This invention is directed to a method for forming an inked image on game balls, golf balls, and the like, through the use of novel curable inks that are low energy curable and require minimal curing through multiple source radiation curing processes, such as UV radiation, visible radiation, and electron beam radiation. Production inks, logo inks, and methods for forming production prints and logos on golf balls, game balls, and the like are disclosed.

The present invention is directed to a process of curing radiation curable inks applied to curved surfaces including spherical surfaces with ultraviolet (UV) and/or visible light and curing with electron beam. More particularly, the invention is directed to a combination of UV light and/or visible light and electron beam curing of radiation curable inks and their application to and curing upon game balls, golf balls and the like. These inks are preferentially applied as single or multiple, clear or color layers for forming logos or production prints on game balls including golf balls.
It is often desirable to apply clear, pigmented or dyed ink coatings or layers to form distinctive logos or production prints on game balls (e.g., golf balls, ping pong balls, billiard balls, baseballs, basketballs, racquet balls, handballs, etc.). Various commercially available inks are commonly used for this purpose.
To clarify the difference between logo printing and production printing, a brief description of these processes as they are applied to game balls such as golf balls (e.g., having curved surfaces) is provided below. Golf balls are commonly one-piece, two-piece or three-piece constructions. One-piece balls are made from a homogeneous polymer shaped into a golf ball. Two-piece golf balls comprise an inner core and an outer surrounding polymeric shell. Three-piece golf balls comprise various combinations of a core (wound or unwound), one or more intermediate polymeric shells and an outer polymeric cover. The cover polymer used in two-piece and three-piece balls may, for example, be balata, an ionomeric polymer (e.g., SURLYN(copyright)) or a polyurethane.
Golf ball covers are commonly painted with a primer coat which may be colored (e.g., white) or transparent. Alternately, the cover itself may contain a colorant. Typically, a tough, often glossy, topcoat is applied over the cover and/or the primer coat to form a protective outer seal on the golf ball. The topcoat may comprise, for example, a two component urethane. The topcoat typically increases the shine (i.e., glossy appearance) of the golf ball to enhance or brighten its appearance.
As used herein, xe2x80x9cproduction printingxe2x80x9d is when ink is applied directly to the cover or to the primer coat and the ink is then further coated with a topcoat. The image produced thereby is a xe2x80x9cproductionxe2x80x9d print and the ink used for this purpose is a xe2x80x9cproductionxe2x80x9d ink. In production printing, for some applications, when ink is applied directly to a cover, the cover surface is first roughened, for example, by sandblasting to enhance the bond between the ink and the cover. Thereafter, the ink is applied to the roughened cover. A transparent water based or solvent based overcoat may be applied over the ink layer and on the roughened cover to smooth out the cover and ink surfaces. Examples of such overcoats include urethane, polyester and acrylic. Thereafter, a topcoat is preferably applied to the overcoat.
Alternatively, xe2x80x9clogo printingxe2x80x9d as also used herein, involves the application of the ink directly onto a topcoat. The image produced thereby is a xe2x80x9clogoxe2x80x9d and the ink is a logo (or custom) ink. Thus, by use of production and/or logo printing one may add decorative markings such as a company trademark, symbol or the like to increase brand recognition and/or to enhance the appearance and/or the visibility of golf balls, game balls and the like. Logo prints therefore adhere to the typically glassy exterior of a topcoat, and have no other protective coating affixed thereto.
Inks used in production and logo printing must have sufficient durability. Durability is influenced by such factors as ink layer flexibility (i.e., ink layer brittleness), ink layer resistance to abrasion, ink migration due to gravity, ink layer hardness, adhesion to golf ball cover polymers such as ionomers (e.g., SURLYN(copyright)), balata, polyurethane, polyolefin and mixtures thereof, adhesion to topcoats, adhesion to primer coats and intercoat adhesion between various layers of inks and/or other overcoats and/or topcoats.
Most commonly, logos and production prints are applied to golf balls by a pad printing process and apparatus. Pad printing uses an etched image plate (i.e., a cliche) having an etching of the desired image. The image plate, typically, is made of a tough material such as metal, steel, other alloy or photopolymer which normally has a uniform thickness except for the area defining the etched image. The plate may optionally be coated with one or more protectant layers or materials, to enhance its useful life. Typically the depth of the etched image is from about 5 microns to about 30 microns.
During pad printing, ink is applied to the image plate, thus filling the etched image. Excess ink is then scraped off of the image plate, leaving behind ink only within the etched image. A printing pad is then momentarily lowered and pressed onto the inked image plate to lift ink off of the etched ink filled cavity onto the printing pad. The ink so lifted defines the shape of the etched image. The inked pad is then momentarily lowered and pressed onto, for example, a golf ball, thereby releasing the ink from the pad to the golf ball. The ink released from the pad forms, on the spherical surface of the ball, an image corresponding to that of the etched cavity.
This process of inking the image plate, scraping off excess ink, lifting off ink onto the printing pad and releasing the ink from the pad to the object (e.g., golf ball) to be inked may be repeated to print a plurality of images on a plurality of types of balls with various inks having desirable ink properties. The process of pad printing is well known. See, for example, U.S. Pat. Nos. 5,513,567 (Froh et al.); 4,896,598 (Leech, Jr.); 4,803,922 (Denesen); 4,745,857 (Putnam et al.); and 5,237,922 (Ho).
Printing pads are made from a resilient material such as silicone rubber which desirably picks up ink from the etched cavity of the image plate during lift-off and releases all of the ink lifted off when brought into contact with the article to be printed. Once the ink is deposited, it is cured, most commonly by a thermal curing process.
However, during manufacturing of printed articles such as game balls and golf balls, ink transfer problems are often encountered. For example, while it is desirable that all of the ink picked up by the printing pad be fully released onto the article to be printed, sometimes complete release is not achieved. Consequently, subsequent articles to be printed upon by the same printing pad member may have excessive ink or misaligned ink deposited thereon. Such improper ink deposition leads to unwanted ink contamination of balls, either directly between balls or indirectly by first transferring ink to ball handling equipment or both. Resolution of such problems requires expensive positioning equipment to prevent unwanted contact between balls, between ink depositing members and balls and between ball handling equipment and balls, respectively.
To overcome such ink transfer problems, intermediate thermal curing steps are introduced into the manufacturing process. There are several disadvantages to thermal curing, however. These include (1) high energy consumption, (2) long cooling cycles, (3) restricted material selection to thermally curable and thermally stable polymeric materials and (4) use of costly ventilating systems to dissipate vapors generated during thermal curing.
In addition to the problems associated with ink transfer before the ink is cured, post manufacturing problems are also commonly encountered even after curing takes place. Ink layers, after cure, may not possess a desirable level of adhesion to a substrate article surface. For example, a logo printed onto a golf ball topcoat is subjected to repeated xe2x80x9chardxe2x80x9d impacts by a golf club during the golf ball""s normal useful life. If adhesion, toughness, flexibility and/or hardness are at an undesirable level, ink deposited upon a topcoat (e.g., a logo printed upon a finished ball having an underlying topcoat or a clear coat) and/or ink deposited under a topcoat (e.g., a production print formed by the ink layer being interposed between the cover or primer coat and an overcoat and/or a topcoat) will abrade, flake, crack or otherwise separate from the golf ball topcoat, overcoat, the cover and/or the primer coats. After repeated impacts, such lack of adhesion, toughness, flexibility and/or hardness yields an unsightly golf ball.
The adhesion of the ink to the ball is in turn affected by the sufficiency of the curing of the ink. When the ink is not properly cured, it tends to detach from the surface of the golf ball. Separation of UV radiation curable ink, and to a lesser extent UV-visible radiation curable ink, from the ball is more likely when the ink or ink layer is thicker because the ink is less likely to be completely through-cured, i.e. cured through the entire thickness of the ink coating.
Also, UV radiation curable inks which contain certain colored pigments are more prone to insufficient curing, even when UV radiation and visible light are used to cure the coating. Pigments, particularly those which impart the colors black, blue, green or white to the ink, absorb the UV light which is necessary to activate the UV photoinitiators which initiate the curing of the ink. Specifically, these pigments and the UV photoinitiators absorb UV light having the same UV wavelengths. Because both the pigments and the UV photoinitiators are competing for the same UV radiation, some of the UV photoinitiators in the ink, particularly those below the ink layer""s outer surface will not absorb enough energy needed to initiate the curing in the lower portions of the ink layer. Also, the UV photoinitiators at the surface of the ink absorb the UV light, thereby limiting the amount of UV light that penetrates to lower depths in the ink layer to permit curing of the ink layer at the substrate interface. As a result, insufficient curing often occurs. The layer of ink nearest the ball may be insufficiently cured, while the outer layer of the ink may look and feel completely cured. To remedy such deficiency, more energy and/or longer curing times can be used. However, increases in energy doses and curing time is not desirable since it leads to inefficient production of golf balls as well as potentially adverse effects on the golf ball materials. For example, to increase the curing energy, the line speed, i.e., the speed by which the balls are moved toward the curing energy source, must be reduced. This decrease in line speed tends to melt or sink the cover on the golf balls due to the heat output of the curing source. Therefore, there exists a need for a method of curing radiation curable inks for golf balls which thoroughly cures upon exposure to radiation without exposing the substrate to substantially greater energy.
To overcome these and other problems, novel curable inks (1) that are low energy curable, (2) that require minimal cooling, if any, (3) that are almost instantaneously cured, (4) that obviate or reduce the need for costly ventilating systems and (5) that permit the use of a broader range of polymeric cover, intermediate shell (or windings) or core golf ball and game ball materials, are sought. Additionally, novel methods of cure of the inks which utilize low energy, that result in minimal heat generation, that do not require costly ventilation systems and/or inert atmospheres, and that permit the use of a broader range of polymeric cover, intermediate shell (or windings) or core golf ball and game ball materials, are sought. These requirements are met by the low power electron beam curable inks and the multiple source curing process which are the subject of the present invention.
The present invention includes a novel, cost-effective, and rapid radiation curing method for forming an ink print on a curved surface such as that found on a game ball, a golf ball, or the like. In one or more embodiments of the present invention, the many advantages obtained may include: a process to cure radiation curable ink, in particular a process of curing which includes exposure to a combination of a first radiation which includes UV radiation, visible light radiation, or both UV radiation and visible light radiation, and a second radiation which includes electron beam radiation, having a high cure rate and allowing for the use of a wide range of color pigments in the ink; a curing process that renders deep and complete curing with a minimum of temperature increase; a method of forming a logo or production print on such a game ball, golf ball, etc. curved surface with improved durability, flexibility, hardness, etc., by the use of radiation curing; UV/visible light and electron beam curable ink compositions having improved durability, flexibility, hardness, abrasion resistance, adhesion and ink transfer properties; UV/visible light and electron beam curable ink compositions suitable for production or logo printing on game balls, golf balls and the like (e.g., sports equipment such as club heads, helmets etc., and other curved surfaces) having improved durability, flexibility, hardness, abrasion resistance, adhesion and ink transfer properties.
