The present invention is directed to a golf ball and a to a process for forming a golf ball having least one layer, where the layer is formed of a saponified polymer/polyamide blend, having from about 1 to about 99 parts of at least one saponified polymer and from about 99 to 1 parts of at least one polyamide polymer, based on 100 parts by weight of the saponified polymer/polyamide blend. The layer may be foamed or unfoamed, and may form at least a portion of any of the cover, the core, or an intermediate layer situated between the cover and the core.

The present invention is directed to methods and compositions for forming at least one layer in a golf ball, and to golf balls, which comprise such a layer, having improved properties. In particular, the invention is directed to golf balls having a cover, a core, and, optionally, at least one intermediate layer situated between the cover and the core, where at least one of the cover or the core or the optional intermediate layer comprises a blend of at least one saponified polymer and at least one polyamide-containing polymer, and to methods of forming such golf balls.
Three-piece, wound golf balls with balata covers are preferred by most expert golfers. These balls provide a combination of distance, high spin rate and control that is not available with other types of golf balls. However, balata is easily damaged in normal play and, thus, lacks the durability required by the average golfer. In contrast, amateur golfers typically prefer a solid, two-piece ball with an ionomer cover, which provides a combination of distance and durability. Because of the hard ionomer cover, these balls are almost impossible to cut, but also have a very hard xe2x80x9cfeelxe2x80x9d, which many golfers find unacceptable, and a lower spin rate, making these balls more difficult to draw or fade. The differences in the spin rate can be attributed to the differences in the composition and construction of both the cover and the core.
Consequently, a need exists for a golf ball composition which provides spin rates and a feel more closely approximating those of balata covered balls, while also providing as high or a higher degree of durability than that provided by the balls presently available or disclosed in the prior art. Golf ball manufacturers have attempted to produce golf ball covers that provide the spin rate of balata with the cut resistance of an ionomer by forming blends consisting essentially of hard ionomers with softer, nonionomer polymers to soften the golf ball and improve its feel and spin rate. However, this approach has proven to be difficult because the ionic character of ionomers imparts a highly polar nature to these materials. Therefore, ionomers and other non-ionic polymers, such as balata and polyolefin homopolymers, copolymers or terpolymers that do not contain ionic, acidic, basic or other polar pendant groups, have not been successfully blended for use in golf ball covers. These mixtures often have poor mechanical properties such as inferior tensile strength, impact strength and the like. Hence, the golf balls produced from these incompatible mixtures will have inferior golf ball properties such as poor durability and cut resistance on impact.
Saponification or hydrolysis of alkyl acrylate units in a crosslinkable polymer chain is disclosed by Gross in U.S. Pat. No. 3,926,891. In U.S. Pat. No. 3,970,626, Hurst discloses heating a mixture of an alkali metal hydroxide, a thermoplastic ethylene-alkyl acrylate copolymer and water to saponify the acrylate units and form an aqueous emulsion.
A different approach to saponification or hydrolysis of an ethylene-alkyl acrylate copolymer is disclosed by Kurkov in U.S. Pat. No. 5,218,057, in which the copolymer is mixed with an aqueous solution of an inorganic alkali metal base at a temperature sufficient for saponification to take place and at which the copolymer undergoes a phase change.
All of the prior saponification methods discussed above require that the polymer component be in contact with water, either by conducting the reaction in an aqueous medium or by adding an aqueous solution to the polymer. However, nonaqueous inorganic alkali metal base solutions, e.g., containing an alcohol or polyethylene glycol solvent, are disclosed by U.S. Pat. No. 5,554,698 to Wang et al., although aqueous solutions are disclosed to be preferred.
McClain, in U.S. Pat. No. 4,638,034, discloses a process whereby ethylene-acrylic acid copolymers or their ionomers are prepared from ethylene-alkyl acrylate copolymers by saponifying the latter in the melt with metal hydroxides to form an ionomer and a by-product, i.e., alkanol, then optionally acidifying the ionomer to form the free acid copolymer.
The processes disclosed by the Kurkov, McClain and Wang references, in particular, are incapable of providing optimal product quality since blending and saponifying in a single operation as taught by the subject references leads to rapid saponification, with a concurrent rapid increase in melt viscosity. Due to this rapid increase in viscosity, the resultant mixture is non-uniform and therefore the material properties of products made from this material are not consistent throughout the product. U.S. Pat. No. 5,869,578 to Rajagopalan, a patent that issued from one of the parent applications of the present invention, overcame the above deficiencies.
It is known that saponified polymers may be blended with ionomers. For example, U.S. Pat. No. 5,508,351 to Horiuchi et al. discloses a golf ball cover comprising a resin composition containing 10 to 80 wt. % of a partially saponified olefin/acrylate ester copolymer with the balance consisting of an ionomer. However, this reference does not disclose or even suggest the use of saponified polymer being blended with polyamide for a golf ball cover or intermediate or core layer compositions.
Saponified polymers of the present invention differ from prior art ionomers, inter alia, in that any pendant groups that are not modified by the saponification process are ester groups in contrast to the pendant carboxylic acid groups that remain after neutralization in prior art ionomers. The new composition can contain binary, ternary, or multi-component blends of metal cations used to neutralize the polymer. Such blends may be further combined with other polymers, such as SURLYN(copyright), IOTEK(copyright) and IMAC(copyright) ionomers, to produce golf balls and golf ball covers with desirable properties. The golf ball composition can be used for both solid and wound construction balls.
It is also known that saponified polymers may be blended with polyamides. For example, U.S. Pat. No. 5,554,698 to Wang et al. discloses low-haze films and peelable seals formed from saponified xcex1-olefin/xcex1,xcex2-ethylenically-unsaturated carboxylic acid ester copolymers which, optionally, may contain polyamide. However, this reference does not disclose or even suggest the use of saponified polymer/polyamide blends in golf balls, or that such blends could provide golf balls having improved properties.
U.S. Pat. No. 5,981,654 to Rajagopalan is directed to compositions and methods for making golf balls, wherein the composition comprises a substantially optical brightener-free nonionomer/polyamide polymer blend. U.S. Pat. No. 5,886,103 to Bellinger et al. discloses a golf ball with covers having a composition comprising a polyamide and an ionomer. Both the Rajagopalan ""654 and the Bellinger ""103 patents do not disclose the saponified polymer/polyamide blends of the present invention.
Numerous attempts have been made to replicate the performance of balata covered balls, some using polyamides as a component of a golf ball composition. Despite these numerous attempts, the golf ball compositions of the prior art generally suffer from low spin rates which makes them difficult to control near the greens. Further, such balls tend to have relatively poor xe2x80x9cfeelxe2x80x9d as compared to the balata covered balls. Additionally, many of the prior art golf ball compositions are made with low flexural modulus ionomer resins which have improved spin and feel characteristics, but relatively low velocity, which results in shorter overall distance.
A need exists in the golf ball art for highly durable golf balls, which have improved performance, and may be tailored to have virtually any combination of feel and spin rate. The present invention provides such a golf ball.
The present invention is directed to a golf ball having at least one layer, where the layer is formed of a saponified polymer/polyamide blend, comprising from about 1 to about 99 parts of at least one saponified polymer and from about 99 to 1 parts of at least one polyamide polymer, based on 100 parts by weight of the saponified polymer/polyamide blend. The layer may further comprise up to about 20 parts per weight of at least one suitable compatibilizer, based on 100 parts by weight of the saponified polymer/polyamide blend. The layer may form a one piece ball or at least a portion of any of a cover layer, a core layer, or, optionally, at least one intermediate or mantle layer situated between the cover and the core. Typically the saponified polymer/polyamide blend has a hardness of at least 15 Shore A, a flexural modulus of at least 500 psi, and a specific gravity of at least 0.7. Preferably, a layer of a golf ball comprising the present invention has a flexural modulus of at least 500 to about 300,000 psi.
A golf ball comprising the present invention has an Atti compression of at least 50 and a coefficient of restitution of at least 0.7. Preferably, the Atti compression of the golf ball is at least 60 to about 100.
Golf balls in accordance with the invention preferably have a cover thickness of at least 0.03 inch to about 0.125 inch and at least 60 percent dimple coverage, and a core diameter of at least 0.5 to about 1.63 inches. Where the golf ball of the present invention further comprises at least one optional mantle or intermediate layer, the mantle or intermediate layer has a thickness of at least 0.02 inches.
Golf balls of the present invention preferably have a cover layer hardness of at least 40 Shore D to about 70 Shore D and a flexural modulus of at least 10,000 to about 100,000 psi, an intermediate layer hardness of at least 20 Shore D to about 70 Shore D and a flexural modulus of at least 500 to about 100,000 psi and a core layer hardness of at least 40 Shore A to about 70 Shore D and a flexural modulus of at least 500 to 150,000 psi. Any of the cover, the core or the center, or the at least one optional mantle or intermediate layer may comprise a density adjusting filler material to increase or decrease the density. The density adjusting filler material may be a metallic powder or a metallic oxide derivative. Preferably, the metallic powder is either titanium, tungsten or copper powder and the metallic oxide derivative is an oxide derivative of titanium, tungsten, copper or tin.
In addition, any of the cover, the core or the center, or the at least one optional mantle or intermediate layer may have a foamed structure. The at least one optional mantle or intermediate layer further comprises a wound tensioned elastomeric material, wherein the tensioned elastomeric material further comprises natural or synthetic elastomers or blends thereof. Preferably the synthetic elastomer is LYCRA. The center may be solid, fluid filled or hollow.
The saponified polymer component of this invention has a Shore D hardness of at least 15, as measured by ASTM method D-2240, a flexural modulus, as measured by ASTM method D-790, of at least 500 psi, preferably about 1000 psi to about 100,000 psi, a specific gravity of at least about 0.7, preferably about 0.75 to about 1, a dynamic shear storage modulus (Gxe2x80x2) at 23xc2x0 C., as described in ASTM D 4092-90, ASTM D 5279-93, and ASTM D 4065-94, of at least 104 dynes/cm2, preferably about 106 to about 101 dynes/cm2, and most preferably from 106 to about 109 dynes/cm2, and a loss tangent (tan xcex4) of no more than about 1, preferably, no more than 0.1, and most preferably from about 0.001 to about 0.01 at 23xc2x0 C.
The saponified polymer typically comprises a first olefinic, monomeric component having from 2 to 8 carbon atoms and a second monomeric component comprising an unsaturated carboxylic acid based acrylate class ester having from 4 to 22 carbon atoms and at least one ester group, wherein at least a portion of the at least one ester group has been saponified with an inorganic metal base. Useful inorganic metal bases include but are not limited to metal bases comprising at least one metallic cation, such as lithium, sodium, potassium, cesium, magnesium, calcium, barium, manganese, copper, zinc and aluminum, and at least one anion, such as hydroxide, alkoxide, acetate, carbonate, bicarbonate, oxide, formate and nitrate.
