted, CT) and 8.95 parts by weight of trimethylolpropane triacrylate (TMPTA) (SMPTA).
artomer Co., West Chester, PA).

The total parts by weight was 99.99.

To provide optimal printing, a solvent made 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 amount of ink before viscosity reduction)
By adding 15% by weight, the viscosity of the ink was reduced to 1200 centipoise.

The ink was printed on a plurality of golf balls. The golf ball was then coated with a two-component polyester / aliphatic polyisocyanate clearcoat and subjected to a wet barrel resistance test procedure. After the wet barrel resistance test, it was found that less than about 20% of the ink logo was removed. The first printed ball had a sharp image. After aging, some pseudoimages appeared.

Example 9 An ATH-containing formulation 4 shown below 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 Black dispersion in oligomer / monomer ⁶ 0.61 Xylene solvent 3.80 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 Ink, Joliette, IL) ⁵ ICU Lithol Rubine 388 (Industrial Color Ink, Joliette, IL) ⁶ ICU386 (Industrial Color Inc., Joliette, IL)

After mixing, the following materials were added: 3.80 parts by weight of propylene glycol monomethyl ether acetate solvent; 0.38 parts by weight of isopropylthioxanthone, a sulfur-based photoinitiator, C ₁₆ H ₁₄ OS, sold by Aceto Chemical, Lake Success, NY I
TX), 0.86 parts by weight of the amine photoactivator ethyl 4-dimethylaminobenzoate, C ₁₁ H ₁₄ NO ₂ (EDB sold by Aceto Chemical, Lake Success, NY), 5.69 Parts by weight of an aliphatic urethane triacrylate (BR-990) (Boma
r Specialties Co., Winsted, CT) and 5.69 parts by weight of trimethylolpropane triacrylate (TMPTA) (SMPTA).
artomer Co., West Chester, PA).

The total parts by weight was 100.02.

The ink was printed on a plurality of golf balls. The image was very dark.
It is believed that a satisfactory image was probably obtained by using a lower level of black variance. The golf ball was then coated with a two-component polyester / aliphatic polyisocyanate clearcoat and subjected to a wet barrel resistance test procedure. After the wet barrel resistance test, it was found that less than about 20% of the ink logo was removed.

As will be apparent to those skilled in the art, various modifications and adaptations of the above-described structure will be readily apparent without departing from the spirit and scope of the invention. The scope of the present invention is defined in the appended claims.

[Brief description of the drawings]

FIG. 1 shows a game ball having a seal comprising a UV curable ink according to the present invention.

FIG. 2 schematically shows a durability test apparatus for determining the durability of the seal of the present invention on a golf ball.

FIG. 3 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 ball surface.

FIG. 4 shows the difference in pad transfer for four UV curable inks.

Claims (22)

[Claims] 1. A game ball having a surface and a stamp attached thereto, wherein the stamp comprises a UV curable ink containing aluminum trihydroxide, wherein the impact resistance of the ink and the adhesion between the stamp and the surface are determined. A game ball that is sufficient to make the ball suitable for use in competition play. 2. The game ball according to claim 1, wherein the game ball is a golf ball. 3. The game ball according to claim 1, wherein the UV curable ink is a pad transferable ink. 4. The game ball of claim 1, wherein the surface to which the seal is applied includes a finish. 5. The game ball according to claim 3, wherein the finish coat is formed on the seal. 6. The game ball according to claim 2, wherein after being subjected to the wet barrel durability test means, ink in a portion of about 50% or more of the surface area of the seal is retained. 7. The game ball according to claim 2, wherein after being subjected to the wet barrel durability test means, the ink in a portion of about 70% or more of the surface area of the seal is retained. 8. The game ball according to claim 1, wherein after being subjected to the wet barrel durability test means, the ink in a portion of about 80% or more of the surface area of the seal is retained. 9. The game ball according to claim 2, wherein after being subjected to the wet barrel durability test means, ink in a portion of about 80% or more of the surface area of the seal is retained. 10. A UV curable resin, an aluminum trihydroxide in an amount suitable to provide improved pad transfer to the ink composition, a colorant, and photopolymerization to initiate polymerization of the UV curable resin. U to form a cured seal having adhesion properties and impact resistance such that the seal is suitable for use on a game ball to be used in competition play.
V-curable ink composition. 11. The UV-curable ink composition according to claim 10, which contains 10 to 50% by weight of aluminum trihydroxide. 12. The UV-curable ink composition according to claim 10, further comprising a diluent. 13. The UV-curable ink composition according to claim 11, wherein the diluent contains at least one constituent material selected from the group consisting of a monomer and a solvent. 14. The UV curable ink composition according to claim 10, wherein the UV curable resin comprises 10 to 90% by weight of the oligomer. 15. A composition having a viscosity of about 1,000 to 28,000 centipoise.
The UV-curable ink composition according to claim 10. 16. The UV curable ink composition according to claim 10, comprising 2 to 60% by weight of a colorant and 1 to 5% by weight of a photopolymerization initiator. 17. The UV-curable ink composition according to claim 10, further comprising a non-UV-curable resin. 18. A. Obtaining an ink composition containing a colorant, aluminum trihydroxide, a photopolymerization initiator, and a UV curable resin, b. Applying the ink composition in the form of a seal by pad printing; c. Curing the ink composition to form a cured film; and d. Applying a coating on the ink, the method comprising the steps of: applying a seal to a game ball, wherein the seal has sufficient impact resistance to render the game ball suitable for use in competition play. A method that has character. 19. The method of claim 18, wherein the ink further comprises a diluent. 20. The method of claim 18, wherein the UV curable resin comprises an oligomer. 21. The method of claim 18, wherein the game ball is a golf ball. 22. When the golf ball is subjected to the wet barrel resistance test procedure, ink is retained on at least about 80% of the seal surface area,
22. The method of claim 21, wherein the ink is formulated and cured.