A dishwashing cleaning wipe comprising a single layer needle punched fabric wherein the fabric is impregnated with a cleaning composition.

The present invention relates to a dishwashing cleaning wipe which is single or multi layer fabric substrate which has been impregnated with a liquid cleaning composition.
The patent literature describes numerous wipes for both body cleaning and cleaning of hard surfaces but none describe wipes for cleaning dishware flatware, pots and pans. U.S. Pat. Nos. 5,980,931, 6,063,397 and 6,074,655 teach a substantially dry disposable personal cleansing product useful for both cleansing and conditioning the skin and hair. U.S. Pat. No. 6,060,149 teaches a disposable wiping article having a substrate comprising multiple layers.
U.S. Pat. Nos. 5,756,612; 5,763,332; 5,908,707; 5,914,177; 5,980,922 and 6,168,852 teach cleaning compositions which are inverse emulsions.
U.S. Pat. Nos. 6,183,315 and 6,183,763 teach cleaning compositions containing a proton donating agent and having an acidic pH. U.S. Pat. Nos. 5,863,663; 5,952,043; 6,063,746 and 6,121,165 teaches cleaning compositions which are oil in water emulsions.
A single use cleaning wipe for dishwashing application comprises a water insoluble substrate, with a cleaning composition containing at least one anionic surfactants and water coated onto and/or impregnated into the water insoluble substrate.
The liquid cleaning compositions of this invention are not an emulsion and do not contain potassium sorbate, a polysaccharide polymer, a polycarboxylate polymer, polyvinyl alcohol polymer, polyvinylpyrrolidone polymer, methyl vinyl ether polymer or a glucoside surfactant
The present invention relates to a cleaning wipe for dishware, flatware, pots and pans which comprises approximately:
(a) 20 wt. % to 95 wt. % of a water insoluble substrate; and
(b) 5 wt. % to 80 wt. % of a liquid cleaning composition being coated onto and/or impregnated into said water insoluble substrate, wherein said liquid cleaning composition comprises:
(i) 5 wt. % to 50 wt. %, more preferably 8 wt. % to 40 wt. % of at least one anionic surfactant selected from the group of sulfate anionic surfactants and sulfonated anionic surfactants and mixtures thereof; and
(ii) the balance being water, wherein the composition has a pH of 3 to 7 and does not contain ammonium hydroxide, an alkali metal hydroxide, potassium sorbate, a polysaccharide polymer, a polycarboxylate polymer, polyvinyl alcohol polymer, polyvinylpyrrolidone polymer, methyl vinyl ether polymer and the cleaning composition has a Gram Positive Residual Effective Index as measured by the method set forth in U.S. Pat. No. 6,284,259 of less than 0.35, preferably less than 0.3.
Suitable water-soluble non-soap, anionic surfactants used in the instant compositions include those surface-active or detergent compounds which contain an organic hydrophobic group containing generally 8 to 26 carbon atoms and preferably 10 to 18 carbon atoms in their molecular structure and at least one water-solubilizing group selected from the group of sulfonate, sulfate and carboxylate so as to form a water-soluble detergent. Usually, the hydrophobic group will include or comprise a C8-C22 alkyl, alkyl or acyl group. Such surfactants are employed in the form of water-soluble salts and the salt-forming cation usually is selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di- or tri-C2-C3 alkanolammonium, with the sodium, magnesium and ammonium cations again being preferred.
Examples of suitable sulfonated anionic surfactants are the well known higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, C8-C15 alkyl toluene sulfonates and C8-C15 alkyl phenol sulfonates.
A preferred sulfonate is a mixture of an alkali metal ammonium salt and an alkaline earth metal salt of a linear alkyl benzene sulfonate having a high content of 3- (or higher) phenyl isomers and a correspondingly low content (well below 50%) of 2- (or lower) phenyl isomers, that is, wherein the benzene ring is preferably attached in large part at the 3 or higher (for example, 4, 5, 6 or 7) position of the alkyl group and the content of the isomers in which the benzene ring is attached in the 2 or 1 position is correspondingly low.
Other suitable anionic surfactants are the olefin sulfonates, including long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. These olefin sulfonate detergents may be prepared in a known manner by the reaction of sulfur trioxide (SO3) with long-chain olefins containing 8 to 25, preferably 12 to 21 carbon atoms and having the formula RCHxe2x95x90CHR1 where R is a higher alkyl group of 6 to 23 carbons and R1 is an alkyl group of 1 to 17 carbons or hydrogen to form a mixture of sultones and alkene sulfonic acids which is then treated to convert the sultones to sulfonates. Preferred olefin sulfonates contain from 14 to 16 carbon atoms in the R alkyl group and are obtained by sulfonating an xcex1-olefin.
Other examples of suitable anionic sulfonate surfactants are the paraffin sulfonates containing 10 to 20, preferably 13 to 17, carbon atoms. Primary paraffin sulfonates are made by reacting long-chain alpha olefins and bisulfites and paraffin sulfonates having the sulfonate group distributed along the paraffin chain are shown in U.S. Pat. Nos. 2,503,280; 2,507,088; 3,260,744; 3,372,188; and German Patent 735,096.
Examples of satisfactory anionic sulfate surfactants are the alkali metal or ammonium salt C8-C18 alkyl sulfate salts the ethoxylated C8-C18 alkyl ether sulfate salts having the formula R(OC2H4)nOSO3M wherein n is 1 to 12, preferably 1 to 5, and M is a metal cation selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di- and triethanol ammonium ions. The alkyl sulfates may be obtained by sulfating the alcohols obtained by reducing glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resultant product.
On the other hand, the ethoxylated alkyl ether sulfates are obtained by sulfating the condensation product of ethylene oxide with a C8-C18 alkanol and neutralizing the resultant product. The alkyl sulfates may be obtained by sulfating the alcohols obtained by reducing glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resultant product. The ethoxylated alkyl ether sulfates differ from one another in the number of moles of ethylene oxide reacted with one mole of alkanol. Preferred alkyl sulfates and preferred ethoxylated alkyl ether sulfates contain 10 to 16 carbon atoms in the alkyl group.
The ethoxylated C8-C12 alkylphenyl ether sulfates containing from 2 to 6 moles of ethylene oxide in the molecule also are suitable for use in the inventive compositions. These surfactants can be prepared by reacting an alkyl phenol with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resultant ethoxylated alkylphenol.