Typically, the first monomeric component is an xcex1-olefin monomer having a terminal point of unsaturation, and may be of the formula:
where R1 is hydrogen or an alkyl group and R2 is hydrogen, lower alkyl including C1-C5, carbocyclic or aromatic. Preferably, the first monomeric component is ethylene.
Typically, the first monomeric component comprises from about 1 to about 99 percent by weight of the total polymer weight, preferably from about 10 to about 95 percent by weight of the total polymer weight and most preferably from about 10 to about 70 percent by weight of the total polymer weight.
The second monomeric component is typically an unsaturated acrylate class ester having the formula:
where R3 is hydrogen or an alkyl group; R4 is hydrogen, lower alkyl including C1-C5, carbocyclic or aromatic; R5 is selected from the group consisting of CnH2n+1, for n=1 to 18 and phenyl, in which from 0 to 5 H within R5 can be replaced by substituents selected from the group consisting of COOH, SO3H, NH2, succinic anhydride and their salts or R5 can be replaced by substituents selected from the group consisting of F, Cl, Br, I, OH, SH, epoxy, silicone, lower alkyl esters, lower alkyl ethers and aromatic rings, wherein optionally R4 and R5 can be combined to form a bicyclic ring. Typically, the second monomeric component comprises from about 99 to about 1 percent by weight of the total polymer weight, preferably, from about 90 to about 5 percent by weight of the total polymer weight and most preferably, from about 90 to about 30 percent by weight of the total polymer weight.
The saponified polymer may also comprise a third monomeric component. Useful third monomeric components include, but are not limited to, carbon monoxide, sulfur dioxide, an anhydride monomer, an unsaturated monocarboxylic acid, an olefin having from 2 to 8 carbon atoms and a vinyl ester or a vinyl ether of an alkyl acid having from 4 to 21 carbon atoms. Preferred third monomeric components include monomers of formula:
wherein:
R6, R7, R8, R11 are independently hydrogen, lower alkyl including C1-C5, carbocyclic or aromatic;
R9 and R12 are independently hydrogen, lower alkyl including C1-C5;
R10 is hydrogen, or is selected from the group consisting of CnH2n+1, for n=1 to 18 and phenyl, in which from 0 to 5 H within R10 can be replaced by substituents selected from the group consisting of COOH, SO3H, NH2 and their salts or R10 can be replaced by substituents selected from the group consisting of F, Cl, Br, I, OH, SH, silicon, lower alkyl esters, lower alkyl ethers and aromatic rings;
R13 is hydrogen, or is selected from the group consisting of CnH2n+1 for n=1 to 18 and phenyl, in which from 0 to 5 H within R13 can be replaced by substituents selected from the group consisting of COOH, SO3H, NH2 and their salts or R13 can be replaced by substituents selected from the group consisting of F, Cl, Br, I, OH, SH, silicon, lower alkyl esters, lower alkyl ethers and aromatic rings, wherein optionally R12 and R13 can be combined to form a bicyclic ring.
Typically, the third monomeric component comprises up to about 49 percent by weight of the total polymer weight of the saponified polymer.
The present invention is also directed to a process for forming a golf ball, which comprises forming a polymer comprising a first olefinic monomeric component having from 2 to 8 carbon atoms and a second monomeric component comprising an unsaturated carboxylic acid based acrylate class ester having from 4 to 22 carbon atoms; applying a sufficient amount of heat to the polymer to convert the polymer to a substantially molten state; forming a mixture by adding an inorganic metal base to the molten polymer, such that the viscosity of the mixture remains substantially unchanged from the viscosity of the molten polymer; and saponifying the mixture to form a saponified polymer, where a sufficient amount of the inorganic metal base is added to the molten polymer in forming the mixture to obtain a degree of saponification of the polymer ranging between about 1 and 90 percent. At least one saponified polymer is then blended with at least one polyamide polymer to form a saponified polymer/polyamide blend which is used to form at least one layer of a golf ball. Preferably, the melting, mixing, and saponification all performed within an extruder.
The present invention is directed in an alternate embodiment to an additional process for forming a golf ball, which comprises forming a polymer comprising a first olefinic monomeric component having from 2 to 8 carbon atoms and a second monomeric component comprising an unsaturated carboxylic acid based acrylate class ester having from 4 to 22 carbon atoms; introducing the polymer into an inlet zone of an extruder comprising an inlet and at least one addition zone; melting and mixing the polymer in the inlet zone; passing the molten polymer through an addition zone within the extruder; forming a mixture at a first temperature above the melting temperature of the polymer and below a second temperature at which saponification takes place by adding a solution comprising at least one metal base into the molten polymer as it passes through the addition zone such that the viscosity of the mixture remains substantially unchanged from the viscosity of the molten polymer, followed by saponifying the mixture at the second temperature within the extruder to form a saponified polymer, where a sufficient amount of the inorganic metal base is added to the molten polymer in forming the mixture to obtain a degree of saponification of the polymer ranging between about 1 and 90 percent. At least one saponified polymer is then melt blended with at least one polyamide polymer using a batch or continuous process known in the art to form a saponified polymer/polyamide blend which is used to form at least one layer of a golf ball.
In either process, the process may further comprise adding to the polymer having a third monomeric component selected from carbon monoxide, sulfur dioxide, an anhydride monomer, an unsaturated monocarboxylic acid, an olefin having from 2 to 8 carbon atoms and a vinyl ester or a vinyl ether of an alkyl acid having from 4 to 21 carbon atoms.
A grafting agent may also be added to at least one of the saponified polymer or the polyamide to form a grafted polymer. The preferred grafting agent is an anhydride having the formula:
where R14 and R15 are the same or different and are selected from the group consisting of hydrogen, linear or branched chain alkyl and substituted or unsubstituted carboxylic groups.
The grafting agent is typically added in an amount of between about 1 to about 50 percent by weight, preferably from about 1 to about 25 percent by weight and most preferably from about 1 to about 15 percent by weight of the polymer.
Typical polyamide polymers include but are not limited to homopolymers, such as polyamide 6, polyamide 11, polyamide 12, polyamide 4,6, polyamide 6,6, polyamide 6,9, polyamide 6,10, polyamide 6,12 and mixtures thereof, and copolymers, such as polyamide 6/6,6, polyamide 6,6/6,10, polyamide 6/6,T, polyamide 6/6,6/6,10 and mixtures thereof. The preferred homopolyamides include polyamide 11 and polyamide 12.
Useful compatibilizers include olefinic block, random, and graft thermoplastics and oligomers, such as block, random, and graft thermoplastics based on homopolymers and copolymers of olefinic monomers with comonomers containing functionalized groups that enable the compatibilizer to be miscible with both the ionomer and the non-polar polymer or polar, but chemically different polymer. One purpose for the compatibilizer is to xe2x80x9creduce the interfacial tensionxe2x80x9d at the interface between the incompatible polymers. Functionalized polymers as compatibilizers useful in the invention include copolymers of olefinic monomers with comonomers containing functionalized groups of acids, esters, epoxies, isocyanates, hydroxys, anhydrides, amines, and thiols, e.g., copolymers of ethylene with alkylacrylates or glycidyl acrylate. Useful compatibilizers also include block copolymers such as copoly(ether ester), such as Du Pont""s Hytrel, and copolyether-amide, such as Pebax. Other useful block copolymers include polysiloxanes, silicones, styrene-butadiene and hydrogenated styrene-butadiene block co-polymers. These block copolymers may also be functionalized with functional groups such as acids, esters, epoxies, isocyanates, hydroxys, anhydrides, amines, and thiols.
As used herein, the terms xe2x80x9csaponified polymerxe2x80x9d and xe2x80x9csaponified ionomerxe2x80x9d refer to a polymer comprising at least one olefin and at least one unsaturated monomer that contains a pendant ester group, where at least some of the pendant ester groups have been saponified or hydrolyzed. Saponified polymers differ from prior art ionomers, inter alia, in that any pendant groups that are not modified by the saponification process are ester groups in contrast to the pendant carboxylic acid groups that remain after neutralization in prior art ionomers.
The term xe2x80x9cpolyamide polymerxe2x80x9d or xe2x80x9cpolyamidexe2x80x9d refers to a thermoplastic with repeating amide groups in the polymer chain. Polyamides can be comprised of a homopolymer, a copolymer, a block copolymer or a blend of two or more variations of any or all of the above types of polyamide polymers, as will be discussed in more detail below.
The term xe2x80x9csaponified polymer/polyamide blendxe2x80x9d as used herein, refers to any polymer blend that comprises at least one saponified polymer and at least one polyamide polymer.
As used herein with regard to a polymer blend, the term xe2x80x9ccompatiblexe2x80x9d refers to a blend of two or more polymers, having useful golf ball properties, that is homogeneous on a macroscopic scale. Compatible blends may be miscible (i.e., homogeneous on a microscopic scale), or at least partially immiscible (i. e., heterogeneous on a microscopic scale, but homogeneous on a macroscopic scale) and have a xe2x80x9creduced interfacial tensionxe2x80x9d at the polymer interface. The term xe2x80x9cincompatiblexe2x80x9d refers to a mixture of at least two polymers that is heterogeneous on both a microscopic scale and a macroscopic scale, such that useful golf ball properties, such as durability, are lacking.
As used herein, the term xe2x80x9clayerxe2x80x9d includes any generally spherical portion of a golf ball or golf ball core, center (hollow, solid, fluid filled type), or intermediate layer, including one-piece cores and one-piece balls. An xe2x80x9cintermediate layerxe2x80x9d (also known as inner layer or mantle layer) is defined herein as a portion of the golf ball that occupies a volume between the cover and the core. Such an intermediate layer may be distinguished from a cover or a core by some difference in the property of the materials comprising the layers. Moreover, a xe2x80x9ccoverxe2x80x9d or a xe2x80x9ccorexe2x80x9d as these terms are used herein may comprise a single layer or a plurality of layers. An intermediate layer may be used, if desired, with a multilayer cover or a multilayer core, or with both a multilayer cover and a multilayer core. Therefore, an intermediate layer is also sometimes referred to in the art as an inner cover layer, as an outer core layer or as a mantle layer.
As used herein, the term xe2x80x9ccoverxe2x80x9d means the outermost portion of a golf ball. A cover typically includes at least one layer and may contain indentations such as dimples and/or ridges. Paints and/or laminates are typically disposed about the cover to protect the golf ball during use thereof.
As used herein, the term xe2x80x9ccorexe2x80x9d means the innermost portion of a golf ball, and may include one or more layers. When more than one layer is contemplated, the core includes a center and at least one mantle layer disposed thereabout. At least a portion of the core, typically the center, is solid or fluid. The core may also include one or more wound layers including at least one tensioned elastomeric material wound about the center. Preferably, the tensioned elastomeric material comprises natural or synthetic elastomers or blends thereof. Preferably, the synthetic elastomer is LYCRA.