These embodiments are accomplished by the use of a novel, cost-effective and rapid method of curing ink layers on the curved surfaces of game balls, golf balls or the like using a combination of UV/visible light and electron beam curing radiation.
In one embodiment of the invention, radiation curable water-insoluble ink is deposited on, e.g., a golf ball to produce a logo or a production print, which is thereafter cured by an initial application of visible light radiation and subsequently by application of electron beam curing radiation.
In one embodiment of the invention, radiation curable water-insoluble ink is deposited on, e.g., a golf ball to produce a logo or a production print, which is thereafter cured by an initial application of UV radiation and subsequently by application of electron beam curing radiation as described in U.S. Pat. No. 6,001,898, the disclosure of which is incorporated herein by reference.
In one embodiment of the invention, radiation curable water-insoluble ink is deposited on, e.g., a golf ball to produce a logo or a production print, which is thereafter cured by an initial application of UV and visible light radiation and subsequently by application of electron beam curing radiation.
In one embodiment of the invention, radiation curable water-insoluble ink is deposited on, e.g., a golf ball to produce a logo or a production print, which is thereafter cured by an initial application of electron beam curing radiation and subsequently by application of visible light radiation, UV radiation, or UV and visible light radiation.
In one embodiment of the invention, a first layer of radiation curable water-insoluble ink is deposited on, e.g., a golf ball to produce a logo or a production print, which is thereafter cured by an initial application of visible light radiation, UV radiation, or UV and visible light radiation. Subsequently, a second layer of radiation curable water-insoluble ink is deposited and is cured by application of a combination of visible light radiation, UV radiation, or UV and visible light radiation plus electron beam curing radiation. The electron beam curing is sufficient to cure uncured ink in both the first and the second layers.
In another embodiment, the invention comprises a radiation curable water-insoluble production ink for forming an inked surface on at least a portion of the surface of a game ball, golf ball or the like wherein at least the inked surface is coated with a topcoat. The ink comprises an ink base containing at least a prepolymer with at least two prepolymer functional moieties. The prepolymer is selected from the group consisting of a first acrylate, an ester and mixtures thereof and a polymerizable monomer.
To increase the cure rate of the ink a photoinitiator is added to the ink. The photoinitiator can also promote sufficient through-curing of the ink. Suitable photoinitiators include UV photoinitiators, visible light photoinitiators, or combinations thereof, a more detailed discussion of which is provided below.
A visible light photoinitiator can be used in addition to or as a substitute for UV photoinitiators. Preferably, a combination of UV and visible light photoinitiators, or a photoinitiator having a significant portion of its absorbance spectrum in both the UV and the visible regions, is included in the ink to promote the complete curing of the coating. As used herein, visible light photoinitiators refer to both photoinitiators which have an absorbance spectrum in both the UV and visible light regions as well as photoinitiators which have an absorbance spectrum only in the visible light region.
As noted earlier, pigments in inks (particularly black, blue, green and white ones) absorb at the same UV light wavelengths at which UV photoinitiators must absorb in order to start the curing of the ink. As a result, the UV photoinitiators in the ink beneath the surface of the ink layer will be deprived of adequate UV light by the pigments and curing of the ink will be limited to the upper ink layer. In other words, the UV photoinitiators and pigments compete for the same UV light, which substantially limits the activating radiation available to photoinitiators nearest to the ball in an ink layer.
By adding to an ink, with or without UV photoinitiators, a visible light photoinitiator which absorbs radiation having longer wavelengths than that absorbed by the pigments and UV photoinitiators, the speed and completeness of the through-cure of the ink will be increased. See U.S. Pat. No. 6,013,330, the disclosure of which is incorporated herein by reference. The amount of energy needed for through-cure can be reduced. Since a light source used for curing can be selected to emit light not only in the UV region of the spectrum (which is absorbed by the pigments and by the UV photoinitiators), but also visible light at certain wavelengths, a visible light photoinitiator added to the ink can absorb such visible light, that would otherwise be wasted and turned to unwanted heat, during the curing of the ink and therefore more effectively initiate the curing of the ink. In other words, inclusion of a visible light photoinitiator will allow the ink to make use of visible light from a UV/vis light source which is not being absorbed by the to the same extent as the UV light by the pigments, thereby promoting the through-cure of the ink and more efficiently using the energy emitted by the light source.
Preferably, the visible light photoinitiator should have a substantial part of its absorbance spectrum (i.e., greater than about 50 percent) at wavelengths greater than about 400 nm. More preferably, the visible photoinitiator should have a maximum absorbance at a wavelength greater than about 400 nm. Also, the amounts of visible light photoinitiators that can be included in the ink range from about 0.01 to 3 parts per 100 parts ink.
Added to the production ink base is an adhesion promoting component which may be a carboxylic acid functional monomer, a carboxylic acid functional oligomer, an ester functional monomer, an ester functional oligomer or mixtures thereof. The adhesion promoting component has at least one adhesion promoting functional moiety comprising at least about 2 moles of a carbonyl functionality per mole of the adhesion promoting component. It is sufficient to maintain adhesion of at least about 75 percent of the curved inked surface to the topcoat and to the surface of the game ball, golf ball or the like after curing and after coating with the topcoat.
A further embodiment is directed to a process for forming a production print on at least a portion of the curved surface of a game ball, golf ball or the like. For example, with golf balls as an example, the process comprises providing a golf ball having a curved surface; coating at least a portion of the golf ball surface with at least a layer of a radiation curable water-insoluble production ink; curing the coating layer with an initial application of visible light radiation and subsequently by application of electron beam radiation; and coating at least the inked surface with a topcoat.
An additional embodiment of the present invention is directed to an improved radiation curable water-insoluble logo ink composition. The water-insoluble logo ink includes an ink base comprising a prepolymer having at least two prepolymer functional moieties. The prepolymer is selected from the group consisting of a first acrylate, an ester and mixtures thereof and at least a polymerizable monomer. Photoinitiators, including visible light photoinitiators, suitable for preparing the radiation curable water-insoluble inks of this invention are also used in formulating these logo inks.
Included in the logo ink base is a toughening agent. The toughening agent is sufficient to maintain adhesion of the logo ink to the topcoat of at least about 75 percent of the inked surface after electron beam radiation curing. The toughening agent may be sterically hindered monomers, dimers, trimers or oligomers, such as sterically hindered acrylates. Preferably, the toughening agents are also reactive diluents, (i.e., they form covalent bonds upon polymerization and are incorporated into the structure of the ink layer).
A still further embodiment involves a process for forming a logo on a game ball or golf ball topcoat. For example, in the case of a golf ball, the process comprises providing a golf ball having a topcoated surface; coating at least a portion of the surface with at least a layer of an electron beam curable water-insoluble logo ink; and curing the ink with an initial application of visible, UV, or visible/UV light radiation and subsequently by application of electron beam radiation.
In another embodiment the electron beam can be applied before the UV, visible, or UV/visible radiation.
In yet another embodiment, the exposure to the electron beam can be of a time sufficient for additional curing of both a logo ink and an underlying production ink.
While the present invention is described mainly in terms of a golf ball, it should be understood that a variety of additional curved substrates (e.g., game balls) may be printed upon using the ink formulations and methods described and claimed herein without departing from the scope of the present invention.
The following detailed description is provided to aid those skilled in the art in practicing the present invention. However, it should not be construed to unduly limit the scope of the present invention. Variations and modifications in the embodiments discussed may be made by those of ordinary skill in the art without departing from the invention.
As used herein, xe2x80x9cradiationxe2x80x9d refers to electromagnetic radiation having wavelengths in the ultaviolet and/or visible light regions of the spectrum, and more specifically, to electromagnetic radiation having a wavelength greater than about 400 nm. xe2x80x9cRadiation curablexe2x80x9d, as used herein, refers to the ability to be cured with electromagnetic radiation having wavelengths in the UV and/or visible light regions of the spectrum and also by electron beam radiation. As used herein, xe2x80x9cwater-insolublexe2x80x9d means the cured ink is resistant to dissolution by water.
The radiation curable water-insoluble production ink of the present invention is formed by modifying an ink base composition. The ink base composition comprises a prepolymer having at least two prepolymer functional moieties and a photoinitiator. The prepolymer is selected from the group consisting of a first acrylate, an ester, and mixtures thereof and at least one polymerizable monomer.
Suitable first acrylates for use in conjunction with the present invention include, but are not limited to, acrylated amines, acrylic acrylates, oil acrylates, melamine acrylates, heterocyclic acrylates, epoxy acrylates, epoxy acrylates of bisphenol A, epoxy acrylates of bisphenol F, epoxy acrylates of bisphenol S, novolak acrylates, urethane acrylates, ether acrylates, polyether acrylates, thiol acrylates, thioether acrylates, polythioether acrylates, silicon acrylates, polystyryl acrylates, ester acrylates, polyester acrylates, aromatic acrylates, aliphatic acrylates, half-ester acrylates, di-ester acrylates, vinyl acrylates, polybutadiene acrylates, allyl acrylates, polyene acrylates, methacrylates, methacrylated amine, acrylic methacrylates, methacrylic methacrylates, oil methacrylates, melamine methacrylates, heterocyclic methacrylates, epoxy methacrylates of bisphenol A, epoxy methacrylates of bisphenol F, epoxy methacrylates of bisphenol S, novolak methacrylates, urethane methacrylates, ether methacrylates, polyether methacrylates, thiol methacrylates, thioether methacrylates, polythioether methacrylates, silicon methacrylates, polystyryl methacrylates, ester methacrylates, polyester methacrylates, aromatic methacrylates, aliphatic methacrylates, half-ester methacrylates, di-ester methacrylates, vinyl methacrylates, polybutadiene methacrylates, allyl acrylates, polyene methacrylates and the like and mixtures thereof.
The first acrylates are acrylated prepolymers having high molecular weights, for example, of at least about 500 grams per mole and have at least 2 polymerizable functionalities (i.e., prepolymer moieties) per molecule of prepolymer. Often, the acrylated prepolymers and the ester prepolymers have a high viscosity (e.g., 100-20,000 centipoise at 25xc2x0 C.) and a molecular weight of between about 500 to about 5,000 grams per mole and between about 2 to 6 reactive prepolymer functional moieties per molecule. The ester may be an unsaturated ester.
The polymerizable monomers are considered reactive diluents. They may be monofunctional monomers or poly-functional monomers. These polymerizable monomers are used to modify (e.g., typically to reduce) the viscosity of the acrylate prepolymer or the ester prepolymer. However, these monomers also aid in the cross-linking of the prepolymers upon electron beam radiation curing thereof. These monomers include, but are not limited to, one or more monofunctional acrylates or one or more polyfunctional acrylates. For example, the monofunctional acrylates have one acryloyl or methacryloyl group per acrylate molecule whereas the polyfunctional acrylates have two or more acryloyl or methacryloyl groups per acrylate molecule.