Other suitable anionic surfactants are the C9-C15 alkyl ether polyethenoxyl carboxylates having the structural formula R(OC2H4)nOX COOH wherein n is a number from 4 to 12, preferably 5 to 10 and X is selected from the group consisting of
wherein R1 is a C1-C3 alkylene group. Preferred compounds include C9-C11 alkyl ether polyethenoxy (7-9) C(O) CH2CH2COOH, C13-C15 alkyl ether polyethenoxy (7-9)
and C10-C12 alkyl ether polyethenoxy (5-7) CH2COOH. These compounds may be prepared by condensing ethylene oxide with appropriate alkanol and reacting this reaction product with chloracetic acid to make the ether carboxylic acids as shown in U.S. Pat. No. 3,741,911 or with succinic anhydride or phthalic anhydride. Obviously, these anionic. surfactants will be present either in acid form or salt form depending upon the pH of the final composition, with salt forming cation being the same as for the other anionic surfactants.
The instant composition can also contain a surfactant selected from the group consisting of amine oxides, alkyl polyglucosides, zwitterionics and C12-14 fatty acid alkanolamides and mixtures thereof.
The instant composition can optionally include 0.1 wt. % to 15 wt. % of a water-soluble zwitterionic surfactant, which can also be used provides good foaming properties and mildness to the present nonionic based liquid detergent. The zwitterionic surfactant is a water soluble betaine having the general formula:
wherein R1 is an alkyl group having 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, or the amido radical:
wherein R is an alkyl group having 9 to 19 carbon atoms and a is the integer 1 to 4; R2 and R3 are each alkyl groups having 1 to 3 carbons and preferably 1 carbon; R4 is an alkylene or hydroxyalkylene group having from 1 to 4 carbon atoms and, optionally, one hydroxyl group. Typical alkyldimethyl betaines include decyl dimethyl betaine or 2-(N-decyl-N,N-dimethyl-ammonia) acetate, coco dimethyl betaine or 2-(N-coco N,N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, lauryl diemethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine, etc. The amidobetaines similarly include cocoamidoethylbetaine, cocoamidopropyl betaine and the like. A preferred betaine is coco (C8-C18) amidopropyl dimethyl betaine.
The instant composition can optionally include 0.1 wt. % to 15 wt. % of an amine oxide semi-polar nonionic surfactants comprise compounds and mixtures of compounds having the formula:
wherein R1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms, R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl, and n is from 0 to 10. Particularly preferred are amine oxides of the formula:
wherein R1 is a C12-16 alkyl and R2 and R3 are methyl or ethyl. The above ethylene oxide condensates, amides, and amine oxides are more fully described in U.S. Pat. No. 4,316,824 which is hereby incorporated herein by reference.
The instant composition can optionally contain 0.1 wt. % to 10 wt. % of a C12-14 alkyl monoalkanol amide such as lauryl monoalkanol amide or a C12-14 alkyl dialkanol amide such as lauryl diethanol amide or coco diethanol amide.
The alkyl polysaccharides surfactants, which can be optionally used at a concentration of 0.1 wt. % to 15 wt. % have a hydrophobic group containing from about 8 to about 20 carbon atoms, preferably from about 10 to about 16 carbon atoms, most preferably from about 12 to about 14 carbon atoms, and polysaccharide hydrophilic group containing from about 1.5 to about 10, preferably from about 1.5 to about 4, most preferably from about 1.6 to about 2.7 saccharide units (e.g., galactoside, glucoside, fructoside, glucosyl, fructosyl; and/or galactosyl units). Mixtures of saccharide moieties may be used in the alkyl polysaccharide surfactants. The number x indicates the number of saccharide units in a particular alkyl polysaccharide surfactant. For a particular alkyl polysaccharide molecule x can only assume integral values. In any physical sample of alkyl polysaccharide surfactants there will be in general molecules having different x values. The physical sample can be characterized by the average value of x and this average value can assume non-integral values. In this specification the values of x are to be understood to be average values. The hydrophobic group (R) can be attached at the 2-, 3-, or 4-positions rather than at the 1-position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside or galactoside). However, attachment through the 1-position, i.e., glucosides, galactoside, fructosides, etc., is preferred. In the preferred product the additional saccharide units are predominately attached to the previous saccharide unit""s 2-position. Attachment through the 3-, 4-, and 6-positions can also occur. Optionally and less desirably there can be a polyalkoxide chain joining the hydrophobic moiety (R) and the polysaccharide chain. The preferred alkoxide moiety is ethoxide.
Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 20, preferably from about 10 to about 18 carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can contain up to about 30, preferably less than about 10, alkoxide moieties.
Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or galactosyls and mixtures thereof.
The alkyl monosaccharides are relatively less soluble in water than the higher alkyl polysaccharides. When used in admixture with alkyl polysaccharides, the alkyl monosaccharides are solubilized to some extent. The use of alkyl monosaccharides in admixture with alkyl polysaccharides is a preferred mode of carrying out the invention. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
The preferred alkyl polysaccharides are alkyl polyglucosides having the formula
R2O(CnH2nO)r(Z)x
wherein Z is derived from glucose, R is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3 preferably 2, r is from 0 to 10, preferable 0; and x is from 1.5 to 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7. To prepare these compounds a long chain alcohol (R2OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkyl polyglucosides can be prepared by a two step procedure in which a short chain alcohol (R1OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkyl polyglucosides can be prepared by a two step procedure in which a short chain alcohol (C1-6) is reacted with glucose or a polyglucoside (x=2 to 4) to yield a short chain alkyl glucoside (x=1 to 4) which can in turn be reacted with a longer chain alcohol (R2OH) to displace the short chain alcohol and obtain the desired alkyl polyglucoside. If this two step procedure is used, the short chain alkylglucosde content of the final alkyl polyglucoside material should be less than 50%, preferably less than 10%, more preferably less than about 5%, most preferably 0% of the alkyl polyglucoside.
The amount of unreacted alcohol (the free fatty alcohol content) in the desired alkyl polysaccharide surfactant is preferably less than about 2%, more preferably less than about 0.5% by weight of the total of the alkyl polysaccharide. For some uses it is desirable to have the alkyl monosaccharide content less than about 10%.
The used herein, xe2x80x9calkyl polysaccharide surfactantxe2x80x9d is intended to represent both the preferred glucose and galactose derived surfactants and the less preferred alkyl polysaccharide surfactants. Throughout this specification, xe2x80x9calkyl polyglucosidexe2x80x9d is used to include alkyl polyglycosides because the stereochemistry of the saccharide moiety is changed during the preparation reaction.