As used herein, the term xe2x80x9cAtti compressionxe2x80x9d is defined as the deflection of an object or material relative to the deflection of a calibrated spring, as measured with an Atti Compression Gauge, that is commercially available from Atti Engineering Corp. of Union City, N.J. Atti compression is typically used to measure the compression of a golf ball and/or a golf ball core.
As used herein, the term xe2x80x9ccoefficient of restitutionxe2x80x9d (COR) is calculated by dividing the rebound velocity of the golf ball by the incoming velocity when a golf ball is shot out of an air cannon. The COR testing is conducted over a range of incoming velocities and determined at an inbound velocity of 125 ft/s.
As used herein, the term xe2x80x9cfoamedxe2x80x9d encompasses xe2x80x9cconventional foamedxe2x80x9d materials that have cells with an average diameter of greater than 100 xcexcm and xe2x80x9cmicrocellularxe2x80x9d type materials that have closed cell sizes on the order of 2 to 25 xcexcm. Examples of conventional foamed materials include those described in U.S. Pat. No. 4,274,637. Examples of microcellular closed cell foams include those foams disclosed in U.S. Pat. Nos. 4,473,665 and 5,160,674.
As used herein, the term xe2x80x9cfluidxe2x80x9d means a gas, liquid, gel, paste, or the like, or a combination thereof.
The term xe2x80x9cabout,xe2x80x9d as used herein in connection with one or more numbers or numerical ranges, should be understood to refer to all such numbers, including all numbers in a range.
The present invention relates to golf balls including at least one layer that comprises a compatible blend of at least one saponified polymer and one or more polyamide polymers, i.e., a saponified polymer/polyamide blend. As noted above, the layer may be in any of the core, the cover, or an intermediate layer situated between the cover and the core.
Typically, the blends of the invention comprise from about 1 to about 99 parts of the polyamide polymer and from about 99 to about 1 parts of the saponified polymer, preferably from about 5 to about 90 parts of at least one polyamide polymer and about 95 to about 10 parts of at least one saponified polymer, more preferably from about 10 to about 80 parts of at least one polyamide polymer and about 90 to about 20 parts of at least one saponified polymer based on 100 parts by weight of saponified polymer/polyamide blend.
As used herein with regard to saponified polymers and polyamide polymers, the phrase xe2x80x9cbranched or straight chain alkylxe2x80x9d means any substituted or unsubstituted acyclic carbon-containing compounds. Examples of alkyl groups include lower alkyl, for example, methyl, ethyl, n-propyl, iso-propyl, -butyl, iso-butyl or tert-butyl; upper alkyl, for example, octyl, nonyl, decyl and the like. The ordinary skilled artisan is familiar with numerous linear and branched alkyl groups, which are within the scope of the present invention.
In addition, such alkyl groups may also contain various substituents in which one or more hydrogen atoms has been replaced by a functional group. Functional groups include, but are not limited to hydroxyl, amino, carboxyl, sulfonic amide, ester, ether, phosphates, thiol, nitro, silane and halogen (fluorine, chlorine, bromine and iodine), to mention but a few.
As used herein, xe2x80x9csubstituted and unsubstituted carbocyclicxe2x80x9d means cyclic carbon-containing compounds, including, but not limited to cyclopentyl, cyclohexyl, cycloheptyl, adamantyl and the like. Such cyclic groups may also contain various substituents in which one or more hydrogen atoms has been replaced by a functional group. Such functional groups include those described above and lower alkyl groups having from 1 to 28 carbon atoms.
As used herein, xe2x80x9csubstituted and unsubstituted aryl groupsxe2x80x9d refers to any functional group comprising a hydrocarbon ring having a system of conjugated double bonds, such as phenyl, naphthyl, anisyl, tolyl, xylenyl and the like. These aryl groups may also be substituted with any number of a variety of functional groups. In addition to the functional groups described above in connection with substituted alkyl groups and carbocyclic groups, functional groups on the aryl groups can include nitro groups.
Saponified polymers useful in the invention may be made, for example, from polymers of formula I:
wherein:
R1 is hydrogen, alkyl such as methyl, ethyl and branched or straight chain propyl, butyl, pentyl, hexyl, heptyl and octyl;
R2, R4, R6, and R7are independently hydrogen, lower alkyl including C1-C5; carbocyclic or aromatic;
R3is hydrogen, alkyl such as methyl, ethyl and branched on straight chain propyl, butyl, pentyl, hexyl, heptyl and octyl;
R5is selected from the group consisting of CnH2n+1, for n=1 to 18 (which includes, for example, CH3, C2H5, C3H7, C4H9, C5H11, C6H13, C7H15, C9H19, C10H21) and phenyl, in which from 0 to 5 H within R5 can be replaced by substituents selected from the group consisting of COOH, SO3H, NH2, succinic anhydride and their salts, or R5 can be replaced by substituents selected from the group consisting of F, Cl, Br, I, OH, SH, epoxy, silicone, lower alkyl esters, lower alkyl ethers and aromatic rings; wherein optionally R4 and R5 can combined to form a bicyclic ring and
wherein a, b and c are the relative percentages of each comonomer repeat unit in the polymer.
Saponified polymers can also be formed, for example, from polymers of formula II:
wherein:
R1, R2, R3, R,, and R5 are as defined above; and wherein d, e and f are the relative percentages of each comonomer repeat unit in the polymer; from polymers of formula III:
wherein:
R1, R2, R3, R4 and R5 are as defined above; and wherein g, h and i are the relative percentages of each comonomer repeat unit in the polymer; and from polymers of formula IV:
wherein:
R1, R2, R3, R4 and R5 are as defined above; R5 is hydrogen, lower alkyl including C1-C5, carbocyclic or aromatic; R9 is hydrogen or lower alkyl including C1-C5 and R10 is hydrogen or is selected from the group consisting of CnH2n+1, for n=1 to 18 and phenyl, in which from 0 to 5 H within R10 can be replaced by substituents selected from the group consisting of COOH, SO3H, NH2, succinic anhydride and their salts, and R10 can be replaced by substituents selected from the group consisting of F, Cl, Br, I, OH, SH, epoxy, silicon, lower alkyl esters, lower alkyl ethers and aromatic rings and wherein k, m and n are the relative percentages of each comonomer, wherein optionally R9 and R10 can be combined to form a bicyclic ring.
In addition, saponified polymers can be formed from polymers of formula V:
wherein:
R1-R5 are as defined above; R11 is hydrogen, lower alkyl including C1-C5, carbocyclic or aromatic; R12 is hydrogen or lower alkyl including C1-C5; wherein optionally R12 and R13 can be combined to form a bicyclic ring and wherein r, s and t are the relative percentages of each comonomer.
Saponified polymers can be random, block or alternating polymers and may made by blending two, three, four, five or more different monomers according to processes well known to one of ordinary skill in the art. Additionally, the subject polymers may be isotactic, syndiotactic or atactic, or any combination of these forms of types of polymers. The pendant groups creating the isotactic, syndiotactic or atactic polymers can be chosen to determine the interactions between the different polymer chains making up the resin to control the final properties of the resins used in golf ball covers. Aromatic and cyclic olefins can be used in the present invention as well as such specific groups as methyl and phenyl.
The comonomers described herein can be combined in a variety of ways to provide a final copolymer with a variety of characteristics. The letters a, d, g, k and represent numbers that can independently range from 1-99 percent, preferably from 10-95 percent, more preferably from 10-70 percent and, most preferably, from about 10-50 percent. The coefficients b, e, h, m and s can independently range from 99-1 percent, preferably from 90-5 percent, more preferably from 90-30 percent and most preferred from 90-50 percent, and c, f, i, n and t can independently range from 0 to 49 percent.
Graft copolymers of the saponified polymers described above can also be prepared for use in forming golf balls. For example, graft polymers can be produced such tat the graft segment making up the linkage between polymer chains comprises an anhydride, wherein xe2x80x9canhydridexe2x80x9d is taken to mean a compound having the formula VI:
wherein:
R14 and R15 are the same or different and are chosen from among hydrogen, near or branched chain alkyl and substituted or unsubstituted carboxylic groups. Alternately, however, other grafting agents containing double or triple bonds can be used. Examples of these materials include, but are not limited to, acrylates and any styrene.
Grafting the polymer molecules of the present invention can be accomplished according to any technique known in the art. See, e.g., Block and Graft Copolymers, by R. Ceresa, pub. by Butterworths, London (1962), incorporated by reference herein. It is preferred that any grafting of the polymers of the present invention be accomplished by adding from about 1 to about 50 percent, or preferably from about 1 to about 25 percent and most preferably from about 1 to about 15 percent of a grafting agent, such as an anhydride according to Formula VI above. The grafting agents can be added either as a solid or a non-aqueous liquid, to a polymer according to the present invention. Such post reaction grafting can make the final grafted polymer more flexible.
Polymers that can be saponified for use in the present invention can be synthesized by a variety of methods, including metallocene catalysis, since it is well known in the art of polymer synthesis that many different synthetic protocols can be used to prepare a given compound.
Polymers useful for saponification preferably comprise: (1) a first monomeric component comprising an olefinic monomer having from 2 to 8 carbon atoms; (2) a second monomeric component comprising an unsaturated carboxylic acid based acrylate class ester having from 4 to 22 carbon atoms; and (3) an optional third monomeric component comprising at least one monomer selected from the group consisting of carbon monoxide, sulfur dioxide, an anhydride monomer, an unsaturated monocarboxylic acid, an olefin having from 2 to 8 carbon atoms and a vinyl ester or a vinyl ether of an alkyl having from 4 to 21 carbon atoms.
Saponified polymers are preferably prepared by adding a metal base or metal salt in the form of a solid or a solution to a polymer, such as the polymers described in the previous paragraph. When the metal base is in the form of a solid, such as a powder or a pellet, the solid preferably has an average powder particle diameter of from about 1 to about 500 microns. More preferably, such powders have an average particle diameter of 10 to 100 microns. In the case of pellets, substantially any commercially available pellet particle size can be used.
Alternatively, the metal base can be added in the form of a solution. The solution may be an aqueous solution or may be formed from at least one organic solvent, i.e., be non-aqueous. Such non-aqueous solutions typically comprise organic solvents such as alcohol, acetic acid and acetic anhydride, although other solvents may, of course, be used.
The metal base comprises at least one metal cation that will provide the ionomeric properties desired in the blend. Although virtually any metal ion that forms a base may be used in the invention, the metal base preferably comprises at least one metal cation selected from the group consisting of: Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Zn, La, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Ru, Os, Co, Ni, Pt, Cu, Ag, B, Al, and Sn. Most preferably, the metal base comprises at least one metallic cation selected from the group consisting of: Li, Na, K, Cs, Mg, Ca, Ba, Zn, Mn, Cu, Al, and at least one anion, such as hydroxide, alkoxide, acetate, carbonate, bicarbonate, oxide, formate or nitrate.
Although other melting and mixing apparatus may be used, the polymers described herein are preferably saponified or hydrolyzed by introducing the polymer into an extruder inlet zone and melting and mixing the polymer in the inlet zone; passing the molten polymer through an addition zone within the extruder downstream from the inlet zone; and adding a metal base into the molten polymer as it passes through the addition zone.