Theoretically, upon exposure to UV and/or visible light it is conceivably possible to cure (i.e., polymerize) a polymerizable ink without a photoinitiator. In practice, however, a photoinitiator is required to achieve an economically feasible cure rate (i.e., increased cure rate). Increased cure rates yield higher production rates and lower per unit production costs of various inked articles such as game balls, golf balls and the like.
Examples of ultraviolet light photoinitiators compatible with the ink base of the present invention (e.g., ink base for production ink or ink base for logo ink) include free radical photoinitiators. (See Jean-Pierre Fouassier, Photoinitiators and Photosensitizers of Polymerization: A Short Review, Vol. 6, European Coatings Journal, pp. 412-419 (1996). Specific examples of free radical photoinitiators include, but are not limited to, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone), 2-hydroxy-2-methyl- 1-phenyl-1-propanone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2,2-dimethoxy-1,2-diphenylethanone, 2-butoxy- 1,2-diphenylethanone, 2-(2-methyl propoxy)- 1,2-diphenylethanone, benzophenone, 2-alpha hydroxy ketone, other alpha hydroxy ketones, other benzophenone derivatives or mixtures thereof. Other photoinitiators (i.e., photo-polymerization initiators) compatible and suitable for use with the inks of the present invention are well known in the art. Additional examples of suitable photoinitiators are listed in U.S. Pat. Nos. 4,670,295 (Quinn et al.) and 4,680,368 (Nakamoto et al.), which are incorporated herein by reference in their entirety.
A preferred photoinitiator is Esacure(trademark) KIP-100F that is commercially available from Sartomer. This photoinitiator (Esacure(trademark) KIP-100F) is a liquid mixture of 70 percent by weight of oligo(2-hydroxy-2-methyl-1-(4-(1 -methylvinyl)phenyl)propanone) with a M.W.=204.7 grains/mole per repeating unit and 30 percent by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone with a M.W.=164.2 grains/mole. This commercially available photoinitiator is a highly reactive, non-yellowing initiator for the polymerization of radiation curable inks. It is further characterized by the following physical properties:
In accordance with the present invention, the photoinitiator(s) is/are added to the ink base in an amount sufficient to increase the cure rate of a radiation curable ink. However, photoinitiators are typically extremely expensive. Therefore, it is preferable to use a minimum amount of photoinitiator without unduly sacrificing cure rates, production rates or production costs. For example, the photoinitiator is present from about 0.05 percent to about 15 percent by weight of the total weight of the ink. However, it is preferred to use from about 0.05 percent to about 5 percent of the photoinitiator, more preferably, from about 0.1 percent to about 0.5 percent by weight. For example, 0.1 percent of Esacure(trademark) KIP-100F is sufficient to formulate an radiation curable production ink or logo ink according to the present invention.
Other suitable commercially available photoinitiators include, but are not limited to, 1-hydroxy cyclohexyl phenyl ketone (Irgacure(trademark) 184); n5-2,4-cyclopentadien-1-yl) ((1,2,3,4,5,6-n)-(1-methyl ethyl)benzene) -iron (+) -hexafluorophosphate (-1) (Irgacure (trademark) 261); 2-benzyl-2-n-dimethylamino-1-(4-morpholinophenyl)- 1 -butanone (Irgacure(trademark) 369); 1 -hydroxycyclohexyl phenyl ketone (50 percent by weight) plus benzophenone (50 percent by weight) (Irgacure(trademark) 500); bis(2,6-dimethoxy benzoyl)-2,4,4 trimethylpentyl phosphineoxide (DMBAPO) (25 percent by weight) plus 2-hydroxy-2-methyl-1-phenyl-propan-1-one (HMMP) (75 percent by weight) (Irgacure(trademark) 1700); 4-(2-hydroxyethoxy) phenyl-(2-hydroxy propyl)ketone (Irgacure(trademark) 2959); 2,4,6-Trimethyl benzoyl diphenyl phosphineoxide (TPO) (50 percent by weight) plus 2-hydroxy-2-methyl-1-phenyl-propan-1-one (HMPP) (50 percent by weight) (Darocur(trademark) 4265); 2,2-dimethoxy-2-phenylacetophenone (BDK) (Irgacure(trademark) 651); bis(n5-2,4-cyclopentadien-1-yl), bis (2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) Titanium (CGI-784); 2-methyl-1-(4-(methylthio)phenyl)-2-morpholino propan-1-one (MMMP) (Irgacure(trademark) 907); 2-hydroxy-2-methyl-1-phenyl-propan-1-one (HMPP) (Darocur(trademark) 1173); or mixtures thereof. These photoinitiators are commercially available from Ciba-Geigy.
In addition, the ink base preferably includes visible light photoinitiator(s) (i.e., a photoinitiator having at least a part of its absorbance spectrum in the visible region or photoinitiator having its entire absorbance spectrum in the visible light region). These visible light photoinitiators can be used in conjunction with or as substitutes for UV photoinitiators. Preferably, a combination of UV and visible light photoinitiators are used. More preferably, the visible light photoinitiator(s) should have a substantial portion, i.e., greater than about 50 percent of its absorbance spectrum at wavelengths greater than about 400 nm. Even more preferable, the visible light photoinitiator should have a maximum absorbance at wavelengths greater than about 400 nm.
When a combination of UV and visible light photoinitiators or photoinitiators having an absorbance spectrum in both the UV and visible light regions are used in the ink, the ink is cured using UV and visible light. When only UV photoinitiators or only visible light photoinitiators having an absorbance spectrum only in the absorbance spectrum are used, then the ink may be cured using only UV or only visible light, respectively.
Visible light photoinitiators compatible with the ink base of the present invention (e.g., ink base for production ink or ink base for logo ink) include photoinitiators having at least a part of their absorbance spectrum in the visible region or photoinitiators having their entire absorbance spectrum in the visible light region. Preferably, the visible light photoinitiator(s) should have a substantial portion, i.e., greater than about 50 percent of its absorbance spectrum at wavelengths greater than about 400 nm. Even more preferable, the visible light photoinitiator should have a maximum absorbance at wavelengths greater than about 400 nm.
When a combination of UV and visible light photoinitiators or photoinitiators having an absorbance spectrum in both the UV and visible light regions are used in the ink, the ink is cured using UV and visible light. When only UV photoinitiators or only visible light photoinitiators having an absorbance spectrum only in the absorbance spectrum are used, then the ink may be cured using only UV or only visible light, respectively.
Visible light photoinitiators which are particularly suitable for the present invention include fluorene derivatives such as those described in U.S. Pat. No. 5,451,343 to Neckers et al., U.S. Pat. No. 5,395,862 to Neckers et al. and Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, vol. III, pp. 228-299, Selective Industrial Training Assocs. Ltd. (1991) (the contents of which are incorporated herein by reference for all purposes).
Preferred fluorene derivatives useful as visible light photoinitiators are 5,7-diiodo-3-butoxy-6-fluorene (with a maximum absorbance at 470 nm); 2,4,5,7-tetraiodo-3-hydroxy-6-fluorene (with a maximum absorbance at 535 nm); and 2,4,5,7-tetraiodo-9-cyano-3-hydroxy-6-fluorene (with a maximum absorbance at 635 nm), all of which are available from Spectra Group Limited, Inc.
Moreover, depending upon the photoinitiator, one or more co-initiators may be used in combination with the visible light photoinitiator to enhance the curing of the ink. One of skill in the art is aware of whether a given visible light photoinitiator should be used with a co-initiator and which co-initiator(s) should be combined with the photoinitiator.
For example, when fluorene derivatives are used as visible light photoinitiators, an onium salt and/or an aromatic amine can be used as co-initiators. Suitable onium salts include iodonium salts (e.g. phenyl-4-octyloxyphenyliodonium hexafluoroantimonate (OPPI), dodecyldiphenyliodonium hexafluoroantimonate (DDPI), and (4-(2-tetradecanol)-oxyphenyl)iodonium hexafluoroantimonate); sulfonium salts; pyrylium salts; thiapyrylium salts; diazonium salts and ferrocenium salts. Suitable amine co-initiators include N,N-dimethyl-2,6-diisopropylaniline (DIDMA), ethyl- or octyl-para-(dimethylamino)benzoate (EDAB or ODAB respectively) and N-phenylglycine (NPG).
Additionally, triarylalkyl-borate ammonium salts can be used in conjunction with the fluorene visible light photoinitiator instead of the amine co-initiator. Examples of such borate co-initiators include tetramethylammonium triphenylbutyl borate and butyryl choline triphenyl butylborate (available from Spectra Group Limited).
Other visible light photoinitiators that are useful for this invention include without limitation titanocene photoinitiators (particularly fluorinated diaryl titanocenes such as bis(xcex75-cyclopentadienyl) bis-[2,6-difluoro-3-(1H-pyrr-1 -yl)phenyl]-titanium); ketocoumarine photoinitiators (e.g. 3-ketocoumarine); acridine dyes (e.g. acriflavine); xanthene dyes (e.g. rose bengale or fluorescein); azine dyes, thiazine dyes (e.g. methylene blue); and polymethine dyes (e.g. cyanines or merocyanines).
Examples of co-initiators which are compatible with the xe2x80x9cdyexe2x80x9d photoinitiators include amines (e.g. triethanolamine); phosphines/arsines (e.g. triphenylphosphine or triphenylarsine); sulphinates (e.g. sodium p-tolysulphinate); enolates (e.g. dimedone enolate); carboxylate (e.g. ascorbic acid); organotin compounds (e.g. benzyltrimethylstannane); borates (e.g. triphenyl borate); and trichloromethyl-s-triazines.
Because of their efficient absorptivity of visible light, the amounts of visible light photoinitiators used in the ink is generally less than the amounts of UV photoinitiators used. In one embodiment, from about 0.01 to 3 parts per 100 parts ink of visible light photoinitiators is included in the ink. Preferably about 0.02 to 0.1 parts is used and more preferably about 0.05 to 0.07 parts is included.
The ratio of the visible light photoinitiator to co-initiator(s) can range from about 1:5 to 1:30. More preferably the ratio is about 1: 10 to 1:25 and even more preferably from about 1:20 to 1:25.
The radiation curable water-insoluble production ink of the present invention is formed by modifying the base composition to incorporate at least an adhesion promoting component. An adhesion promoting component added to the ink base to yields a production ink. The adhesion promoting component improves the adhesion of the production ink to, for example, a golf ball cover or a primer coat when applied thereto and after being cured by radiation. The adhesion promoting component also improves the adhesion of the ink to a topcoat (e.g., a urethane topcoat) or to an overcoat (e.g., a water based urethane coat or a solvent based coat) when such coats are applied over the cured production ink.
The adhesion promoting component is selected from among carboxylic acid functional monomers, carboxylic acid functional oligomers, ester functional monomers, ester functional oligomers and mixtures thereof. The adhesion promoting component has at least one adhesion promoting functional moiety comprising at least about 2 moles of a carbonyl functionality per mole of the adhesion promoting component. The adhesion promoting component is added to the ink base to promote intercoat adhesion of the production ink. Intercoat adhesion, as used herein, is defined as adhesion to an underlying cover and/or primer coat and adhesion to a topcoat and/or overcoat.
Preferably, the adhesion promoting component is selected from acrylate oligomers, aromatic acid acrylate esters, aromatic acid acrylate half esters, aromatic acid methacrylate esters, aromatic acid methacrylate half esters and mixtures thereof. The adhesion promoting component has at least about 2 moles of a carbonyl functionality, typically between about 3 to about 12 moles of a carbonyl functionality per mole of the adhesion promoting component or any value therebetween. Preferably, the adhesion promoting component has between about 3.5 to about 11 moles of a carbonyl functionality per mole of the adhesion promoting component. Further, the adhesion promoting component has a molecular weight of about 1,000,000 grams per mole or less, typically between about 200 grams per mole to about 1,000,000 grams per mole.
The carbonyl functionality of the adhesion promoting component can be a carboxylic acid functional moiety, an ester functional moiety, an anhydride functional moiety or a mixture thereof. Preferably, the adhesion promoting functional moiety is a carboxylic acid having, for example, an acid number of at least about 100. The acid number is defined as the quantity of base, expressed in milligrams of potassium hydroxide, that is required to neutralize the free acids present in one gram (1 gm) of the adhesion promoting component of the production ink, logo ink, etc. The acid number of the adhesion promoting component is about 300 or less, typically between about 100 to about 300 or any number therebetween. Preferably the acid number is between about 150 to about 250 and most preferably between about 200 to about 230.