An especially preferred APG glycoside surfactant is APG 625 glycoside manufactured by the Henkel Corporation of Ambler, Pa. APG25 is a nonionic alkyl polyglycoside characterized by the formula:
CnH2n+1O(C6H10O5)xH
wherein n=10 (2%); n=122 (65%); n=14 (21-28%); n=16 (4-8%) and n=18 (0.5%) and x (degree of polymerization)=1.6. APG 625 has: a pH of 6 to 10 (10% of APG 625 in distilled water); a specific gravity at 25xc2x0 C. of 1.1 g/ml; a density at 25xc2x0 C. of 9.1 lbs/gallon; a calculated HLB of 12.1 and a Brookfield viscosity at 35 C., 21 spindle, 5-10 RPM of 3,000 to 7,000 cps.
The C12-C14 fatty acid alkanolamides can be optionally included in the instant compositions at a concentration of 0.1 wt. % to 10 wt. %.
The instant composition can optionally contain 0.1 wt. % to 10 wt. % of a polyethylene glycol is depicted by the formula:
HOxe2x80x94(CH2xe2x80x94CH2O)nxe2x80x94H
wherein n is about 8 to about 225, more preferably about 10 to about 100,000, wherein the polyethylene glycol has a molecular weight of about 200 to about 1,000. One preferred polyethylene glycerol is PEG1000 which is a polyethylene glycol having a molecular weight of about 1000.
The instant composition can optionally contain 0.05 wt. % to 4 wt. % of a proton donating agent is selected from the group consisting of inorganic acids such as sulfuric acid and hydrochloric acid and hydroxy containing organic acid, preferably a hydroxy aliphatic acid, wherein the hydroxy contains organic acid is selected from the group consisting of lactic acid, citric acid, orthohydroxy benzoic acid and glycolic acid and mixtures thereof.
The water is present in the composition at a concentration of about 5 wt. % to 70 wt. %.
The cleaning composition of this invention may, if desired, also contain other components either to provide additional effect or to make the product more attractive to the consumer. The following are mentioned by way of example: Antibacterial agents such as 2,4,4xe2x80x2-trichloro-2xe2x80x2hydroxydiphenyl ether colors or dyes in amounts up to 0.5% by weight; pH adjusting agents, such as sulfuric acid or sodium hydroxide, can be used as needed.
Preservatives which can be used in the instant compositions at a concentration of 0.005 wt. % to 3 wt. %, more preferably 0.01 wt. % to 2.5 wt. % are: benzalkonium chloride; benzethonium chloride,5-bromo-5-nitro-1,3dioxane; 2-bromo-2-nitropropane-1,3-diol; alkyl trimethyl ammonium bromide; N-(hydroxymethyl)-N-(1,3-dihydroxy methyl-2,5-dioxo-4-imidaxolidinyl-Nxe2x80x2-(hydroxy methyl) urea; 1-3-dimethyol-5,5-dimethyl hydantoin; formaldehyde; iodopropynl butyl carbamata, butyl paraben; ethyl paraben; methyl paraben; propyl paraben, mixture of methyl isothiazolinone/methyl-chloroisothiazoline in a 1:3 wt. ratio; mixture of phenoxythanol/butyl paraben/methyl paraben/propylparaben; 2-phenoxyethanol; tris-hydroxyethyl-hexahydrotriazine; methylisothiazolinone; 5-chloro-2-methyl-4-isothiazolin-3-one; 1,2-dibromo-2,4-dicyanobutane; 1-(3-chloroalkyl)-3,5,7-triaza-azoniaadamantane chloride; and sodium benzoate. PH adjusting agents such as sulfuric acid or sodium hydroxide can be used as needed.
The product of the present invention comprises a water insoluable substrate with one or more layers. Each layer may have different textures and abrasiveness. Differing textures can result from the use of different combinations of materials or from the use of different manufacturing processes or a combination thereof. A dual texture substrate can be made to provide the advantage of a more abrasive side for cleaning difficult to remove soils. A softer side can be used for fine dishware and flatware. The substrate should not dissolve or break apart in water. It is the vehicle for delivering the cleaning composition to dishware, flatware, pots and pans. Use of the substrate enhances lathering, cleaning and grease removal.
A wide variety of materials can be used as the substrate. It should have sufficient wet strength, abrasivity, loft and porosity. Examples include, non woven substrates, wovens substrates, hydroentangled substrates and sponges.
Examples of suitable non woven water insoluable substrates include, 100% cellulose Wadding Grade 1804 from Little Rapids Corporation, 100% polypropylene needlepunch material NB 701-2.8-W/R from American Non-wovens Corporation, a blend of cellulosic and synthetic fibres-Hydraspun 8579 from Ahlstrom Fibre Composites, and and0% Viscose/30% PES Code 9881 from PGI Nonwovens Polymer Corp.
Another useful substrate is manufactured by Jacob Holm-Lidro Rough. It is a composition material comprising a 65/35 viscose rayon/polyester hydroentangled spunlace layer with a hydroenlongated bonded polyeser scribbly layer.
Still another useful substrate is manufactured by Texel xe2x80x9cTIxe2x80x9d. It is a composite material manufactured from a layer of coarse fiber 100% polypropylene needlepunch, an absorbent cellulose core and a fine fiber polyester layer needlepunched together. The polypropylene layer can range from 1.5 to 3.5 oz/sq. yd. The cellulose core is a creped paper layer ranging from 0.5 to 2 oz./sq. yd. The fine fiber polyester layer can range from 0.5 to 2 oz./sq. yd.
Still another composite material manufactured by Texcel from a layer of coarse fiber 100% polypropylene needlepunch layer, an absorbent cellulose core and a fine fiber polyester layer needlepunched together. The polypropylene layer can range from 1.5 to 3.5 oz/sq. yd. The cellulose core is a creped paper layer ranging from 0.5 to 2 oz/sq. yd. The fine fiber polyester layer can range from 0.5 to 2 oz/sq. yd. The polypropylene layer is flame treated to further increase the level of abrasivity. The temperature of the flame and the length of time the material is exposed can be varied to create different levels of surface roughness.
The abrasiveness is tested by cutting one quarter inch thick Lucite boards to fit an abrader bed. The boards are marked to indicate the track of the wipes during abrasion (approximately 2xc2xc and 4xc2xd inches from one long edge) and three spots along the track (6, 9 and 12 inches from the short end). This gives unique and reproducible locations at which to do gloss measurements which are in the center of the abrasion track.
Using a BYK-Gardener Haze-Gloss glossmeter, the indicated spots are measured for starting gloss. An average and standard deviation is reported for each track using the three measurements.