In particular, the metal base is mixed with the polymer under non-saponification conditions. Instead of simultaneously mixing and saponifying or hydrolyzing as practiced in the prior art, these operations are carried out separately, In the first step, the polymer is heated to a substantially molten state at a temperature typically between about 50-350xc2x0 C., depending upon the polymer chosen, to facilitate subsequent mixing with a metal base. This pre-heating step assures a greater degree of homogeneity in the final product and provides a final product having correspondingly improved properties.
In the next step, the metal base is added to the molten polymer and the polymer and metal base are extensively mixed under conditions in which no substantial saponification occurs. A sufficient amount of metal base must be added overall to obtain a degree of saponification of the polymer between about 1 and about 90 percent, preferably between about 1 and about 50 percent. The mixing is carried out at a temperature slightly higher than the melting temperature of the polymer. For mixing on an extruder, the screw speed can be varied between about 20-500 rpm, depending upon the material""s viscosity. Furthermore, as would be well understood by one of ordinary skill in the art, the depth of the conveying element of the extruder is chosen to prevent substantial saponification of the material during mixing.
Alternately, the mixing may be accomplished using a roll mill. In such a case, the cylinder roll speed is adjusted to between about 5-100 rpm depending upon the viscosity of the material. Additionally, the mill gap is adjusted as necessary to control the amount of shear and, thus, the degree of saponification. The metal base may be added all at once to the molten polymer, or alternately it may be introduced in batches or stages.
In a third step, conditions are provided such that a saponification or hydrolysis reaction occurs between the polymer and the metal base. Saponification is achieved by continuous mixing of the polymer and base at an elevated temperature, which is substantially higher than the melting point temperature. The extent of saponification is determined by methods well known to those of ordinary skill in the art, for example, by the melt index of the partially saponified polymer or by titrating versus an acid.
The process of the present invention offers several improvements over the methods disclosed in the prior art. First, it provides for greater ease of mixing of the reactants before the reaction begins. Because the melt viscosity of the non-salt polymer is much lower than the salt polymer form, the melt mixing of the polymer and metal base is more readily carried out with lower input power requirements. Additionally, mixing of polymer and metal base is more uniform because there are no substantially saponified or hydrolyzed regions of high melt viscosity present within regions that have not yet reacted and, therefore, have low melt viscosity. Furthermore, the degree of mixing or dispersion of the base in the polymer is more easily controlled since melt viscosity is more uniform throughout the volume of molten polymer.
The process of the present invention is preferably accomplished using a twin screw extruder wherein the twin screw extruder comprises melting, addition and mixing zone means. The process can further be accomplished using a master batch comprising a concentrated amount of metal base in a polymer, with the same or different composition as the polymer introduced into the inlet zone, wherein the master batch is added from a side-stream extruder. The side-stream extruder can be a twin screw extruder comprising melting, addition and mixing zone means.
Alternatively, the continuous process of saponifying or hydrolyzing the polymers useful in the invention comprises introducing the polymer into an inlet zone of an extruder and melting and mixing the polymer in the inlet zone; passing the molten polymer through at least two addition zones connected in series; adding a portion of a metal base into the molten polymer as it passes through each addition zone; then passing the mixture through at least one saponification zone under conditions such that the polymer is at least partially saponified.
For use in saponified polymer/polyamide blends of the present invention, a saponified polymer can be blended with the other similar polymers, having a different metal base cation or distribution of cationic species than used to make the first saponified polymer, to yield a blend with desirable golf ball properties. Alternatively, two different saponified polymers with ionomeric character, having the same metal base cation can be blended to yield a useful blend. The two polymers can differ in their degree of saponification, degree of subsequent acidification, molecular weight, molecular weight distribution, tacticity, blockiness, etc.
Blends of polyamide polymers and ionomers have superior golf ball properties, including performance and durability. For example, as demonstrated in the examples provided in co-pending application Ser. No. 08/815,659, a compatible blend of a polyamide and an ionomer results in a golf ball cover composition which provides a higher durability, shear resistance and/or spin rate when compared to covers comprising conventionally-produced ionomers, e.g., a blend of a conventional ionomer and a high acid ionomer or a VLMI, i.e., a very low modulus ionomer.
The use of saponified ionomer in combination with polyamides provides golf balls with a lower cover, intermediate layer, and/or core hardness and better feel than prior art golf balls, thereby providing better playability. Moreover, where the saponified polymer is formed with the preferred method of the invention, the resulting blends are significantly less yellow than blends formed using prior art saponification methods. As a result, covers formed from the blends of the invention require less whitener e.g., TiO2, than prior art blends.
The polyamide polymer component useful in forming the blends of this invention is a thermoplastic with repeating amide groups, commonly known as nylons. This component can be comprised of a homopolymer, a copolymer, a block copolymer or a blend of two or more variations of any or all of the above types of polyamide polymers. Additionally, polyamide present in the form of a fiber or a film is not contemplated for use in the blends of the present invention as such forms of polyamide, when present in a blend, would be inhomogeneous on a macroscopic scale, i.e., incompatible. Preferably, the polyamide polymer component is a homopolymer, a copolymer or a blend of two or more variations of either or both of these types of polyamides.
Preferred polyamide homopolymers include polyamide 4, polyamide 6, polyamide 7, polyamide 11, polyamide 12, polyamide 13, polyamide 4,6, polyamide 6,6, polyamide 6,9, polyamide 6,10, polyamide 6,12, polyamide 12,12, polyamide 13,13 and mixtures thereof. More preferred polyamide homopolymers include polyamide 6, polyamide 11, polyamide 12, polyamide 4,6, polyamide 6,6, polyamide 6,9, polyamide 6,10, polyamide 6,12 and mixtures thereof. The most preferred polyamide homopolymers are polyamide 11 and polyamide 12.
Polyamide copolymers are also useful in forming the blends of this invention. They are commonly designated by separating the symbols for the homopolymers by the symbol xe2x80x9c/xe2x80x9d. For the purposes of this application, the component named first can be either the major or a minor component of the copolymer.
Preferred polyamide copolymers include polyamide 6/6,6, polyamide 6,6/6,10, polyamide 6/6,T wherein T represents terephthalic acid, polyamide 6/6,6/6,10 and mixtures thereof.
Block polyamide copolymers are materials which contain main-chain blocks or segments of polyamide or copolyamide separated by main-chain blocks of a different polymer. The separating polymer block may be a polyether, such as a poly(alkylene oxide). When poly(ethylene oxide) is used as the separating polymer block, this material is known commercially as PEBAX(copyright), available from Elf Atochem S.A., GRILAMID(copyright), available from Emser, or VESTAMID(copyright), available from Hxc3xcls.
Although it has been previously known in the art to utilize block copoly(amide-ether)s such as PEBAX(copyright) in golf balls, the applicant has now surprisingly determined that other main-chain separating blocks can be used to replace the polyether separating block in block polyamide copolymers of the compositions and methods of the invention to give golf balls with good properties. Block polyamide copolymer compositions of the invention include main-chain separating blocks comprising polyester, polyurethane, polythioether, polythioester, xcex1,xcfx89-hydroxybutadiene oligomer and hydrogenated xcex1,xcfx89-hydroxybutadiene oligomer.
Preferred block polyamide copolymer compositions useful in the invention include those having block polyamide copolymer compositions useful in the invention include those having main-chain separating blocks comprising polyester, which are available commercially under the trade name K-FLEX(copyright) from King Industries and under the trade name the BAYTEC(copyright) MS from Bayer, and those having main-chain separating blocks comprising polyurethane, which are available commercially under the trade names ESTANE(copyright) from the B.F. Goodrich Company and PELLETHANE(copyright) from Dow Chemical, PANDEX(copyright) from the Dainippon Ink and Chemical Company (Japan) as well as xcex1,xcfx89-hydroxybutadiene oligomers and hydrogenated xcex1,xcfx89-hydroxybutadiene oligomers, wherein the degree of hydrogenation may be partial or substantially complete, which are available commercially as POLYBD(copyright) resins from Elf Atochem S.A. Block polyamide copolymers comprising mixtures of these main chain blocks are also preferred. These materials are particularly desirable because they provide an alternative to the costly block polyamide copolymers with polyether separating blocks. Typically, block polyamide copolymers have a hardness of at least 30 Shore A and a flexural modulus of at least 500 psi.
The polyamide homo and co-polymer component of this invention has a Shore D hardness of at least 50, as measured by ASTM method D-2240, a flexural modulus, as measured by ASTM method D-790, of at least 30,000 psi, preferably at least 75,000 psi to about 500,000 psi.
The saponified polymer/polyamide blends of the present invention can be prepared with or without the addition of a compatibilizer and with varying molecular architecture of blend components, such as varying molecular weight, tacticity, degrees of blockiness, etc., as is well known to those knowledgeable in the art of blending polymers.
Blending of the saponified polymer/polyamide blends is accomplished in a conventional manner using conventional equipment by methods familiar to those in the polymer blending art. For example, a two roll mill, a Banbury mixer or a single or twin-screw extruder may be used to produce a compatible blend. Preferably, when an extruder is used, the normally higher-melting polyamide component is first melted in the main extruder and the molten saponified polymer is introduced as a side-stream into a main extruder conveying molten polyamide where the two melts are intermixed to form a compatible blend. The single screw extruder may optionally have a grooved barrel wall, comprise a barrier screw or be of a shortened screw design. The twin screw extruder may be of the counter-rotating non-intermeshing, co-rotating non-intermeshing, counter-rotating fully intermeshing or co-rotating fully intermeshing type.
Good results have been obtained by mixing the comonomers or resins in a solid, pelletized form and then placing the mix into a hopper which is used to feed the heated barrel of an injection molding machine. Further mixing is accomplished by a screw in the heated barrel. The injection molding machine is used either to make preformed golf ball half-shells for compression molding about a core or for molding flowable cover stock about a core using a retractable-pin mold, as discussed in more detail below. The saponified polymer/polyamide blends of the present invention may be used alone or blended with other polymers or ionomers, according to methods well known in the art, to form compositions useful for forming golf balls.