Further, the adhesion promoting component is present in an amount of at least about 1 percent by weight of the total weight of the production ink. All weight percentages provided below are relative to the total weight of the ink containing a given component unless specifically indicated otherwise. The adhesion promoting component is present in an amount of about 75 percent by weight or less, typically between about 1 percent to about 60 percent or any value therebetween (e.g., about 10 percent to about 20 percent) and most preferably between about 5 percent to about 25 percent by weight.
Examples of suitable adhesion promoting components include products from SARTOMER Company, Inc. (Exton, Pa.) designated as SARBOX(trademark) SB-501, SARBOX(trademark) SB-401, SARBOX(trademark) SB-510E35 and SARBOX(trademark) SB-520E35. SB-501 is a highly functional, carboxylic acid terminated oligomer blended in 40 percent by weight (of the total weight of SB-501) of ethoxylated trimethylolpropane triacrylate monomer (designed as SR-454). SB-501 is further characterized as indicated below:
SB-401 is a highly functional, carboxylic acid terminated, solid oligomer dissolved in 30 percent by weight (of the total weight of SB-401) of solvent. SB-401 is further characterized as indicated below:
SB-510E35 is a 35 percent by weight (of the total weight of SB-510E35) moderately functional carboxylic acid containing methacrylate oligomer (i.e., aromatic acid methacrylate half ester resin) blended in 65 percent by weight (of the total weight of SB-510E35) of ethoxylated trimethylolpropane triacrylate monomer (designated as SR-454, the chemical structure of which is incorporated herein by reference). SB-510E35 is further characterized as indicated below:
SB-520E35 is a 35 percent by weight (of the total weight of SB-520E35) moderately functional carboxylic acid containing acrylate oligomer (i.e., aromatic acid acrylate half ester resin) blended in 65 percent by weight (of the total weight of SB-520E35) of ethoxylated trimethylolpropane triacrylate monomer (designated as SR-454). SB-520E35 is further characterized as indicated below:
Both SB-510E35 and SB-520E35 contain 100 percent reactive solids. These products are described in SARTOMER COMPANY PRODUCT MANUAL AND APPLICATION GUIDE.
The production ink of the present invention may further comprise a viscosity reducing component and/or a flexibility promoting component. The viscosity reducing component is any low molecular weight reactive diluent that reduces the viscosity of the production ink. Examples of viscosity reducing components (produced and sold by the SARTOMER Company) compatible with the present invention include, but are not limited to, highly propoxylated glyceryl triacrylate (SR-9021), ethoxylated3 trimethylolpropane triacrylate (SR-454), ethoxylated6 trimethylolpropane triacrylate (SR-499), ethoxylated9 trimethylolpropane triacrylate (SR-502), ethoxylated15 trimethylolpropane triacrylate (SR-9035), ethoxylated20 trimethylolpropane triacrylate (SR-415), pentaerythritol triacrylate (SR-444), propoxylated glyceryl triacrylate (SR-9020), propoxylated3 trimethylolpropane triacrylate (SR-492), propoxylated6 trimethylolpropane triacrylate (SR-501), trimethylolpropane triacrylate (SR-351), trimethylolpropane trimethylacrylate (SR-350), tris(2-hydroxy ethyl) isocyanurate triacrylate (SR-368, SR-368D and SR-290), dipentaerythritol pentaacrylate (SR-399), di-trimethylolpropane tetraacrylate (SR-355), etboxylated pentaerythritol tetraacrylate (SR-494), pentaacrylate ester (SR-9041), pentaerytbritol tetraacrylate (SR-295) and mixtures thereof. The preferred viscosity reducing agent is ethoxylated3 trimethylolpropane triacrylate (SR-454) having a molecular weight of about 428 grams. Typically, the viscosity reducing component is present between about 10 percent to about 50 percent by weight of the total weight of the adhesion promoting component and any value therebetween, and, preferably, from about 0.1 percent to about 37.5 percent.
The flexibility promoting component compatible with the present invention has a post cure elastic modulus of between about 200 to about 60,000 pounds per square inch, a post cure tensile strength of between about 50 to about 2,500 pounds per square inch and a post cure elongation of between about 5 percent to about 350 percent. Further, the flexibility promoting component is any component that has a glass transition temperature (i.e., Tg) below about room temperature (e.g., below about 25xc2x0 C.) The flexibility promoting component includes, but is not limited to, a second acrylate, a ring opening heterocycle, or mixtures thereof, wherein the ring opening heterocycle is selected from the group consisting of cyclic esters, cyclic lactones, cyclic sulphides, cyclic acetals, cyclic siloxanes and mixtures thereof. The second acrylate is selected from the group consisting of an aliphatic urethane acrylate, an aromatic urethane acrylate, a polyether acrylate, an acrylated amine, a polybutadiene acrylate, a melamine acrylate and mixtures thereof. The cyclic ester of the flexibility promoting component includes an epoxide.
Additional examples of flexibility promoting components compatible with the present invention include, but are not limited to, urethane acrylate base resins designated by the SARTOMER Company as CN-962, CN-965, CN-966, CN-972, CN-973 and CN-981 and urethane acrylate resin/monomer blends designated as CN-965A80, CN-966A80, CN-966H90, CN-966J75, CN-973A80, CN-973H85, CN-973J75 and CN-981B88 and described in the SARTOMER COMPANY PRODUCT MANUAL AND APPLICATION GUIDE. Of these, CN-962, CN-965 and CN-966 are aliphatic urethane acrylate oligomers having a polyester backbone. CN-973 is an aromatic urethane acrylate having a polyester backbone. CN-972 is an aromatic urethane acrylate having a polyester backbone. CN-981 is an aliphatic urethane acrylate having a polyester backbone. In CN-965A80, CN-966A80, CN-966M90, CN-966J75, CN-973A8, CN-973M85, CN-973J75 and CN-981B88, the CN-966, CN-973 and CN-981 are the base resins, respectively. The letters A, B, H and J as used in the SARTOMER product designations refer to the monomers blended with the base resins. The number following the monomer letter designation indicates the percent by weight of the base resin, the remainder being the amount of the monomer making up the blend (i.e., totalling 100 percent by weight). Monomers A, B, H and J correspond to the SARTOMER designations tripropylene glycol diacrylate (SR-306), 1,6-hexanediol diacrylate (SR-238), 2(2-ethoxyethoxy) ethylacrylate (SR-256) and isobomyl acrylate (SR-506), respectively.
The flexibility promoting component is optionally added to the production ink composition in an amount of about 75 percent by weight or less, typically between about 5 percent to about 60 percent by weight or any value therebetween. Preferably, the flexibility promoting component is present between about 10 percent to about 30 percent by weight and most preferably between about 15 percent to about 20 percent by weight.
Additionally, the production ink may optionally contain a solvent in an amount of between about 1 percent to about 30 percent by weight of the total weight of the ink composition. In some embodiments it is preferred to have substantially no, i.e., less than 0.5 percent, of non-polymerizable organic solvents. Examples of solvents compatible with the present invention include, but are not limited to, (Fast Evaporating Rate Solvents): acetone, ethylacetate (85 to 88 percent), ethyl acetate (95 to 98 percent), ethyl acetate (99 percent), methyl acetate (80 percent), methyl ethyl ketone, iso-propyl acetate (95 to 97 percent), iso-propylether, tetrahydrofuran; (Medium Evaporating Rate Solvents): iso-butyl acetate (90 percent), n-butyl acetate (90 to 92 percent), n-butyl acetate (99 percent), sec-butyl acetate (90 percent), sec-butyl alcohol, tert-butyl alcohol, 1,1,1-trichloroethane, ethyl ketone, ethyl alcohol 200 PRF. ANHD, ethyl alcohol 190 PRF. ANHYD, ethyl alcohol 190 PRF. (95 percent), methyl alcohol, methyl isobutyl ketone, methyl isopropyl ketone, methyl n-propyl ketone, 2-nitropropane, n-propyl acetate (90 to 92 percent), iso-propyl alcohol, n-propyl alcohol; (Slow Evaporating Rate Solvents): amyl acetate (ex Fuel Oil) (85 to 88 percent), amyl acetate primary (mixed isomers)(95 percent), amyl alcohol primary (mixed isomers), tert-amyl alcohol, iso-butyl alcohol, n-butyl alcohol, butyl dioxitol(trademark) glycol ether, butyl oxitol(trademark) glycol ether, m-cresol, cyclohexanol, cyclohexanone, diacetone alcohol, dibasic ester, diethylene glycol, diethylene glycol monobutyl ether acetate (95 percent), diisobutyl ketone, dimethyl formamide, diethylene glycol, monoethyl etherxe2x80x94low gravity, diethylene glycol monoethyl etherxe2x80x94high gravity, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, ethyl butyl ketone, ethyl-3-ethoxy propionate, ethylene glycol, 2-ethyl hexanol, 2-ethyl hexyl acetate (95 percent), ethylene glycol monoethyl ether acetate (95 percent), ethylene glycol monoethyl ether acetate (99 percent), ethylene glycol monobutyl ether acetate, hexylene glycol, isobutyl isobutyrate, isophorone, methyl n-amyl ketone, diethyl glycol monomethyl ether, methyl isoamyl ketone, methyl isobutyl carbinol, ethylene glycol monomethyl ether, n-methyl-2-Pyrrolidone, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono tertiary butyl either, triethylene glycol; (Aliphatic Hydrocarbon Solvents): Mineral spirits, naphtha, or mixtures thereof and (Aromatic Hydrocarbon Solvents): Toluene, xylene or mixtures thereof. These solvents may be obtained from the Shell Chemical Company. Additional solvents well known in the art may be used.
Faster evaporating solvents are preferred for higher production rates (i.e., more balls production printed or logo printed per unit time). However, faster evaporating solvents typically yield higher levels of volatile organic compounds (VOCs) making them susceptible to greater regulation. On the other hand, slower evaporating solvents produce lower VOCs, but require longer drying times thereby lowering production rates.
The production inks may also optionally contain colorants such as pigments or dyes that are well known to those skilled in the ink formulation art in amounts sufficient to impart a desired color.
The logo ink of the invention differs from the production ink in that it contains different additive components due to differences in performance requirements of logos versus production prints. The logo ink comprises an ink base and at least a toughening agent. A further, optional additive to the logo ink base is a friction reducing agent commonly referred to as a slip and mar agent. For logos, the same ink base as described for the production inks is used, i.e., comprising a prepolymer having at least two prepolymer functional moieties, wherein the prepolymer is a first acrylate, an ester or mixtures thereof and a polymerizable monomer. Further, the ink base contains a photoinitiator. The photoinitiators compatible with logo inks are the same as those compatible (as previously listed) with production inks. Further, the percent by weight amounts of the photoinitiators compatible with production inks are also compatible with logo inks. Preferably, the visible light photoinitiator should have a substantial portion, i.e., greater than about 50 percent of its absorbance spectrum at wavelengths greater than about 400 nm. Even more preferable, the visible light photoinitiator should have a maximum absorbance at wavelengths greater than about 400 nm. Such visible light photinitiators are generally combined with one or more ultraviolet light photoinitiators (such as those described earlier) to promote complete cure of the ink.
Preferred fluorene derivatives useful as visible light photoinitiators are 5,7-diiodo-3-butoxy-6-fluorene (with a maximum absorbance at 470 nm); 2,4,5,7-tetraiodo-3-hydroxy-6-fluorene (with a maximum absorbance at 535 nm); and 2,4,5,7-tetraiodo-9-cyano-3-hydroxy-6-fluorene (with a maximum absorbance at 635 nm), all of which are available from Spectra Group Limited, Inc.
Suitable toughening agents are sterically hindered acrylates, preferably, monomers, dimers, trimers or oligomers. Further examples of toughening agents compatible with the logo inks of the present invention include, but are not limited to, epoxy acrylate, isobomyl acrylate (SR-506), tetrahydrofurfuryl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, vinyl toluene (styrene), isobomyl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyl oxyethyl methacrylate and mixtures thereof. The toughening agents preferably are reactive diluents which increase both the hardness and the flexibility of the ink base to yield a logo ink.
The toughening agent is present typically between about 5 percent to about 75 percent by weight, or any value therebetween, of the total weight of the logo ink, preferably between about 5 percent to about 30 percent by weight and most preferably between about 10 percent to about 20 percent by weight.