Pieces of the wipes are cut approximately 3 inches by 2 inches. This piece is wrapped around a piece of sponge that fits in a holder for the abrader. (Indication should be made of whether the material is being used in the machine or cross direction). This wrapped sponge is placed in the holder, tucking all the edges of the wipe into the holder so that it is kept firmly in place. The dry sponge is wetted with approximately 20-25 g of water (either deionized, distilled or tap as the experiment desires). This is done so that there are two wipes in the trial.
The gloss measured Lucite board is placed in the abrader bed. Set the abrader for 500 cycles and start.
After the abrader cycles have ended, the Lucite board is removed. It is wiped dry with paper towel to remove any residual water. It is also inspected for any fingerprints incurred during handling and these are also wiped clean. Remeasure the gloss at the specified spots again and again report the average of these three spots and the standard deviation for each track.
The higher the abrasiveness of the wipe, the more that it roughens the surface of the Lucite and the more the gloss is reduced. The most abrasive of the wipes therefore give the greatest decrease in gloss. Results for this test are given below.
Ahlstrom Manufacturers:
A hydroentangled nonwoven created from a blend of cellulosic and polyester and/or polypropylene fibers with an abrasive side. The basis weight can range from 1.2 to 6 ounces per square yard.
Kimberly Clark Manufacturers:
A composite dual textured material manufactured by Kimberly Clark comprises a coarse meltblown polypropylene, polyethylene, or polyester and high loft spunbond polyester. The two materials can be laminated together using chemical adhesives or by coprocessing the two layers. The coarse meltblown layer can range from 1 to 3 ounces per square yard while the highloft spunbond layer can range from 1 to 3 ounces per square yard.
Another example of a composite is a dual textured material composed of coarse meltblown polypropylene, polyethylene, or polyester and polyester/cellulose coform. The two materials can be laminated together using chemical adhesives or by coprocessing the two layers. The coarse meltblown layer can range from 1 to 3 ounces per square yard. The coform layer can range in composition from 30% cellulose and 70% polyester to 70% cellulose and 30% polyester and the basis weight can range from 1.5 to 4.5 ounces per square yard.
The product of the present invention comprising mutliple layers may be ultrasonically bonded after applying the coating of one or more of the layers. Alternatively layers may be bonded together by needlepunch, thermal bonding, chemical bonding, or sonic bonding prior to applying the coating and/or impregnation.
The following examples illustrate liquid cleaning compositions of the described invention. Unless otherwise specified, all percentages are by weight. The exemplified compositions are illustrative only and do not limit the scope of the invention. Unless otherwise specified, the proportions in the examples and elsewhere in the specification are by weight.


An auto-registration method for scanners. The method includes implanting a serial number into a scanner. When the scanner operates, the serial number is automatically retrieved. If the scanner is linked to a network, the serial number is transmitted to a documentary file inside a registration center through the net. On the other hand, if the scanner is not connected to a network, other data transmission means can be used to carry out the registration. According to the registered information, various post-registration services are executed.

1. Field of the Invention
The present invention relates to the registration of a scanner. More particularly, the present invention relates to the auto-registration of a scanner.
2. Description of the Related Art
The serial number of a scanner is conventionally registered manually after the purchase of the scanner. In other words, documents containing the serial number and related information of a scanner are provided by a manufacturer. After the scanner is sold to a customer or a reseller, the documents are sent back to the manufacturer by mail or fax.
Although the above document processing arrangement has been in use for many years, there are many drawbacks. First, the identification of serial number holder is difficult because the serial number documents accompanying the machine can be separated out. Due to errors in filing or maintenance, these serial number documents are sometimes lost. Normally, the lost of serial number documents in unlikely to have serious consequences. However, problems may occur when the machine needs to be serviced or repaired within manufacturer""s warrantee period. Arguments often break out between the manufacturer and the buyer when serial number data are lost or erroneous.
In addition, since the serial number is kept outside the machine, anybody besides the actual user also has access to the serial number data leading to other problems. For example, as a promotion, manufactures will often offer a rebate, a discount or a gift to customer after receiving back the serial number data. If people other than the user have access to the serial number data, the rules for obtaining the benefits can be breached easily.
Aside from registering the serial number provided by manufacturers, manufacturers sometimes implant the serial number data directly inside a hardware circuit. Although such an arrangement is capable of eliminating the aforementioned drawbacks, each hardware circuit must be fabricated slightly differently because different serial number data has to be incorporated inside each circuit. Hence, cost of production is likely to increase.
In general, the major drawbacks of conventional scanner registration method includes:
1. The serial number may be lost due to filing error. Arguments between the manufacturers and the user concerning the maintenance and repair of the scanner can arise, especially during the warrantee period.
2. Since other people besides the user can have access to the serial number data, intended rebate and gifts can be misused.
3. The implantation of serial number data directly in hardware will increase production cost.
The invention provides an auto-registration method for scanners. The method includes implanting a serial number into a scanner. When the scanner operates, the serial number is automatically retrieved. As soon as the scanner is connected to a network, the serial number is transmitted to a documentary file inside a registration center.
The serial number is implanted into the scanner by attaching a barcode representing the serial number in a location within image-scanning area of the scanner. Alternative, the serial number is hardwired to an application specific integrated circuit (ASIC) within the scanner so that the serial number can be automatically sensed once the scanner is turned on.
Furthermore, several post-registration services can be carried out after serial number data are established. These post-registration services include return material authorization (RMA), rebate or the establishment of a user file.
The invention also provides a second auto-registration method for scanners. A serial number is implanted into a scanner. When the scanner operates, the serial number is automatically retrieved.
The serial number is implanted into the scanner by attaching a barcode representing the serial number in a location within image-scanning area of the scanner. Alternative, the serial number is hardwired to an application specific integrated circuit (ASIC) within the scanner so that the serial number can be automatically sensed once the scanner is turned on.
In brief, by attaching a bar code representing the serial number to a scanner or hardwiring the serial number to application specific integrated circuit, persons having access to the serial number is limited. By limiting access to the serial number, post sales services such as RMA, rebate or gift award programs can be carried out more smoothly. In addition, the creation of a user file for each customer helps to provide prompt and quality services.
Accordingly, the present invention is to provide an auto-registration method for scanners capable of resolving after-sales services such as return material authorization (RMA) and related problems. In addition, the method facilitates the execution of any rebate or gift award programs to customers as well as the creation of a user file for each customer so that customer can be serviced promptly and appropriately.
It is to be understood that both the foregoing general description and the following detailed description are exemplary, and are intended to provide further explanation of the invention as claimed.