For example, the saponified polymer/polyamide blends of the present invention may be combined with thermoplastic ionomers, such as ethylene methacrylic acid ionomers and ethylene acrylic acid ionomers and their terpolymers, which are sold commercially under the trade names SURLYN(copyright) and IOTEK(copyright) by DuPont and Exxon respectively.
The saponified polymer/polyamide blends of the present invention may also be combined with other thermoplastic polymers, including a functionalized polymer, a copolymer or a functionalized copolymer, or mixtures thereof. As used herein, a xe2x80x9cfunctionalizedxe2x80x9d polymer or copolymer incorporates additional functionalities, such as acidic or basic groups, by reacting the polymer, such as polystyrene or a polystyrene copolymer including a block copolymer of polystyrene, with a functionalizing reagent, such as a carboxylic acid or sulfonic acid. Thermoplastic polymers which can be used in conjunction with the polymers of the claimed invention in golf ball compositions include but are not limited to polycarbonate; poly(phenylene oxide); imidized, amino group containing polymers; high impact polystyrene (hereafter HIPS); polysulfone; poly(phenylene sulfide); reinforced engineering plastics; polytetrafluoroethylene; nonionic olefinic homopolymers and copolymers, such as those produced by using free radical, ionic, Ziegler-Natta or metallocene or single-site non-metallocene catalysts, including but not limited to a polymer comprising an xcex1-olefin containing from 2 to 10 carbon atoms, poly(ethylethylene), poly(heptylethylene), poly(isopentylethylene), poly(ethylene-propylene), poly(ethylene-butene), poly(ethylene-vinyl acetate) and poly(ethylene-vinyl alcohol); poly(butyl acrylate); poly(2-ethylbutyl acrylate); poly(heptyl acrylate); poly(2-methylbutyl acrylate); poly(3-methylbutyl acrylate); poly(N-octadecylacrylamide); poly(octadecyl methacrylate); poly(butoxyethylene); poly(methoxyethylene); poly(pentyloxyethylene); poly(1,1-dichloroethylene); poly(cyclopentylacetoxyethylene); poly(4-dodecylstyrene); poly(4-tetradecylstyrene); poly(oxyethylethylene); poly(oxytetramethylene); poly(oxytrimethylene); poly(oxycarbonylpentamethylene); poly(oxycarbonyl-3-methylpentamethylene); poly(a-methylstryrene); poly(ethylene terephthalate); poly(trimethylene terephthalate); poly(butylene terephthalate); poly(vinyl alcohol); poly(vinyl acetate); polysilane; poly(siloxane); poly(vinylidene fluoride); poly(methyl acrylate); poly(methyl methacrylate); acrylonitrile-butadiene-styrene copolymer (hereafter ABS); poly(urethane); and poly(urea); as well as the classes of polymers to which they belong and blends thereof.
More preferably, the other polymers that can be used in conjunction with saponified polymer/polyamide blends in golf ball layers include: (1) block copolymers of a poly(ether-ester), such as HYTREL(copyright) available from DuPont; (2) block copolymers of a poly(ether-amide), such as PEBAX(copyright) available from Elf Atochem; (3) styrene-butadiene-styrene block copolymers, such as the KRATON D(copyright) grades available from Shell Chemical; (4) styrene-(ethylene-propylene)-styrene or styrene-(ethylene-butylene)-styrene block copolymers, such as the KRATON G(copyright) series from Shell Chemical, either of the KRATON(copyright)s with maleic anhydride or sulfonic graft or functionality, such as the KRATON FD(copyright) or KRATON FG(copyright) series available from Shell Chemical; (5) olefinic copolymers, such as the ethylene-acrylate or ethylene methacrylate series available from Quantum; (6) homo and copolymers produced from non-metallocene catalysts, such as single-site catalysts; (7) ethylene-octene copolymers made from metallocene catalysts, such as the AFFINITY(copyright) or ENGAGE(copyright) series available from Dow Chemical and DuPont-Dow Elastomers; (8) ethylene-alpha olefin copolymers and terpolymers made from metallocene catalysts, such as the EXACT(copyright) series available from Exxon Chemical; (9) block poly(urethane-ester) or block poly(urethane-ether) or block poly(urethane-caprolactone), such as the ESTANE series available from BF Goodrich, the PELLETHANE(copyright) series available from Dow Chemical, ELASTOLLAN(copyright) available from BASF, DESMOPAN(copyright) and TEXIN(copyright) available from Bayer, Q-THANE(copyright) available from Morton International, and PANDEX(copyright) from Dannippon Ink and Chemical Company (Japan); (10) polyethylene glycol, such as CARBO WAX available from Union Carbide; (12) polycaprolactone; (13) polycaprolactam; (14) polyesters, such as EKTAR(copyright) available from Eastman; (15) ethylene-propylene-(diene monomer) terpolymers and their sulfonated or carboxylated derivatives and (16) thermoplastic and elastomer blends such as SANTOPRENE(copyright) from Monsanto.
The amounts of polymers used in the present invention can vary from 1 to 99 parts of the saponified polymer/polyamide blend to 99 to 1 parts of other polymers or ionomers, based on the total weight of polymers. More preferred ratios of 95 to 5 parts of the saponified polymer/polyamide blend with 5 to 95 parts of one or more other polymers. Most preferred is from about 95 to about 10 parts of the subject saponified polymer/polyamide blends and from about 5 to about 90 parts of the other polymer or ionomer. Optionally, the blends of the invention may contain from about 1 to about 20 parts of a suitable compatibilizer.
Compatible blends in accordance with the invention, comprising a saponified polymer and a polyamide polymer and optionally containing one or more of the other polymers or ionomers described above, may be thermoformed and, thus, can be either compression or injection molded to form a layer of foamed or unfoamed material in the cover, core or intermediate layer of a golf ball according to the invention. Typically, the layer has a thickness of at least 0.005 to about 0.125 inch and a Shore D hardness of at least to about 80. Where the layer is foamed, the polymer blends may be foamed during molding by any conventional foaming or blowing agent. Preferably, foamed layers incorporating a saponified polymer/polyamide blend have a flexural modulus of at least 1,000 to about 150,000 psi.
Golf balls according to the invention may incorporate cores comprising saponified polymer/polyamide blends, as well as grafted saponified polymers or polymer blends, non-grafted saponified polymers or polymer blends, polyamide polymers or polymer blends, or conventional materials. Cores comprising a blend of at least one saponified polymer and at least one polyamide polymer may be either one-piece, comprising a single piece of foamed or unfoamed saponified polymer/polyamide blend, or multi-piece, comprising a fluid, solid, or hollow core or center and one or more layers in which any of the center or at least one of the layers comprises a foamed or unfoamed blend of a saponified polymer and a polyamide polymer.
Conventional materials useful in centers, cores, or core layers of the golf balls of the invention include, but are not limited to, compositions having a base rubber, a crosslinking agent and a filler. The base rubber typically includes natural or synthetic rubbers. A preferred base rubber is 1,4-polybutadiene having a cis-structure of at least 40 percent. Natural rubber, polyisoprene rubber and/or styrene-butadiene rubber may be optionally added to the 1,4-polybutadiene. Crosslinking agents include metal salts of unsaturated xcex1,xcex2-fatty acids, such as zinc or magnesium salts acrylic or methacrylic acid. The density adjusting filler typically includes materials such as zinc oxide, barium sulfate, silica, calcium carbonate, zinc carbonate, metallic powders and the like. Golf balls of the invention may also have conventional wound cores, where the core comprises a fluid, solid or hollow center wrapped in elastomeric windings.
Golf balls of the invention may also include at least one intermediate layer situated between the cover and the core. Preferably, the intermediate layer comprises a least one foamed or unfoamed layer that comprises a saponified polymer/polyamide blend, but may also be formed from a grafted or non-grafted saponified polymer or polymer blend, a polyamide polymer or polymer blend, or from any other suitable polymeric material having the desired properties, including, but not limited to, block copolymers of a poly(ether-ester), such as HYTREL(copyright), available from DuPont, block copolymers of a poly(ether-amide), such as PEBAX(copyright), available from Elf Atochem, and styrene-butadiene-styrene and styrene-(ethylene-propylene)-styrene or styrene-(ethylene-butylene)-styrene block copolymers, such as KRATON D(copyright) and KRATON G(copyright) from Shell Chemical.
Any of the cover, the core and the intermediate layer(s) may incorporate at least one layer of a foamed or unfoamed saponified polymer/polyamide blend. Moreover, the core may be a one-piece core, a multi-layer core, or a wound core, having a solid or fluid center.
Golf balls according to the invention may also incorporate cover layers comprising foamed or unfoamed saponified polymer/polyamide blends, polyamide polymers or polymer blends, or conventional materials, including balata and ionomer cover stock. Saponified polymer/polyamide blend cover layers according to the invention may be used with conventional solid or wound cores, as well as those comprising saponified polymers or polyamide polymers or polymer blends. Preferably, the cover of a golf ball according to the invention is formed from a blend comprising at least one polyamide polymer and at least one saponified polymer.
The use of a foamed saponified polymer/polyamide blend also allows the golf ball designer to adjust the density or mass distribution of the ball to adjust the angular moment of inertia and, thus, the spin rate and performance of the ball. Foamed materials also offer a potential cost savings due to the reduced use of polymeric material.
Additional components which can be added to the golf ball compositions of the present invention include, but are not limited to, UV stabilizers; light stabilizers; antioxidants; dyes; optical brighteners; white, colored and/or fluorescent pigments; violet agents; density adjusting fillers, including reactive and non-reactive fillers, such as zinc oxide, barium sulphate and tungsten carbide; softening agents; waxes; surfactants; processing aids; plasticizers, including internal and external plasticizers; impact modifiers; toughening agents; reinforcing materials and metallic powders, such as titanium, tungsten and copper powders. All of these materials, which are well known in the art, are added for their usual purpose in typical amounts, as is well known to the person of ordinary skill in the art.
In particular, nucleating agents may optionally be added to the polyamide component or to the blends of the invention. The more uniform crystalline texture produced by the added nucleating agent may result in increased flexural modulus and hardness. Nucleating agents such as finely dispersed silicas may be added in typical amounts, as is known to those with skill in the art.
Once the compatible blends are formed in the extruder or in other polymer processing equipment known in the art, conventional equipment used in the production of golf balls may be used to form the golf balls of the invention. For example, golf balls comprising cover compositions of the invention can be made by injection molding cover stock formed from the compatible saponified polymer/polyamide blends of the invention around a core or by compression molding pre-formed half-shells of the cover stock into a half-shell mold in a conventional manner.
Forming a compatible blend of two or more saponified polymers and polyamides dramatically improves the ability to control the mechanical properties of the blends, including flexural modulus and hardness. Golf balls and golf ball covers produced from incompatible polymer blends lack durability and crack or split into pieces when hit with a golf club. In contrast, the compatible blends of the invention provide golf balls and covers a having the durability and distance of ionomer covered two-piece balls and the feel and control of balata covered three-piece balls.
The present invention can be used in forming golf balls of any desired size. While xe2x80x9cThe Rules of Golfxe2x80x9d by the USGA dictates that the size of a competition golf ball be no less than 1.680 inches in diameter, golf balls of any size can be used for leisure golf play. The preferred diameter of the golf balls is at least 1.680 inches to about 1.800 inches.