In addition to the toughening agent, as noted above a friction reducing agent may be optionally added to the base ink to form a preferred logo ink. The friction reducing agent minimizes abrasion of the logo ink by sand, dirt and other abrasive materials or surfaces commonly encountered during golfing or during other typical uses of game balls. The friction reducing agent decreases the friction between the logo (i.e., printed with the logo ink) and external abrasive materials on contact, thereby minimizing the degradation of the logo. Examples of friction reducing agents compatible with the logo ink of the present invention include, but are not limited to, a solution of polyether modified dimethylpolysiloxane copolymer (BYK(trademark)-306; BYK(trademark)-341;BYK(trademark)-344), polyether modified dimethylpolysiloxane copolymer (BYK(trademark)-307; BYK(trademark)-333), a solution of acrylic functional, polyester modified dimethylpolysiloxane (BYK(trademark)-371), silicon acrylates and mixtures thereof. Of these, the reactive friction reducing agents such as silicon acrylates and acrylic functional, polyester modified dimethylpolysiloxanes (BYK(trademark)-371) are preferred because they form bonds and become integrated into the structure of the logo ink upon electron beam radiation curing. The BYK(trademark) friction reducing agents are listed in the BYK product catalogue and may be obtained from BYK-Chemie USA of Wallingford, Conn. The friction reducing agents (e.g., dimethylpolysiloxanes) can be obtained from various companies such as Dow Corning (Midland, Mich.) and OSI Specialties (Endicott, N.Y.).
The friction reducing agent is present in an amount of about 10 percent by weight (of the total weight of the logo ink) or less, typically between about 0.1 percent to about 10 percent by weight or any value therebetween, preferably between about 0.6 percent to about 4 percent by weight and most preferably between about I percent to about 2 percent by weight.
The logo ink may further comprise from about 1 percent to about 50 percent by weight of solvent, preferably about 30 percent by weight. Suitable logo ink solvents are the same as those previously listed for use with production inks. It should be noted that certain volatile solvents evaporate to varying degrees. Thus, it is often necessary to continuously or intermittently replenish the volatilized solvent to maintain from about 1 percent to about 50 percent of the solvent in the ink composition.
During the curing step, to prevent overheating of the ink layers (e.g., production ink layers or logo ink layers), topcoats, overcoats and/or other parts of the substrate (e.g., golf ball) as well as the radiation lamps, one or more cooling gases (e.g., circulated by a cooling fan) may be provided to envelope the substrate and to dissipate heat. Such gases should be non-reactive with the substrate, the ink layers, the topcoat, the overcoat and/or other layers, especially during exposure to the radiation. Examples of suitable cooling gases include, but are not limited to, the inert gases (e.g., helium, argon etc.), nitrogen, air or mixtures thereof. In some embodiments it is preferred to have less than 1 percent oxygen in the gas. Other suitable gases are known to those skilled in the art.
Once the inks are applied and any solvents optionally removed by flashing (e.g., with infrared heat, or held at ambient temperature for 10-30 minutes or heated by forced hot air to a ball surface temperature of about 120xc2x0 F. or less for about 8-60 seconds), these inks are then cured. Curing is carried out rapidly by the novel and cost-effective use of radiation, e.g., UV/visible light and electron beam.
In the case of logo inks, the ink is first deposited, in one embodiment, on a golf ball topcoat and the solvent is then optionally removed by flashing. In another embodiment, the logo ink is deposited before the top coat is applied. The logo ink is subjected to electromagnetic irradiation, either first with UV radiation and subsequently with electron beam radiation, or first with electron beam radiation and subsequently with UV radiation.
In contrast, the production ink layer is first deposited directly upon the cover surface or primer coat, the solvent is optionally removed by flashing and the ink layer is radiation cured. Finally, overcoats and/or topcoats are applied to the radiation cured ink layer.
It is believed, although applicant is not bound by this theory, that radiation, e.g., UV and/or visible light radiation ionizes components, for example, within the ink and/or in a layer in contact with the ink. Further, without being bound by theory, it is believed that the photoinitiator within the ink formulation absorbs radiation and yields reactive intermediates such as free radicals through intermolecular and/or intramolecular interactions. These reactive intermediates increase the cross-linking rate (e.g., photopolymerization rate) of the various components of the inks of the present invention with the substrate layers or articles in contact with such inks. The cross-linking imparts greater durability, intercoat adhesion, abrasion resistance and the like to production prints or logos printed with such inks. In the subsequent electron beam radiation step, it is believed that the electron beam ionizes components, for example, within the ink and/or a layer in contact with such ink, to form free radicals. These free radicals aid in the cross-linking of the various components and agents of the inks of the present invention with the substrate layers or articles in contact with such inks, thereby imparting greater durability, intercoat adhesion, abrasion resistance and the like to production prints or logos printed with such inks.
Once the inks are applied, they are cured. In one embodiment, curing is carried out by the novel use of irradiation with UV radiation, followed by irradiation with electron beam radiation. In another embodiment the radiation for curing the ink can be produced from a TV and visible light source, or from a separate UV source and a separate visible light source, simultaneously or in series. If photoinitiators which only absorb UV or only visible light are used, then the radiation can be produced from a source which primarily emits UV or visible light, respectively. Irradiation with the UV or visible light source leads to surface curing of the ink, with a fraction of the ink remaining uncured. The uncured ink is cured by subsequent irradiation using electron beam radiation. The electron beam radiation is generated with the use of an electron beam source chamber (e.g., by an electron beam tube). A suitable low power electron beam generating apparatus is made by American International Technologies (AIT) of Torrance, Calif. and designated as the MIN-EB(trademark) CBT-101 model fitted with a ST-01-5050 model electron beam tube which requires minimal radiation shielding. See U.S. Reissue No. 35,203, incorporated herein by reference. Suitable radiation shielding materials include, but are not limited to, leaded acrylic, lead oxide epoxy, lead, other metals and leaded glass such as those available from Nuclear Associates of New York.
As stated before, inks containing certain pigments are difficult to cure using only UV radiation, and may also be difficult to cure using both UV and visible light curing. Additionally, the thickness of the ink layers must be kept thin using these conventional curing techniques. The current invention, however, allows deep curing of ink. It is now possible to, for example, apply several layers of ink on a ball. This may be desirable for, for example, a multicolor logo. The use of electron beam curing allows for thicker layers of ink. The plurality of ink layers can subsequently be fully cured by exposure to the electron beam.
In another embodiment, the plurality of inks can be applied to a given surface, wherein the inks do not overlap.
The use of a low power electron beam source allows more efficient dosage of electrons and also helps prevent unwanted reactions with substrate components.
The electron beam tube is a vacuum tube having a base end and a window end. An extended filament is disposed within the beam tube proximate to the base end. The filament generates electrons in conjunction with electron beam forming electrodes. The electrons from the filament (i.e., electron beam source) are directed toward and through the beam window of the electron beam tube. A low power electron beam tube is preferred. The beam energy from a low power beam tube is below about 125 kV (kilovolts), typically between about 15-80 kV (or any value therebetween), more typically between about 20-75 kV and most typically between about 30-65 kV. The voltage to the power supply (input voltage from about 10 to about 1,000 volts) is preferably about 110 volts (or less) and its operating power is preferably about 100 watts (or less). However, the output voltage of the beam tube may be between 20-100 kV or any value therebetween. Likewise, the operating power of the electron beam may be from about 10-1,000 watts or any value therebetween.
The window of the low power beam tube should be sufficiently transparent to the low power electron beam to transmit sufficient energy to cure the logo ink or the production ink of the present invention. For example, the window should be sufficiently transparent to permit passage of sufficient E-beam energy to cure a layer of a logo ink or a production ink on a golf ball or game ball.
The electron beam filament is displaced at a first distance from the beam window within the electron beam tube. The first distance is from about 0.01 to about 15 centimeters or any value therebetween, typically, from about 1.0 to about 12 centimeters (cm) and, more typically, from about 1.5 to about 4 centimeters. The electron beam window in a low power beam tube is typically made of a thin (e.g., about 1-10 microns or any value therebetween; preferably about 2.5 microns), low Z material such as carbide, nitride, or doped silicon (e.g., boron nitride, silicon carbide, silicon nitride, boron carbide, boron nitride hydride, boron doped silicon, and titanium foil), or mixtures thereof. Preferably, the beam window has dimensions of about 2xc3x9725 mm.
The logo ink layer or the production ink layer is maintained at a second distance from the beam window. The second distance is typically from about 1 mm to about 15 centimeters or any value therebetween, more typically between about 0.5 cm to about 5 cm and most typically between about 1.0 to about 2.0 centimeters. For suitable cure, as the second distance is increased, the operating power is also increased and vice versa. Further, if logo ink or production ink is to be cured, for example at multiple locations on a golf ball, the ball is rotated, preferably fully rotated, during EB irradiation and cure. The rotation rate should be sufficient to irradiate and cure any ink logos or production prints on the golf ball, game ball, or the like as they pass the electron beam tube curing station on the assembly line.
Without being bound by theory, it is believed that curing using electron beam radiation is inhibited by oxygen. Thus, the use of electron beam radiation curing requires that the material to be cured be surrounded by a gas, for example, an inert gas (e.g., argon, helium) or nitrogen, or mixtures thereof during irradiation and cure. The method of the present invention initially cures the surface of the ink using UV radiation, and, therefore, eliminates the need for the use of an inert atmosphere. The method of the present invention thus eliminates problems associated with uncured ink due to oxygen inhibition, and is more cost-effective than standard electron beam curing applications due to there being no requirement to provide an inert atmosphere for curing.
In one embodiment of the invention the cooling gas is air. While in many instances it is preferred to use the UV, visible, or UV/visible curing step before the electron beam curing step, the use of the electron beam curing step before the UV, visible, or UV/visible curing step is also envisioned.
During electron beam curing, the electron beam causes the beam window temperature to rise. Thus, the beam window is preferably exposed to at least one of these gases at a flow rate sufficient to prevent cracking, breaking, overheating, melting or otherwise damaging the beam window (i.e., maintaining the integrity of the beam window). Typically, the gas flow over the window prevents rapid temperature increases (i.e., overheating) of the beam window. The gas flow rate should be sufficient to maintain the transparency and the integrity of the window. For example, nitrogen gas at a flow rate from about 0.5 to about 30 cubic feet per minute (CFM) or more is sufficient to maintain the integrity of the beam window during curing. Further, the irradiation time (i.e., residence time) is about 10 seconds or less, typically from about 0.1 seconds to about 10 seconds or any value therebetween. Preferably, the residence time is from about 300 millisecond (ms) to about 3 seconds and most preferably from about 500 ms - 1.5 seconds. It is preferred to use a minimum residence time to maximize production.
Further, it is preferred that the electron beam have a beam width suitable to expose the ink surface to be cured. Preferably, the cure speed achievable with electron beam radiation is in the order of about 200 ft/second or less. The electron beam irradiation and curing may be accomplished with an array of electron beam tubes or with a single electron beam tube.
Having described the invention, the following example is provided to illustrate specific applications thereof, including the best mode now known to perform the invention. The specific example is not intended to limit the scope of the invention described herein.