A semiconductor device includes a lead frame, a semiconductor element mounted on the lead frame, and a frame-like member formed on the lead frame, surrounding the semiconductor element, and covering a side surface of the lead frame and exposing a lower surface of the lead frame. The frame-like member has at least one concave portion in a side surface thereof. The concave portion has a ceiling portion located at the same height as or lower than an upper surface of the lead frame, and a bottom portion located higher than the lower surface of the lead frame.

The present disclosure relates to semiconductor devices, lead frame assemblies, methods for fabricating semiconductor devices, and methods for fabricating lead frame assemblies. More particularly, the present disclosure relates to assemblies of surface mount lead frames, resin encapsulated semiconductor devices employing the lead frame assemblies, methods for fabricating the lead frame assemblies, and methods for fabricating the semiconductor devices.
In recent years, demands for smaller-size and higher-performance electronic apparatuses have lead to increased miniaturization of semiconductor devices. There are commercialized small-size resin encapsulated semiconductor devices employing lead frames, such as a land grid array (LGA) package, a quad flat non-leaded (QFN) package, a small outline non-leaded (SON) package, etc., in which elements are encapsulated on substantially only one side. These semiconductor devices are typically formed as follows. A sheet of metal base is initially processed by stamping, etching, etc. to form a multiple lead frame arrangement in which a plurality of lead frames are attached to rails. On the multiple lead frame arrangement, semiconductor elements are mounted, a resin is molded, etc. to form packages. The packaged lead frames are removed from the rails to obtain individual completed semiconductor devices.
In the multiple lead frame arrangement, typically, the lead frames are attached to the rails by tie bars, and the lead frames are removed from the rails by cutting the tie bars. However, when the tie bar is cut, large shear stress needs to be applied to the tie bar, and therefore, the package is likely to be damaged in the vicinity of the tie bar. It is contemplated that the tie bar may be narrowed to facilitate cutting. In this case, however, the tie bar may have insufficient holding strength. Therefore, an attempt has been made to provide an auxiliary tie bar around the tie bar (see, for example, Japanese Patent Publication No. H03-105959). The auxiliary tie bar is not attached to the lead frame, and a tip portion of the auxiliary tie bar is buried in the package resin. Because the lead frame is held by the tie bar and the auxiliary tie bar, the holding strength is increased. Moreover, the lead frame can be removed by pulling the auxiliary tie bar out of the package resin, and therefore, the package is less likely to be damaged compared to when a thicker tie bar is used.

Semiconductor device, lead frame assembly, and method for fabricating the same


A fast-curing polyurethane coating system for a game ball is described herein. The coating system comprises a mixture of a polyol, an isocyanate, a solvent and a surprisingly high level of catalyst which accelerates the curing process. The coating is a two-part polyurethane system which is preferably applied by spraying. The coating is particularly well-suited for use on golf balls, and also can be applied to other game balls such as softballs, baseballs, and cricket balls.

The present invention relates generally to game balls, and more particularly to a quick-cure coating for game balls.
For decades, golf balls were finished by applying one or more coats of paint or the like to the outer surface of a golf ball cover. To achieve a desirable white appearance, a multicoat paint system typically comprising a primer coat followed by one or more opaque coatings was applied to the golf ball. Such golf balls are typically referred to as xe2x80x9cpainted ballsxe2x80x9d. In the 1980""s, the concept of incorporating pigment into the cover material prior to molding the cover of the golf ball was introduced, thereby eliminating the step of painting the golf ball. Such golf balls are typically referred to as xe2x80x9cpigmented ballsxe2x80x9d.
Whether the golf balls are painted or pigmented, identifying indicia such as the manufacturer""s trademark or logo, or a model or identification number, are stamped on the ball. In order to prevent the stamped indicia from being rubbed off, and also to impart a desirable glossiness to the ball, one or two clear outer coatings are applied to the ball. Typically, such clear coatings consist of a clear solvent based primer or water borne primer followed by a clear urethane top coat. The logo or other indicia typically is stamped on the primed ball before application of the top coat. The urethane top coat is usually a two-part polyurethane, consisting of a polyol and a polyisocyanate mixed together and reacted to form the urethane coating.
In golf ball manufacturing, the period of time required to apply and cure the final glossy top coat encompasses a large percentage of the total time required for golf ball manufacture. Known golf ball finish coatings typically require 6-8 hours of curing at an elevated temperature. Curing is generally conducted in a batch-type manner in large ovens.
One advantage of the conventional method for finishing golf balls is that the long cure time of the final top coat ensures that adhesion of the finish coating to the golf ball is strong, and as a result, the golf ball has a long, useful life. Another advantage is that the pot life of the mixed coating is relatively long. However, known methods are disadvantageous in that the 6-8 hour curing time prevents same day delivery of golf balls, particularly customized logo balls. Furthermore, one or more very large ovens are required if a sizable number of golf balls are to be manufactured daily.
In a conventional polyurethane finish coating system for coating golf balls, a polyol and a polyisocyanate are mixed in a pressure pot without a catalyst. The mixture in the pressure pot is then sprayed on the outer surface of the golf balls. Most of the mixture remains in the pot for some period of time before spraying. Thus, it is important to include enough solvent in the coating mixture to prevent the coating mixture from curing while it is still in the pressure pot and to provide for acceptable flowout of the coating mixture. However, it would be environmentally beneficial to be able to reduce the quantity of solvents in the coating system.
An object of the invention is to provide a fast curing coating system for game balls, such as golf balls, softballs, baseballs, cricket balls and the like.
Another object of the invention is to provide a game ball having a fast curing coating that demonstrates adhesion and abrasion resistance which is comparable or superior to prior known urethane coatings.
Yet another object of the invention is to provide a game ball coating system having a high solids concentration.
Yet another object of the invention is to provide a low V.O.C. coating system for a game ball.
Further objects of the invention will become apparent from the following description.
The invention in a preferred form is a game ball coating system comprising a mixture of a polyol, a polyisocyanate is present in a quantity appropriate to provide of xe2x80x94Nxe2x95x90Cxe2x95x90O equivalents to xe2x80x94OH, in the range of 0.90 to or more preferably 0.90 to 1.5%, up to 65 wt % of a solvent, and a compatible catalyst. The catalyst is present in a quantity such that the coating composition will be cured to a Sward rocker hardness of at least 10 in less than about 1.5 hours at an elevated temperature. The quantity of catalyst is preferably sufficient to provide for an at least 100% increase in viscosity of the coating system within 30 minutes at 25xc2x0 C., 1 atm and 60% relative humidity.