Golf ball compositions comprising saponified polymer and polyamide blends


Provided herein are methods of evaluating efficacy of a treatment in a subject having eye inflammation (e.g., a subject having dry eye syndrome) and selecting a subject for participation in a clinical study. Also provided are methods of treating a subject having eye inflammation (e.g., a subject having dry eye syndrome).

Eye inflammation is common and occurs in humans of all ages. It can last from a few minutes to years, depending on the type and severity of the underlying disease, disorder, or condition. Non-limiting causes of eye inflammation include infection (e.g., bacterial, fungal, viral, or parasitic infection), allergy, autoimmune disorders (e.g., ankylosing spondylitis, Behcet's syndrome, dermatomyositis, Graves' disease, juvenile rheumatoid arthritis, multiple sclerosis, psoriatic arthritis, Reiter's syndrome, rheumatoid arthritis, Sjogren's syndrome, systemic lupus erythematosus, and Wegener's granulatomatosis), dry eye syndrome, irritation, and injury or trauma to the eye or eyelid.
Dry eye syndrome is one of the most common eye problems affecting the general population. Dry eye syndrome can cause problems that range in severity from mildly irritating to debilitating. In healthy subjects, the eye produces a tear film that covers and protects the surface of the eye. The tear film is normally a stable, homogenous layer that provides the cornea and conjunctiva with protection from the air. Patients with dry eye syndrome lack a sufficient tear film (e.g., lack of tears and/or unstable tears) on some surfaces on the cornea and conjunctiva that leads to symptoms of irritation and changing vision. Patients having eye inflammation (e.g., subjects having dry eye syndrome) are commonly prescribed artificial tears, an oral antibiotic, and/or cyclosporine, and occasionally short-term use of steroids.


Regions within editable objects of electronic document can be defined such that specific editing permissions can be granted to specific users for specific regions. The regions can be expressed in a ML format such that a variety of applications that consume ML content can operate in accordance with the granted permissions.

Markup Languages have attained wide popularity in recent years. One type of markup language, Extensible Markup Language (XML), is a universal language that provides a way to identify, exchange, and process various kinds of data. For example, XML is used to create documents that can be utilized by a variety of application programs. Elements of an XML file have an associated namespace and schema.
In XML, a namespace is a unique identifier for a collection of names that are used in XML documents as element types and attribute names. The name of a namespace is commonly used to uniquely identify each class of XML document. The unique namespaces differentiate markup elements that come from different sources and happen to have the same name.
XML Schemata provide a way to describe and validate data in an XML environment. A schema states what elements and attributes are used to describe content in an XML document, where each element is allowed, what types of text contents are allowed within it and which elements can appear within which other elements. The use of schemata ensures that the document is structured in a consistent manner. Schemata may be created by a user and generally supported by an associated markup language, such as XML. By using an XML editor, the user can manipulate the XML file and generate XML documents that adhere to the schema the user has created. XML documents may be created to adhere to one or more schemata.
Electronic documents are often edited by multiple users. For example, a document can be written by a reporter, and then modified by a news editor. In other cases, a former document can be provided by an employer, which is then "filled out" by employees. In such cases, it is desirable to only allow certain regions of the electronic document to be edited. In some cases, electronic documents may be edited by applications that do not "understand" the file protection scheme used by the application that was used to originally author the electronic documents. What is needed is a way to easily handle a variety of protection settings and editing rights when transforming a document into an ML format.

This patent is subject to a terminal disclaimer.

Representing user edit permission of regions within an electronic document


The present invention is related to glucose sensors that are capable of detecting the concentration or level of glucose in a solution or fluid having either low or high ionic strength. The glucose sensors of the present invention comprise a polymerized crystalline colloidal array (PCCA) and a molecular recognition component capable of responding to glucose. The molecular recognition component may be a boronic acid, such as a phenylboronic acid, glucose oxidase, a combination of phenylboronic acid and poly(ethylene)glycol or crown ether, or another component capable of detecting glucose in various fluids and solutions. The glucose sensors of the present invention may be useful in the development of noninvasive or minimally invasive in vivo glucose sensors for patients having diabetes mellitus.