Method for curing reactive ink on game balls


An online application system and a method for implementing an online application system are disclosed. A method for implementing the online application system includes a) receiving a user search request from a user browser; b) searching for a match according to the search request and obtaining an online application that matches with the search request to form a search result page; and c) presenting the online application before the user browser in a form as a canvas page which is embedded in the search result page and is directly accessible from the search result page. The present disclosure also provides an online application system. The technical solutions disclosed herein allow a user to directly search out an online application via a search engine without a need to click multi-level linkages, thereby providing a quick and convenient search process which enhances the users' experiences with networks.

1. Technical Field
The present application relates to network technology, and particularly to an online application system and a method for implementing an online application system.
2. Description of the Related Art
In times of Web 2.0, a user demands much more from the Internet than simply acquiring desired information. The user wants to be more involved and have interactions with the Internet. An online application is one of the important ways for these interactions between the user and Internet. The online application refers to a browser-based Web application that provides network interacting capability. However, in view of the development of the existing online applications, the user needs to log in various websites that offer these online applications and click various links thereon to eventually obtain an online application program.
So far, a user has been allowed to search for an online application using a search engine. Disadvantageously, the user is only given a link to the corresponding online application, and needs to click that link to enter the Website offering that online application to gain access to the online application. Besides, even though the user may search out the desired online application via the search engine, he or she needs to conduct plenty of actions after clicking the link to enter the corresponding Website. For example, the user has to click multi-level links or advertisements to finally obtain the desired online application. Furthermore, there are chances that these links to the online applications are connected to certain malicious websites, leading to poor network security.

Method and apparatus for monitoring state of online application

Baidu Online Network Technology (Beijing) Co., Ltd.


An aspect includes a transportable fold-out at least partial enclosure including: a center stationary section; a pair of primary platform assemblies, each primary platform including a first panel pivotally joined on opposite sides of the center stationary section and a second panel pivotally joined to the first panel on a side opposite the first panel; and at least one wall assembly pivotally joined to center stationary section and one of the primary platforms.

The discussion below is merely provided for general background information and is not intended to be used as an aid to determine the scope of the subject matter.
Various forms of portable enclosures for camping have been around for ages. Covered wagons, perhaps a more modern form of trailers given the history, provided covered living space during travel. More recent times have rendered the "pop-up" vehicle pulled trailer in which the trailer has a couple positions, a compacted travel position and an expanded use position. In addition to trailers, various forms of campers have been mounted to the bed or box of a pickup.
Early on, fuel consumption for the vehicle towing or carrying the camper was a relatively low concern. As fuel consumption rose and the expense of fuel reached new levels, society became more interested in energy efficiency. This trend expanded into an awareness of the need to protect the environment from wasteful uses of fuel. Trailers or large pickup mounted campers in the travel profile are at odds with fuel efficiency. In addition, large trailers or pickup mounted campers are difficult to store and transport.


A device for matching information between a plurality of circuitry-related documents includes a tree generation unit which generates a tree that represents relations between the circuitry-related documents, a matching-mask storage unit which stores a matching mask that specifies matching objects, and a matching unit which matches the matching objects between the circuitry-related documents within a specified range in the tree.