When applied to a game ball, the polyurethane finish coating preferably has an average initial wet thickness of no more than about 3.5 mils. In a particularly preferred form of the invention, the coating system is a two-part system including a first part containing the polyol, the catalyst and at least a portion of any solvent which is used, and a second part containing the polyisocyanate and/or polyisocyanurate.
The polyol preferably comprises at least one of a polyester, polyether or acrylic, and has a hydroxyl equivalent weight of 50-1500, and more preferably 100-1000. Blends of different polyols can be used. More preferably, the polyol is a saturated polyester polyol, and most preferably is the reaction product of an organic acid which includes at least one member selected from the group consisting of adipic acid, phthalic acid and isophthalic acid, an anhydride, and a glycol which includes at least one member selected from the group consisting of ethylene glycol and trimethylol propane.
The polyisocyanate or preferably includes at least one member selected from the group consisting of biurets and isocyanurate trimers of hexamethylene diisocyanate. Blends of polyisocyanates can be used. The solvent preferably includes one or more members selected from the group consisting of ketones, esters and acetates.
The catalyst preferably comprises at least one member selected from the group consisting of dibutyl tin dilaurate, dibutyl acetylacetonate, dibutyl tin dibutoxide, dibutyl tin sulphide, dibutyl tin di-2-ethylhexanoate, dibutyl tin (IV) diacetate, dialkyltin (IV) oxide, tributyl tin laurylmercaptate, dibutyl tin dichloride, organo lead, tetrabutyl titanate, tertiary amines, mercaptides, stannous octoate, potassium octoate, zinc octoate, diaza compounds, and potassium acetate. The catalyst preferably is present in a quantity of 0.01-10 weight % active catalyst (not including any carrier) based on total resin solids (polyol plus polyisocyanate, excluding solvents). The quantity of catalyst will depend upon the type of catalyst, polyol, polyisocyanate or polyisocyanurate, and solvents which are used, as well as the curing temperature and desired curing time. When dibutyl tin dilaurate is used as the catalyst, it preferably is present in an amount of about 0.05-0.35 weight % active catalyst based upon total resin solids, and more preferably 0.08-0.15 weight % based upon total resin solids. Excellent results have been achieved using about 0.1 weight % dibutyl tin dilaurate based upon total resin solids. Other catalysts preferably are used at levels which will produce the same state of cure as 0.05-0.35 weight % or more preferably 0.08-0.15 weight % active dibutyl tin dilaurate. The catalyst preferably is present in an amount sufficient to reduce the curing time of the coating by at least about 75% as compared to a coating system which does not contain the catalyst but is otherwise identical.
The invention accordingly consists in the features of construction, combination of elements and arrangement of parts which will be exemplified in the construction hereafter set forth and the scope of the application which will be indicated in the appended claims.
The invention is a coating system which will form a highly durable polyurethane coating on a game ball. The coating system contains an amount of catalyst which far exceeds the quantity of catalyst recommended by polyurethane coating manufacturers. When the high level of catalyst is used in conjunction with the mixing parameters of the invention, an excellent game ball coating can be formed at a surprisingly fast rate. By using an unexpectedly large amount of catalyst in the coating system, continuous production is facilitated. The coating system of the invention also provides for the uniform application of a game ball coating on a dimpled game ball such as a golf ball in which minimal dimple flooding occurs.
The coating system of the invention can be used for application of primer and/or top coatings, and is particularly useful as a finish coating system for a game ball. When the coating system is used to form a final top coating, the coating can be applied to game balls which have a variety of types of primer coatings, including waterborne and solvent-borne polyurethanes, and epoxies.
The final coating can be applied to a primed ball after the primer has been cured under conditions sufficient to drive off 90-98% of the water and solvent in the primer coating system, e.g. after the primed ball has been in a dry oven at 150xc2x0 F. for about 10 minutes. Furthermore, the coating of the invention can be applied as a final top coating directly to a game ball cover, without the use of a primer coating, when the particular coating system which is used provides for sufficient adhesion to the game ball cover without the use of a primer. In eliminating the primer coating, it is important to take into consideration the difficulty in adhering polymer coatings to certain game ball covers, such as golf ball covers which are made of ionomers or blends of ionomers with other cover materials, due to the presence of olefins in the ionomer. Thus, in some cases, it may be beneficial to treat an unprimed ionomer-containing cover before applying the top coat in a manner appropriate to promote adhesion. For game balls with a cover made of an ionomer having a relatively high zinc content, a thermoplastic polyurethane, or mixtures of ionomers and polyurethanes, it is likely that neither a primer coat nor treatment of the unprimed cover is necessary if the correct top coat is used.
Typically, the average thickness of the final coating is about 0.3 to 2.5 mils after curing, and preferably is about 0.3-2.0 mils after curing.
The coating systems of the present invention are two-part coatings with a first part comprising a polyol and a second part comprising a polyisocyanate. The polyols include acrylic, polyether and polyester polyols as well as alkyds. One particularly preferred coating system according to the invention is a two part solvent-borne polyurethane system in which the first part comprises a hydroxyl functional polyol having an hydroxyl equivalent weight in the range of 50 to 1500, with the most preferred equivalent weight being 200 to 800. Preferably, the hydroxyl functional polyol is ethylenically saturated. Suitable saturated polyesters for use herein include poly (oxydiethylene adipates) that are condensation products of diethylene glycol and adipic acid, branched with trimethylolpropane or pentaerythritol, and polycaprolactone (hydroxycaproic acid) polyesters. Suitable saturated polyethers include polymers of propylene oxide or propylene oxide/ethylene oxide. Such materials are usually triols or diols with molecular weights between 1000 and 7000. Suitable saturated acrylics include derivatives of acrylic acid, such as methyl methacrylate, co-polymerized with hydroxyl functional monomers, such as 2-hydroxy-ethyl methacrylate. Suitable (non-limiting) examples of polyols include Desmophen 651A-65, 800, 670A-80, 680-70 and 631A-75, which are saturated polyester resins, available from Bayer Corp., Aroplaz 1133-X-69, a short oil alkyd marketed by Spencer Kellogs Products Div., Reichhold Chemicals, Inc., Minneapolis, Minn., Pentalyn 802A, a phenolic modified polyester resin marketed by Hercules Inc., Wilmington Del., and VMCA, a hydroxyl functional vinyl resin marketed by Union Carbide, Danbury, Conn.