An ever-increasing demand exists for materials and methods that provide continuous, noninvasive or minimally invasive glucose monitoring because of the increase in the number of people diagnosed with diabetes mellitus, more commonly referred to as type 1, insulin dependent diabetes. Clark, Jr., Diabetes Care, 21:Supp. 3, C1 (1998); Davidson, Diabetes Care, 21:2152 (1999). The need for minimally invasive glucose monitoring has also increased due to the recognition that the long-term health of patients with diabetes mellitus is dramatically improved with careful glucose monitoring and control. Picup et al., BMJ, 319:1289 (1999). However, many methodologies for glucose monitoring are invasive and often show poor patient compliance, which leads to negative health consequences for the patient.
The need for minimally invasive, easy-to-use glucose sensors and methods of detecting glucose concentration has motivated the investigation of numerous approaches. For example, early work in near-infrared absorption spectroscopy, which took advantage of tissue transparency in the 600 to 1300 nm spectral range, showed initial promise as a truly non-invasive glucose sensor. Heinemann et al., Diabetologia, 41:848 (1998). In this technique, near-infrared radiation is allowed to penetrate biological tissues within the therapeutic window of 600 to 1300 nm, and the spectrum of the tissue is then acquired through either a transmission or a reflectance measurement. Arnold et al., Anal. Chem., 70:1773 (1998). The acquired spectrum contains a mixture of overlapping spectral bands for the various components of the tissue, such as water, fat, protein, and glucose, and the spectrum is used to determine the level of glucose in the tissue. However, the accuracy of this technique is negatively affected by factors such as blood flow and temperature, which are difficult to control.
Various optical methods have also been investigated for noninvasive glucose monitoring. For example, luminescent glucose sensors have been developed based on the intrinsic green fluorescence of the glucose oxidase enzyme (referred to herein as "GOD"), the enzyme involved in the conversion of glucose to gluconic acid. Trettnak et al., Analytica Chimica Acta, 221:195 (1989). The flavin moiety, which is present at the active site of the GOD, becomes reduced when glucose is converted to gluconic acid. Because the flavin moiety and its reduced form exhibit different fluorescence spectra, the change in the fluorescence spectrum of the GOD may be monitored to determine the glucose concentration in a solution or fluid.
Other researchers have attached fluorescent probes to the GOD molecule for fluorescence-based glucose sensing, since the binding of glucose to the GOD molecule changes the fluorescence probe. James et al., Angewandte Chemie Int'l Edition in English, 33:2207 (1994). In another approach, fluorescent probes are attached to glucose binding proteins (also called maltose binding proteins), where the glucose binding proteins undergo dramatic conformational changes which alter the fluorescence of the probe. Marvin et al., Proc. Natl. Acad. Sci., USA, 94:4366 (1997); Marvin et al., J. Am. Chem. Soc., 120:7 (1998). Additionally, other techniques such as photoacoustic spectroscopy (MacKenzie et al., Clinical Chemistry, 45:1487 (1999)), near-infrared absorption spectroscopy (Gabriely, et al., Diabetes Care, 22:2026 (2000)), and near-infrared fluorescence spectroscopy (Rolinski et al., J. Photochem. Photobiol. B: Biology, 54:26 (2000)) have also been investigated for determining the level of glucose in tissues.
Recently, various minimally invasive approaches to glucose monitoring have attempted to determine glucose levels in extracted interstitial fluid. These approaches utilize microdialysis (Boutelle et al., Anal. Chem., 64:1790 (1992)) or electric fields (Tamada et al., Diabetes, 47:Supp. 1, 62A (1998)) to obtain the interstitial fluids through the skin, and such techniques use primarily electrochemical methods to determine the glucose concentration. The last approach has been commercialized as a watch-type device to electrochemically determine the glucose level in fluid that is extracted through the skin. Picup et al., BMJ 319:1289 (1999). However, the perspiration on a patient's skin may interfere with the accuracy of such a watch-type device.
More invasive approaches of glucose monitoring involve the implantation of electrochemical and fluorescent sensors in tissue. For example, one approach provides for the monitoring of the intensity of the fluorescence of the glucose sensors through the skin by using small external spectrometers. Ballerstadt et al., Anal. Chem., 72:4185 (2000). Other approaches provide for the implantation of electrochemical glucose sensors within the body, and some of these approaches utilize external circuits to determine the electrochemical signals given off by the glucose sensors, while others completely implant the sensors and utilize various remote readouts to monitor glucose levels. Wilson et al., Clin. Chem., 1613 (1992). All of these approaches to glucose monitoring face the challenges of sensor stability, tissue rejection, ease of use, and cost.
A variety of electrochemical glucose sensors are known in the art. One such electrochemical glucose sensor involves an amperometric enzyme electrode, which uses immobilized glucose oxidase (GOD). Generally, the conversion of glucose to gluconic acid can be described by the following reaction scheme:GOD-FAD+β-D-glucose→GOD-FAD·H2+D-glucono-δ-lactoneGOD-FAD·H2+O2→GOD-FAD+H2O2  (1)wherein "FAD" represents the flavine-adenine dinucleotide prosthetic group that is attached to the GOD enzyme, while FAD·H2 represents the reduced form of FAD. Referring to the above reaction scheme, GOD amperometric sensors are able to monitor the concentration of glucose by monitoring the change in the flow of current caused by the electrochemical reduction of hydrogen peroxide as shown in the reaction designated "(1)" in the above scheme.
Another electrochemical glucose sensor that utilizes GOD involves the use of pH-responsive hydrogels. Dorski et al., Polym. Prepr., 37:475 (1996); Podual et al., Biomaterials, 21:1439 (2000); Jung et al., Macromolecules, 33:3332 (2000). The GOD-induced catalysis of glucose to gluconic acid results in a decrease in the pH of the solution. This pH decrease actuates the swelling or shrinking of the hydrogel materials. These hydrogel volume changes alter the diffusion constant of electrochemically active species in the solution. The resultant changes in the electrochemistry (for example, changes in conductivity and current flow) may be used to monitor the glucose concentration. Such an approach may also be useful for developing in vivo insulin supplying devices. Schwarte et al., Polym. Prepr., 38:596 (1997); Bell et al., Biomaterials, 17:2023 (1996). This type of electrochemical approach to detecting glucose in a solution require the use of electrical wires and instrumentation.
Other electrochemical approaches for monitoring glucose levels in fluids have utilized polymer hydrogels that have been functionalized with phenylboronic acids, which bind glucose and other diols. Kitano et al., Makromol. Chem., Rapid Commun., 12, 227–233 (1991). The binding of glucose results in the swelling or shrinking of a hydrogel, where the hydrogel is coated on the surface of an electrode. The changing volume of the hydrogel is monitored through its effects on the diffusion constant of electrochemically active species with respect to the electrode. Even though the detection scheme for measuring glucose levels disclosed by Kitano et al. employs a hydrogel that swells and shrinks, such an electrochemical sensing method requires the use of electrical wires and instrumentation in order to detect glucose levels. Thus, a hydrogel glucose sensor according to Kitano et al. could not be used in a contact lens type format nor as an optical insert, as it would be impossible to connect electrical wires and/or instrumentation to the sensor while the sensor is in a patient's eye.
As mentioned above, some glucose sensors known in the art have employed polymer hydrogels. For example, glucose sensing materials have been disclosed which comprise a polyacrylamide hydrogel wherein a crystalline colloidal array is embedded. The polymerized crystalline colloidal array chemical sensing materials (which have been referred to as "PCCA"s) have been described in, for example, U.S. Pat. Nos. 6,187,599, 5,854,078, and 5,898,004, all of which are hereby incorporated by reference in their entireties herein. Such PCCA materials have been described with respect to their ability to detect metal cations, pH, ionic strength, and the concentration or level of glucose.
In previous disclosures where PCCA chemical sensing materials have been used in conjunction with measuring levels of glucose, the sensing materials have relied upon GOD, the enzyme described earlier. Specifically, the conversion of glucose to gluconic acid, which is catalyzed by the GOD enzyme, results in the reduction of FAD, whereby the FAD becomes negatively charged and causes the hydrogel (in which the PCCA is embedded) to swell. This swelling of the hydrogel results in a red-shift of the Bragg diffraction, which enables a user to determine the concentration of glucose.
A need exists for the development of accurate, reliable, continuous, and noninvasive or minimally invasive glucose sensors that may improve the lives of patients having diabetes and may decrease such patients' risk of developing hypoglycemia and hyperglycemia.

Intelligent polymerized crystalline colloidal array carbohydrate sensors


A method for simultaneously recording motion and still images, includes the steps of: capturing a motion image sequence and accompanying audio of a scene with a digital video camera adapted to record both motion and higher resolution still images; simultaneously capturing a still image sequence having a higher resolution and lower frame rate than the motion capture sequence; compressing the motion image sequence using interframe compression and the accompanying audio and storing the compressed motion image and audio data; and compressing the still images using intraframe coding and storing the compressed still image data.

Currently, it is common for consumers to use camcorders to capture motion video images, which are viewed on a TV display, and film cameras to capture still images which are developed and optically printed to provide hardcopy prints. Carrying both types of devices is burdensome, however. Thus, there is interest in having a digital camcorder type device that captures motion images, while also allowing high quality prints to be produced from selected image frames.
Recent advances in digital camcorders include the ability to capture both motion and still images (commonly referred to as MOST cameras), and associated audio information, such as those from JVC (GR-DV1) and Sony Corp. (DCR-PC7) which allow the capture of motion video and still imagery. For example, the GR-DV1 from JVC allows a user to capture a snapshot while recording live video. Basically, the snapshot is indicated by overlaying a white border on the particular still frame of the captured live video. See U.S. Pat. No. 5,382,974, issued Jan. 17, 1995 to Soeda et al. entitled Movie Camera Having Still Picture Photographing Function and Method of Photographing Still Picture Therewith, which shows a movie camera capable of also capturing still images. Although these cameras allow one to capture motion and still images, they do not provide adequate still image quality. Furthermore, the user must decide before taking the picture whether a still or motion type image is desired. Often, the user would like to have both a motion video sequence and a still image of the same event (e.g. their daughter scoring the winning soccer goal). This is difficult to do with these prior art systems, where the user must press a special button to obtain a "still" image, rather than deciding at a later time what images they would like to have as high resolution prints.
A high definition camcorder could store a high resolution (e.g. 1280×960 pixels) motion sequence for each image frame, to provide higher quality still images. However, to produce good motion rendition of high speed objects, a high frame rate (e.g. 30 frames/sec) is required. The amount of data that would need to be processed and stored per second (e.g. 1280×960×30 pixels) would be excessive, requiring a high cost, power-hungry design having a limited recording time.
There is a need therefore for a digital motion/still camera design that reduces the processing and storage requirements, while providing both good motion rendition and the ability to obtain high resolution prints from any desired scene after it has been captured.