1. Field of the Invention
The present invention relates to a method, a device, and a memory medium having a program recorded therein for matching parts between a circuit diagram, a print-circuit-board diagram, and a bill of material.
2. Description of the Related Art
When a product having an electrical circuit therein is designed, a circuit diagram is created first based on a circuit design, and, then, a print-circuit-board diagram is created by arranging circuit parts on a board based on a print-circuit-board design. In a separate form, sizes and specifics of the circuit parts are specified in a bill of material.
Since the circuit diagram, the print-circuit-board diagram, and the bill of material are produced separately, it is conventionally an incumbent on the design engineers to check the diagrams and the table so as to make sure that there is no inconsistency therebetween. Such a check process requires excessive time and labor.
Accordingly, there is a need for a scheme which can match parts between a circuit diagram, a print-circuit-board diagram, and a bill of material so as to check consistency therebetween.
Accordingly, it is a general object of the present invention to provide a scheme which can satisfy the need described above.
It is another and more specific object of the present invention to provide a method, a device, and a memory medium having a program embodied therein for matching parts between a circuit diagram, a print-circuit-board diagram, and a bill of material so as to check consistency therebetween.
In order to achieve the above objects according to the present invention, a device for matching information between a plurality of circuitry-related documents includes a tree generation unit which generates a tree that represents relations between the circuitry-related documents, a matching-mask storage unit which stores a matching mask that specifies matching objects, and a matching unit which matches the matching objects between the circuitry-related documents within a specified range in the tree.
According to the present invention, the device as described above is such that the circuitry-related documents include a circuit diagram, a print-circuit-board diagram, and a bill of material.
Moreover, a method and a memory medium having a program embodied therein for matching parts between a circuit diagram, a print-circuit-board diagram, and a bill of material are achieved in a like manner as the device described above is achieved.
Other objects and further features of the present invention will be apparent from the following detailed description when read in conjunction with the accompanying drawings.

Matching circuit parts between circuitry-related documents


A method for installing objects such as cabinets on a vertical surface such as a wall includes the use of a novel support device having an adjustable leg and an upper portion including two vertically spaced support surfaces. Two of the support devices are first placed at a selected height at an angle to the wall for initially supporting the object on a first support surface. The support devices are then sequentially moved to extend between a front portion of the object and the floor so that the object rests on the second support surface thus freeing both hands of the installer.

1. Field of the Invention
The invention disclosed and claimed in this application is directed to a support mechanism for supporting objects such as cabinets during installation of the objects on a vertical surface. Two of the supports can be utilized in such a manner so as to allow installation of the object by a single installer.
2. Description of Related Art
Prior art devices for installation of objects such as cabinets on walls include an adjustable upright support having an adjustable carrier for supporting the cabinet. Such a device is shown in U.S. Pat. No. 6,612,533. This device is designed to hold cabinets in place before installation only on a level surface with level walls. This product has adjustments for correcting cabinet for level but not for plumb, which is detrimental for cabinet installation. This design is also bulky, utilizing too much space for tool storage and transportation, and also adds to the amount of tools needed by the installer rather than eliminating tools already needed for cabinet installation.
Another prior art device disclosed in U.S. Pat. No. 5,718,473 consists of a bracket securing the load and weight of the cabinet, but still requires more than one person to install cabinets correctly using a series of steps that are eliminated by the support device of this invention.


Improvement has been made in an image forming method comprising charging electrically an image holding member, forming a latent electrostatic image on the image holding member, developing the latent image with a toner, transferring the toner image onto a toner image receiving medium, and recovering untransferred toner. In this method, a magnetic brush formed from magnetic particles electrifies the image holding member by contact with the image holding member surface, recovers temporarily at least a part of the toner remaining on the image holding member after the image transfer, and transfers the recovered toner further again onto the image holding member, wherein the toner has a weight-average particle diameter of not larger than 1/3 of average particle diameter of the magnetic particles and the magnetic particles contain particles of diameter of not larger than 1/3 of the average particle diameter of the magnetic particles at a content ranging from 0 to 50% by volume. Thereby, contamination of the magnetic particles by the toner and interception of the electric conduction path in the magnetic brush are prevented, and deterioration of the toner is prevented without excessive shearing of the recovered toner with magnetic particles.

1. Field of the Invention
The present invention relates to an image forming method, and an image forming apparatus applicable to copying machines, printers, and facsimile machines. In particular, the present invention relates to an image forming method, an image forming apparatus, and a process cartridge in which the toner remaining on a photosensitive member after the image transfer is recovered by a development device.
2. Related Background Art
For miniaturizing the image forming apparatus, several techniques are known for cleaning an untransferred toner remaining on a photosensitive member after image transfer (hereinafter referred to as a remaining toner) simultaneously with electric charging or simultaneously with development by charging apparatus or developing apparatus.
Electric charging has been conducted conventionally by corona charging. However, the charging method is shifting to contact charging which generates less ozone by electric discharge from the standpoint of ecology. The contact charging member includes rollers, blades, fur brushes, and magnetic brushes.
However, in the case where a remaining toner on an image-holding member after image transfer is recovered temporarily by a magnetic brush charger formed by magnetic attraction of magnetic particles, some high-resistance toner particles (remaining toner after image transfer) enter an magnetic brush charger to lower the charging performance of the magnetic brush charger disadvantageously.
The toner recovered by the magnetic brush charger is again transferred onto the image-holding member, and is collected in the development device in a development step. However, the toner deteriorates in the magnetic brush charger, and causes problems as below. The recovered toner is not completely transferred onto the image holding member; the toner accumulates in the magnetic brush charger during the repeated image formation to lower the charging ability; the toner being transferred from the magnetic brush charger onto the image holding member and having been deteriorated in the magnetic brush charger cannot be recovered completely, causing fogging of the images; and the deteriorated toner recovered into the development device cannot be sufficiently utilized for the development, causing fogging of the images and scattering of the toner.

Image forming method, image forming apparatus and process cartridge


Nucleotide and amino acid sequences of cartilage-derived morphogenetic proteins (CDMP-1 and CDMP-2) from human and bovine cartilage extracts. These proteins exhibit chondrogenic activity and can be used to repair cartilage defects in a mammal.

Bone morphogenetic proteins (BMPs) are members of the TGF-β superfamily that can induce endochondral bone formation in adult animals. This superfamily includes a large group of structurally related signaling proteins that are secreted as dimers and then cleaved to result in biologically active carboxy terminal domains of the proteins. These bioactive proteins are characterized by 7 highly conserved cysteine residues. Interestingly, these proteins have different roles at various stages of embryogenesis and in adult animals. Recombinant BMPs are now available and have been shown to induce endochondral bone formation when assayed in vivo.
Indeed, the initial discovery of the BMPs was facilitated by such in vivo assays for cartilage and bone development. These assays were based on the observation that bone development could be initiated by subcutaneous or intramuscular implantation of compositions comprising an extract of demineralized bone and residual bone powder. The novel proteins identified in the extracts were termed "bone morphogenetic proteins." These proteins were subsequently classified as members of the TGF-β superfamily by virtue of amino acid sequence relatedness. Screening of genomic and cDNA libraries led to the isolation of polynucleotides encoding BMP-2, -3, -4, -5, -6 and -7.
One deficiency of the bone induction assay regards its inability to distinguish the physiological roles of different BMP family members. The cartilage and bone inducing activity of the BMPs is remarkable because the normal stages of endochondral bone formation that occur during ontogeny are recapitulated in the adult animal. These stages include mesenchymal condensation, cartilage and bone and bone marrow formation and eventual mineralization to produce mature bone.
Several observations suggest that BMPs have wide-ranging extraskeletal roles in development. First, localization studies in both human and mouse tissues have demonstrated high levels of mRNA expression and protein synthesis for various BMPs in kidney (BMPs-3, -4, -7), lung (BMPs-3, -4, -5, -6), small intestine (BMPs-3, -4, -7), heart (BMPs-2, -4, -6, (BMPs-2, -4, -5, -7) and teeth (BMPs-3, -4, -7). Second, several members of the family, including BMP-4 and -7, are key molecules in epithelial-mesenchymal interactions, for instance during odontogenesis. Third, BMP-2 and BMP-4 are involved in the signaling pathway that controls patterning in the developing chick limb and BMP-4 is a ventralizing factor in early Xenopus development. Fourth. Drosophila homologs of the BMPs, the decapentaplegic (dpp) and 60 A gene products, have the capacity to induce bone in mammals whereas human BMP-4 confers normal embryonic dorso-ventral patterning in Drosophila transformants defective in dpp expression. Thus, the BMPs are now appreciated as pleiotropic cytokines.
Interestingly, none of the known BMPs are strongly expressed in the chondroblasts and chondrocytes of the cartilage core of developing long bones. The hypertrophic chondrocytes, where both Vgr-1 (BMP-6, (Lyons et al., Development 109:833 (1990)) and OP-1 (BMP-7)(Vukicevic et al., Biochem. Biophys. Res. Commun. 198:693 (1994)) have been found are exceptions in this regard.

The United States of America as represented by the Department of Health and Human Services


A mattress suspension system for a vehicle for comfortably supporting an individual resting upon a mattress within a moving vehicle. The mattress suspension system for a vehicle includes a lower frame attached to a floor of a vehicle, a plurality of pivot members pivotally attached to the lower frame and pivotally attached to a pair of first support members and a pair of second support members, a first shaft and a second shaft attached to the first support members and slidably extending through the pair of second support members, a plurality of pivot members pivotally attached to the first and second support members extending upwardly and pivotally attached to an upper frame, a support device attached between the lower frame and the upper frame, and a shock attached between the upper frame and the lower frame. The support device is preferably comprised of an air sleeve or other device capable of providing an upward force upon the upper frame.