As indicated above, in addition to a polyol, the two-part polyurethane system comprises a crosslinking agent which is polyisocyanate and which preferably is carried in a solvent. Various diisocyantes, including but not limited to hexamethylene diisocyanate (HDI), methylene diisocyanate (MDI), toluene diisocyanate (TDI), and isophorone diisocyanate (IPDI) can be used. Aliphatic isocyanates are preferred. Superior color retention, adhesion, and abrasion resistance in the polyurethane top coating can be achieved in the polyurethane top coating when the crosslinking agent is a biuret or isocyanurate trimer of HDI. The biuret of HDI has the following idealized formula:
The isocyanurate trimer of HDI has the following idealized formula:
One advantage of the biurets and trimers used herein is that they result in a urethane coating that is U.V. stable per se. Thus, it is contemplated that the coatings of the present invention can be manufactured with lower amounts of U.V. stabilizers incorporated therein, resulting in lower costs of production for the coatings.
The biurets and isocyanurate trimers of HDI utilized in the present invention preferably have a viscosity within the range of about 3 to 10,000 cps, with the preferred range being from about 50 to 5,000 cps. Low viscosity biuret and trimer crosslinking agents are preferred because they allow the total coating system to have a higher solids content and still have a viscosity that facilitates spray painting/air atomization of the coating system on the outer surface of the game ball. Biurets and trimers of HDI contemplated for use herein are sold by Bayer Corp. under the trademark DESMODUR. One such composition is DESMODUR N-3200, which is a low viscosity biuret of HDI.
The polyisocyanate equivalent weight of the biuret or trimer crosslinking agent used herein preferably is within the range of 100 to 1,200, with 150 to 300 being preferred. The biuret or trimer is preferably carried in a solvent, with the solvent solution containing from a minimum of about 40% (or less, if a quite dilute solution is preferred for some reason), alternatively about 60%, alternatively about 70%, to a maximum of 100%, alternatively about 85%, by weight of the biuret or trimer.
Suitable solvents for the polyisocyanate crosslinking agent include methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, butyl acetate and propylene glycol monomethyl ether acetate, or mixtures thereof. In a particularly preferred form of the invention, the solvent is present in an amount of 20-65 weight % and even more preferably 40-60 weight % based upon the total weight of the coating system. Urethane grade solvents (i.e. low-moisture solvents) preferably are used.
It is important that the initial viscosity of the coating immediately after the parts of the coating are combined is low enough that the coating can be applied to the game ball surface in a suitable way, such as by spraying. The coating mixture of the present invention preferably has an initial viscosity of 20-100 centipoise, more preferably 25-50 centipoise, and most preferably 30-40 centipoise immediately after the two parts are mixed.
In the two-part systems described above, it is preferable to include a slight excess of the polyisocyanate or polyisocyanurate with at least two xe2x80x94Nxe2x95x90Cxe2x95x90O groups to insure that all of the polyol will be polymerized. If any excess polyol is present, it will not polymerize and tends to act as a plasticizer, thus resulting in a coating of decreased hardness. Preferably, the index, i.e. ratio of polyisocyanate xe2x80x94Nxe2x95x90Cxe2x95x90O groups to polyol OH groups is 0.90-1.8, more preferably 1.0-1.3, and even more preferably 1.0-1.1. The most preferred ratio is about 1.05, as this ratio takes into account any water that may be present in the polyol, and any water vapor present in the air.
The polyol, preferably, although not necessarily, is carried in a solvent. If the material is not heated and contains no flow additives, the solvent is preferably added in an amount of about 30-50 wt % of the polyol. If heating and/or flow additives are used, the solvent optionally can be reduced down to 0 wt %. Generally, no more than 65 wt % solvent is added to the polyol part of the coating. Suitable solvents for use herein include the known polyurethane solvents, for example, butyl acetate, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, propylene glycol monomethyl ether acetate, and mixtures thereof. Especially preferred as the solvent or co-solvent is methyl amyl ketone because its high dipole constant permits a greater amount of polyol or other resin solids to be dispersed therein. Surface tension modifiers also can be added. If solvent is present only in one of the two parts of the coating, it preferably is present in the polyol part.
The use of methyl amyl ketone as the solvent for the polyol component, together with a low viscosity biuret or trimer of HDI as the isocyanate component enables a substantially higher solids content to be in the coating system than was traditionally used in game ball coating systems. Some prior known top coat coating systems typically have a solids content of 35%. The coating system of the present invention, however, preferably has a solids content of from 40 to 100%. The higher solids content results in increased transfer efficiency and decreased volatile organic carbon air emission if the coating is applied in a spray coating operation. The increased efficiency allows a reduction at least of about 5-10% in the amount of the coating material applied to the ball while still achieving the same coverage as prior art balls.
The catalyst conveniently can be carried in the mixture which includes the polyol. The selection of an appropriate catalyst will depend upon the polyisocyanate which is used, and the type of polyol which is used.
The catalyst is added in an amount which far exceeds that which is recommended by polyurethane coating manufacturers. The amount of any particular catalyst to be used is that which will result in an at least 100% increase in viscosity of a volume of the coating within 30 minutes after combining the first and second parts of the coating if the volume of the coating is maintained at 25xc2x0 C., 1 atm and 60% relative humidity. The catalyst typically is added in an amount of 0.01-10 weight % active catalyst (not including any carrier) based on total resin solids (polyol plus poylyisoyanate excluding solvents. When the catalyst is dibutyl tin dilaurate, it preferably is added in an amount of 0.05-0.35 weight % active catalyst based upon total resin solids and more preferably 0.08-0.15 weight % based upon total resin solids. Other catalysts can be used alone or in combination, preferably in amounts which produce a result that is equivalent to the result which is obtained with amounts of dibutyl tin dilaurate. Factors such as the activity of the active hydrogen atoms of the coating system, as well as catalyst cost, curing temperature and desired curing time, which may depend upon curing oven availability, may affect the decision as to what quantity of catalyst should be used. Generally, it is desirable to use a quantity of catalyst which is sufficient to achieve at least a 75% reduction in curing time, and more preferably an 85-95% reduction in curing time as compared to the curing time of a coating of the same thickness and having the same composition except that no catalyst is included, and which is cured under the same curing conditions.
Other additives can be included in the first part of the coating system. These additives include U.V. stabilizers and absorbers, leveling agents, optical brighteners, mar and slip agents, antioxidants, and defoaming agents. These materials are added in amounts of 0-20 wt % of the total coating system, or more preferably 1-5 wt %.
U.V. stabilizers function to tie up free radicals in the top coating that are produced upon exposure to ultraviolet radiation, thus maintaining the integrity of the coating. A non-limiting example of a suitable U.V. stabilizer is Tinuvin 292, a hindered amine light stabilizer sold by Ciba-Geigy Corporation, Ardsley, N.Y.