1. Field of the Invention
The present invention relates generally to vehicle bed devices and more specifically it relates to a mattress suspension system for a vehicle for comfortably supporting an individual resting upon a mattress within the vehicle while in motion.
2. Description of the Prior Art
Bed support devices for vehicles have been in use for years. Typically, conventional bed support devices for vehicles such as semi-tractors are not suitable for resting or sleeping upon while the vehicle is in motion. Conventional bed support devices for vehicles do not smoothly support an individual resting upon reducing the quality of the resting or sleep thereby leading to increased driver fatigue.
Examples of patented bed support devices which are illustrative of such prior art include U.S. Pat. No. 4,541,134 to Black et al.; U.S. Pat. No. 4,196,483 to Lefler et al.; U.S. Pat. No. 4,144,601 to Anderson et al.; U.S. Pat. No. 3,760,436 to Zach et al.; U.S. Pat. No. 5,598,591 to Kelley; U.S. Pat. No. 4,868,939 to Tagtow; U.S. Pat. No. 4,107,797 to Maxwell, Sr.; U.S. Pat. No. 5,638,560 to Rigdon et al.; U.S. Pat. No. 5,218,728 to Lloyd et al.; U.S. Pat. No. 4,989,281 to Christensen; U.S. Pat. No. 4,669,139 to Richter, Jr.; and U.S. Pat. No. 3,612,599 to Sternberg.
While these devices may be suitable for the particular purpose to which they address, they are not as suitable for comfortably supporting an individual resting upon a mattress within the vehicle. Conventional bed support devices for vehicles are very rough and difficult to sleep upon for a team of drivers while the vehicle is in motion.
In these respects, the mattress suspension system for a vehicle according to the present invention substantially departs from the conventional concepts and designs of the prior art, and in so doing provides an apparatus primarily developed for the purpose of comfortably supporting an individual resting upon a mattress within a moving vehicle.
In view of the foregoing disadvantages inherent in the known types of bed support devices now present in the prior art, the present invention provides a new mattress suspension system for a vehicle construction wherein the same can be utilized for comfortably supporting an individual resting upon a mattress within a moving vehicle.
The general purpose of the present invention, which will be described subsequently in greater detail, is to provide a new mattress suspension system for a vehicle that has many of the advantages of the bed support devices for vehicles mentioned heretofore and many novel features that result in a new mattress suspension system for a vehicle which is not anticipated, rendered obvious, suggested, or even implied by any of the prior art bed support devices for vehicles, either alone or in any combination thereof.
To attain this, the present invention generally comprises a lower frame attached to a floor of a vehicle, a plurality of pivot members pivotally attached to the lower frame and pivotally attached to a pair of first support members and a pair of second support members, a first shaft and a second shaft attached to the first support members and slidably extending through the pair of second support members, a plurality of pivot members pivotally attached to the first and second support members extending upwardly and pivotally attached to an upper frame, a support device attached between the lower frame and the upper frame, and a shock attached between the upper frame and the lower frame. The support device is preferably comprised of an air sleeve or other device capable of providing an upward force upon the upper frame.
There has thus been outlined, rather broadly, the more important features of the invention in order that the detailed description thereof may be better understood, and in order that the present contribution to the art may be better appreciated. There are additional features of the invention that will be described hereinafter and that will form the subject matter of the claims appended hereto.
In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purpose of the description and should not be regarded as limiting.
A primary object of the present invention is to provide a mattress suspension system for a vehicle that will overcome the shortcomings of the prior art devices.
A second object is to provide a mattress suspension system for a vehicle for comfortably supporting an individual resting upon a mattress within the vehicle while in motion.
Another object is to provide a mattress suspension system for a vehicle that reduces the roughness and bumps associated with conventional bed support devices utilized within vehicles while in motion.
An additional object is to provide a mattress suspension system for a vehicle that can be utilized most types of vehicles including but not limited to semi-tractors, trucks, buses and campers.
A further object is to provide a mattress suspension system for a vehicle that provides a more restful sleep for an individual thereby reducing stress and fatigue which can be dangerous.
Another object is to provide a mattress suspension system for a vehicle that increases the safety of drivers of commercial vehicles during extended periods of travel.
Other objects and advantages of the present invention will become obvious to the reader and it is intended that these objects and advantages are within the scope of the present invention.
To the accomplishment of the above and related objects, this invention may be embodied in the form illustrated in the accompanying drawings, attention being called to the fact, however, that the drawings are illustrative only, and that changes may be made in the specific construction illustrated and described within the scope of the appended claims.

Mattress suspension system for a vehicle


A replay signal, obtained on reproducing a recording medium, on which has been recorded a digital signal, is supplied to an input terminal (1), and quantized by an A/D converter (8). The so quantized signal is processed by an integrator (20), formed by a first order IIR filter, so as to be adjusted in gain by an amplifier (21). The quantized replay signal is also processed by a differentiator formed by a combination of a first order FIR filter (22) and a first order IIR filter (23) so as to be then adjusted in gain by an amplifier (24). The resulting signal is then supplied to an adder (25) where it is subtracted from an output signal of the amplifier (21). In this manner, the differentiation/integration equalizer, formed by an analog circuit, is constructed by a digital circuit of a simplified configuration without raising the number of orders of the filters. The replay signal is processed by differentiation/integration such as to satisfy the equalization standard.

In a digital data recording and/or reproducing apparatus, partial response (PR) is exploited in recording symbols in order to suppress inter-symbol interference. The PR means an equalization system in which the inter-symbol interference is positively applied to the waveform to achieve efficient transmission. Recently, this PR is frequently used in a so-called PRML (partial response maximum likelihood) signal processing system in which a pre-correlated data sequence is combined with the viterbi decoding system in which the maximum likelihood sequence is selected and reproduced. There are several types of the PR, from which the PR matched to characteristics of the transimission channel in use or to characteristics of the recording and/or reproducing system in use is selected.
Among these PR types, the response characteristics of the PR1(=PR(1, l)) and PR2(=PR(1, 2, l)) are represented as (1+D) and (1+2·D+D·D), where D is a unit delay or one-sample delay. With the PR1 and PR2, if it is attempted to effect equalization so as to satisfy the Nyquist standard, the characteristics achieved are the low range emphasizing characteristics. For example, in the frequency response of PR1, shown in FIG. 1, the replay signals are needed as from the DC components.
However, in a recording and/or reproducing apparatus, for example a magnetic recording apparatus, DC components are not transmitted, while low range loss is encountered due to use of a magnetic recording medium. For compensation, an integration equalizer is needed. In particular, compensation of the low range loss by the aforementioned integration equalization is critical in case of application to the PRML signal processing system, combined with the decoding of the ML system, especially in consideration of the importance in raising the waveform reproducibility.
Heretofore, such a circuit structure, shown in FIG. 2, has been known as a signal processing circuit, inclusive of an integration equalizer, implemented as an analog circuit. Referring to FIG. 2, a replay signal, supplied to an input terminal 101, has its low range components equalized by integration with an integrator 102 formed by an LPF (low-pass filter), and the amplitude of the integrated replay signal is adjusted by an amplifier 103. Since the high range components, resulting from processing by the integrator configuration, undergo phase distortion, the replay signal, supplied from the input terminal 101, are sent to a differentiator 104, formed by a HPF (high-pass filter), for compensating the phase of the high range components. The amplitude of the differentiated replay signal is adjusted by an amplifier 105. An output signal from the amplifier 105 is supplied to an adder 106 where it is subtracted from the replay signal sent from the integrator 102 through the amplifier 103. It is noted that the amplifiers 103, 105 adjust the signal gain into matching with the equalization standard for the integrator side frequency and for the differentiator side frequency, respectively. This type of the integration equalizer is termed a differentiation/integration equalizer. An output from the adder 106 is sent through an anti-aliasing LPF (low-pass filter) 107 to an AID converter (analog-to-digital converter) 108 and quantized. The quantized signal is PR-equalized by an adaptive equalizing filter 109 and taken out at an output terminal 110. In the circuit of FIG. 2, the portions encircled by a broken line (integrator 102, differentiator 104, amplifiers 103, 105, adder 106 and LPF 107) are formed by analog circuits.
The above-described circuit operates as follows: It is assumed that a NRZ (non-return-to-zero) signal pattern, shown in FIG. 3, has been recorded on a recording medium by a recording and/or reproducing apparatus. The replay signal from the recording and/or reproducing apparatus at this time is as shown in FIG. 4 and is supplied to the input terminal 101 of FIG. 2. The replay signal has its low range components extracted by the integrator 102 of FIG. 2, and an integrated output shown in FIG. 5 is obtained. The signal output from the integrator 102 is amplified by the amplifier 103 into meeting with the equalization standard for this frequency. On the other hand, the replay signal, supplied to the input terminal 101, has its high range components extracted by the differentiator 104, and a differentiated output shown in FIG. 6 is obtained. The signal output from the differentiator 104 is amplified by the amplifier 105 into meeting with the equalization standard for this frequency. The replay signal, equalized for each frequency, is supplied to the adder 106 of FIG. 2 where the replay signal sent through the differentiator 104 and the amplifier 105 is subtracted from the replay signal sent through the integrator 102 and the amplifier 103. The resulting replay signal is shown in FIG. 7. After rough equalization by the differentiation/integration equalizer, the replay signal is quantized by the A/D converter 108 of FIG. 2 and processed by the adaptive equalization filter 109 with equalization to higher accuracy.
If the case of the PR1 is taken as an example, the frequency response is as shown in FIG. 1. If, in a system with low range cut-off characteristics, such as a magnetic recording and/or reproducing apparatus, the replay signal is to be equalized to the corresponding equalization standard, the DC component is not reproduced. Thus, in order to provide a sufficient S/N ratio, the gain of the amplifier 103 on the output side of the integrator 102 of FIG. 2 is significant. If such analog circuit is to be implemented as an LSI, a large operating range needs to be provided, so that the driving current for the circuit is correspondingly increased to render it difficult to lower the voltage or power consumption.

Signal processing apparatus and method, and digital data reproducing apparatus


A laminated flat mop head which includes a flat foam layer laminated with a fabric material without using glue or adhesive.

Mop heads made of foam have existed for sometime due to their ability to easily absorb and retain liquids during mopping. Such mop heads may be permanently attached to the end of a mop or they may be removable and replaceable. However, whether or not the foam mop heads are permanently attached or replaceable, minute particles and/or pieces of the foam mop heads become separated from the mop head over time during normal wearing of the mop head. As a result, the utility of the mop head decreases over time. In addition, the minute particles and/or pieces of the foam mop heads may result in further contamination of a site or space for which the mop is being used to clean. Accordingly, there is a need for a foam mop head with improved durability where particle removal that results from the wearing of the mop is decreased.