U.V. absorbers function to absorb ultraviolet radiation and re-emit it as heat. Non-limiting examples of suitable U.V. stabilizers for use in the present invention are Tinuvin 1130, a benzotriazole U.V. absorber sold by Ciba-Geigy Corporation, and Sanduvor 3206, an oxalamide derivative sold by Sandoz Chemicals Corporation, Charlotte, N.C.
Suitable leveling agents which reduce the surface tension of the coating for improved coating flow include Fluorad FC-430, a fluorochemical surfactant sold by 3M Industrial Chemical Products Division, St. Paul, Minn., and DOW 57, a silicone additive sold by Dow Corning Corporation, Midland, Mich.
Optical brighteners can be added to the coating system so that the coating coverage can be checked under U.V. light. Suitable optical brighteners include Uvitex OB, 2,2xe2x80x2-(2,5-thiophenediyl) bis (5-ter-butylbenzoxazole), sold by Ciba-Geigy Corporation, Ardsley, N.Y., and Lucopure EGM, a coumarin optical brightener sold by Sandoz Chemicals Corporation, Charlotte, N.C.
In addition to the additives, film-forming agents and/or co-reactants can be incorporated into the polyol or polyamine portion of the coating system. Co-reactants can be, for example, compositions that further polymerize with heat. Film-forming agents include compositions that form a film after the solvent is evaporated during the polyurethane polymerization process. Such materials do not react with the polyisocyanate portion of the coating system, but instead act independently to improve the final coating properties. A suitable polymerizing co-reactant for use herein is Cymel 303, a melamine resin sold by American Cyanamid. An example of a suitable film-forming resin is A-101, an acrylic, non-hydroxyl containing resin sold by Rohm and Haas, Philadelphia, Pa.
When the two parts of a polyurethane coating system are combined, the total system has the following general formulation:
One Example of a preferred coating formulation is provided below, on Table I.
The coating system is applied to a game ball and preferably to a dimpled golf ball which is typically made of an ionomer such as Iotek (a trademark of Exxon Chemical Co., Baytown, Tex.) or Surlyn (a trademark of E.I. DuPont de Nemours and Co., Wilmington, Del.), natural or synthetic balata, or a thermoplastic polyurethane. When the cover is applied over a primer, the fully dried primer preferably, although not necessarily, consists essentially of from about 90% by weight to about 96% by weight, preferably about 90% by weight, of a water-borne dispersion of a resin selected from the group consisting of acrylic resin, polyurethane resin, and combinations thereof, and from about 4% to about 10% by weight, preferably about 5% by weight, of a polyfunctional aziridine crosslinker material. (As used here, xe2x80x9cdispersionxe2x80x9d includes colloidal emulsions, lattices, and other dispersed forms of the composition.)
The waterborne resin dispersion used in the primer may be an acrylic emulsion or lacquer, for example a material sold by Zeneca Resins Division of Imperial Chemical Industries, PLC, of Wilmington, Del. under the trademark NeoCryl. Particular materials of this type include NeoCryl A-601 and NeoCryl B-723, among others.
The waterborne resin dispersion used in the primer may instead be a polyurethane prepolymer emulsion, for example a material sold by Zeneca, under the trademark NeoRez. A specific NeoRez dispersion useful herein is NeoRez R-960 emulsion. Another material which may be used is WITCOBOND W-234, supplied by Witco, Organics Division, Chicago, Ill.
Combinations of acrylic and polyurethane dispersions are also contemplated within the scope of the present invention. The water-borne dispersions contemplated herein contain from about 5% to about 90% solids, preferably from about 20% to about 40% solids.
One of ordinary skill in the art is readily able to select a resin dispersion which is useful in a primer for the ball cover materials specified above.
The polyfunctional aziridine crosslinker materials useful herein are preferably tri or more highly functional compounds. The preferred materials include: pentaerythritol-tris-(xcex2-(N-aziridinyl) propionate); trimethylol-propane-tris-(xcex2(N-aziridinyl)propionate); mixtures of different polyfunctional aziridines identified in U.S. Pat. No. 5,057,371 (for example, from column 3, line 45 to column, line 19); the polyaziridine materials identified in U.S. Pat. Nos. 5,091,239 and 4,842,950; and other polyfunctional aziridines. The patents listed in this paragraph are hereby incorporated herein by reference to exemplify polyfunctional aziridines. Representative polyfunctional aziridines which are useful herein are sold under the trade designations CX-100; XAMA-2; and XAMA-7 by the manufacturers listed in the patents previously incorporated by reference.
Other additives such as flattening agents, surfactants, flow agents, thickeners and defoamers known to those skilled in the art can be incorporated into the primer composition.
The two-part coating can be applied to the surface of a game ball by spraying, dipping, pouring, brushing, wiping or the like. Whether the coating is applied directly to a golf ball cover or over a primer coat, it is preferred that the coating is applied by spraying. When the coating is sprayed, the first and second parts of the coating are mixed and immediately sprayed onto the surface of the game ball using a spray gun. The coating is typically sprayed at an average wet thickness of no more than about 3.5 mils per coat. The two-part mixture should not be held for more than about 10 minutes and preferably no more than about 5 minutes before spraying, or it may tend to coat the inside surfaces of the spray gun. The limit as to how long it can be held will vary depending on the exact composition of coating system.
After spraying, the coated game ball is transferred to a hot, 40-60% relative humidity oven for curing. The required curing time-temperature combination will depend upon the composition and thickness of the coating, as well as the type and concentration of catalyst which is used. When temperatures within the range of 100-175xc2x0 F. are used, curing is likely to take about one hour at 100 deg. F. or as little as about 5 minutes at 175 deg. F. Particularly preferred curing times are 5-60 mins or even more preferably 5-15 mins, as a rapid curing time of this duration will reduce the total manufacturing time for a game ball by about 5-5xc2xe hours. To achieve these curing times, preferred curing temperatures range from 110-180xc2x0 F., more preferably 150-170xc2x0 F. or even more preferably about 160xc2x0 F., 40-60% RH. The dry coating has an average thickness of about 0.4 to 0.8 mils, and has a Sward rocker hardness (ASTM D 2134-66) of at least 10 in less than 1.5 hours, and preferably in less than 10 minutes. The fully cured coating typically has a Sward rocker hardness of 40-70.
One of the important advantages of the quick-cure coating of the invention over prior known coatings is that the reduced curing time lends itself to use of a continuous curing process, as compared to a conventional batch type curing process. Another advantage is that the total energy use for curing a given quantity of game balls is substantially reduced. A third advantage is that because the coating system of the invention is mixed only a short period of time before it is sprayed, coating materials are conserved by mixing only the required quantity.