Digital camera for capturing a sequence of full and reduced resolution digital images and storing motion and still digital image data


A deployable/retractable expandable bag system for enclosure and release of space objects, constructed from materials exhibiting abrasion resistance and ballistic protection. Pressurized expandable textile trusses support textile membrane materials exhibiting radial contracting or collapsing contracting directional qualities. Stabilizing wires define bag length and minimize rotational forces of the captured object. Upon entry of the space object into the bag system, pressurized gas in trusses is released. The expandable trusses and membranes retract over and onto the space object. The expandable bag may be re-pressurized, and the bag re-opened, for removal and redirection of the space object; upon re-stowing, the system is ready for another capture mission.

In response to the relatively small meteor which broke up near Chelyabinsk, Russia in February 2013 and ongoing investigation of Near Earth Object (NEO) close encounters with earth which could seriously impact life on earth, the U.S. Congress has issued a mandate to the National Aeronautics and Space Administration (NASA) to protect planet Earth. NASA has since issued a Grand Challenge to capture an asteroid, or remove a boulder on a larger asteroid, and return samples to earth in about 2025.
The United Nations also has an international task force to investigate an asteroid re-direct demonstration project, currently planned for 2023. Several businesses are planning to mine asteroids in space. To optimally mine the asteroids, the asteroids may need to be transferred to other locations in space such as the earth-moon Lagrange Point L1 or into an orbit around the moon.
Man-made space-object debris is an additional concern. An estimated 4.4 million pounds of space-object debris are in low-earth orbit. These space objects can be catastrophic for humans and spacecraft. The International Space Station dodges man-made space-object debris each year.
Expandable capture bag concepts to capture an asteroid or other space objects have been promoted by NASA and various private enterprises. While these prior art expandable bags can be stowed somewhat compactly and deployed to a larger size to contain a space object, they typically are constructed from non-expandable/non-stretchable textiles impregnated with an elastomer to form a pressure barrier to contain the pressurized gas.
Expandable/stretchable textile fibers are similar to a coiled spring. The fibers uncoil under tension, and then return to their coiled configuration when the tension is removed. Expandable/stretchable textiles are difficult to impregnate with an elastomer and still allow the textile to expand or stretch. When an elastomer is impregnated into an expandable textile, the elastomer prevents the textile fibers from uncoiling. The result is that the textile becomes essentially non-expandable and non-stretchable.
Prior art capture bag systems utilize non-stretchable pressurization (hose/tube) systems because the impregnated elastomer restricts the textiles' ability to stretch and expand. Consequently, the entire deployed length of the hose or tube must be stowed. The result is a system having a large stowed volume and a relatively high mass.
In addition, the prior art capture bag systems deploy to a large diameter and block sensors onboard the spacecraft used to identify and accurately locate a space object.
Accordingly, there is an as of yet unmet need in the art for a space-object capture apparatus that: 1) is made of components that may be compactly stowed at a size and length significantly less than when deployed; 2) is made of components having a lower combined mass than prior art systems; 3) maintains an adequate pressurized gas barrier without components constructed from non-expandable elastomer-impregnated materials; 4) is constructed using materials that are simultaneously expandable, stretchable, abrasion resistant, and impervious to ballistics; and, 5) upon deployment, continues to allow spacecraft sensors to operate and operators to view space from within the apparatus.

Stretch skin receptacle for space object capture and release


A method and apparatus for regulating an input voltage to a power conversion module. In one embodiment, the method comprises computing a voltage regulation threshold based on an output voltage for the power conversion module; comparing an input voltage of the power conversion module to the voltage regulation threshold; and generating, when the input voltage satisfies the voltage regulation threshold, an average input voltage less than the voltage regulation threshold, wherein the average input voltage is generated from the input voltage.

Field of the Invention
Embodiments of the present disclosure relate generally to power conversion and, in particular, to regulating an input voltage to a power converter.
Description of the Related Art
Use of distributed generators (DGs) to produce energy from renewable resources is steadily gaining commercial acceptance due to the rapid depletion of existing fossil fuels and the increasing costs of current methods of generating power. One such type of DG may be a solar power system comprising a plurality of photovoltaic (PV) modules that convert solar energy received from the sun into a direct current (DC). One or more inverters then convert the DC current from the PV modules into an alternating current (AC). The AC power generated may then be used to run appliances at a home or business, or may be coupled to the commercial power grid and sold to the commercial power company.
One type of inverter that may be utilized for such DC-AC power conversion is a current source inverter (CSI). A CSI inverter is the dual of a voltage source inverter (VSI); for a CSI, the DC power supply is configured as a current source rather than a voltage source as for the VSI. One advantage of the CSI is that it increases the voltage towards the grid, negating the need for an additional DC-DC boost stage generally required by a VSI. Such an increase in voltage requires that the input voltage to the CSI must be lower than its output voltage.
In some large-scale DG installations, such as utility-scale installations, the grid voltage may drop, requiring additional power to be injected from the DG onto the grid to maintain operation of the grid. Such a drop in grid voltage may result in an output voltage at the CSI that is lower than the CSI input voltage, causing an unstable condition where current generation by the CSI cannot be controlled.
Therefore, there is a need in the art for a method and apparatus for regulating an input voltage to a power conversion module.

Method and apparatus for power converter input voltage regulation


A power-split transmission comprises an electric variator (9) and an electric variator (10) which can be connected, by way of a clutch (8), for forward driving, and a clutch (7), for reverse driving, to the drive output shaft (5) in such manner that the drive output shaft (5) can be purely electrically driven even when the input shaft (2) is static.

Power-split transmissions of this type can be driven by an internal combustion engine and comprise a first electric variator and a second electric variator. Between the internal combustion engine and the power-split transmission a clutch is often arranged in order to be able to drive the vehicle even without the internal combustion engine.
In this context the term variator is understood to mean a variator machine.
CN 1 04 494 415 B discloses a power-split transmission with a clutch between the internal combustion engine and the power-split transmission, wherein the power-split transmission comprises a first electric variator and a second electric variator. The clutch enables the vehicle to be driven purely electrically.


Chrominance image information is generated based upon input image information. A determination target area to undergo determination of a target object within a determination target image constituted with the chrominance image information is set. An average chrominance value for each of the determination target area and a plurality of peripheral areas set around the determination target area is calculated based upon the chrominance image information corresponding to each area. Color information expressed by the average chrominance value calculated for the determination target area is evaluated to determine whether or not the color information matches a characteristic color defined in advance in correspondence to the target object. A difference between the average chrominance value in the determination target area and the average chrominance values in the peripheral areas is evaluated to determine whether or not the determination target area is an image area separate from the peripheral areas. A decision is made as to whether or not the determination target area contains the target object based upon results of an evaluation indicating whether or not the average chrominance value in the determination target area matches the characteristic color and the result of an evaluation indicating whether or not the determination target area is an image area separate from the peripheral areas.

In an image processing method known in the related art, a person's face in a photographed image is detected by executing face determination processing on a face candidate area, which is an image area containing skin color and has been detected as a face candidate. (See patent reference literature 1).
Patent reference literature 1: Japanese Laid Open Patent Publication No. 2000-48184

Image processing method, image processing program and image processing apparatus for detecting object of an image


Brake disc for a vehicle disc brake, comprising a radially inner hub portion (1a), intended to be non-rotatably joined to a wheel hub, and a surrounding, radially outer disc portion with opposing friction surfaces. The outer disc portion is formed by two disc elements (4) joined to the hub portion, and which are separated by spacers (7a–7f), which define passages for cooling air and of which at least some (7a, 7b) are in the form of fan vanes to generate an airflow from the passage inlets (10) at the outer periphery of the disc to the passage outlets (11) at the outer periphery of the disc.

The present invention relates to a brake disc for a vehicle disc brake, comprising a radially inner hub portion intended to be non-rotatably joined to a wheel hub, a surrounding, radially outer disc portion with opposing frictional surfaces and passages formed in the outer disc portion, said passages being arranged to conduct cooling air in the disc material between the frictional surfaces.
So-called ventilated brake discs, which are made to increase the cooling effect of the ambient air by diverting heat generated during braking, occur in two principle types. One type has channels which extend radially through the disc from the inner periphery of the hub to the outer periphery of the surrounding disc portion. The channels thus have inlet openings in the inner periphery and outlet openings in the outer periphery. As the disc rotates, a guided airflow is created through the channels from the inlet to the outlet. The other type of ventilated brake disc consists of two disc elements, which are fixed to a hub and to each other side-by-side with an intermediate space created by a plurality of spacers in the form of pillars.
By ventilating the disc, the mean temperature of the disc is reduced. Since the wear on the disc and linings is strongly depending on temperature, a reduction in temperature will have a positive effect on this wear. Furthermore, the highest temperature of the disc is reduced for most driving styles, which in turn reduces the risk of brake fade and the risk of cracking. One disadvantage of having channels opening into the inner periphery of the hub is, however, that the material mass is reduced in that portion of the brake disc where the stresses are greatest, both as regards braking force and temperature difference. The high stresses in connection with the holes in the hub increase the risk of cracking. In the other type of brake disc with spacers in the form of pillars between two disc elements, one does not have the above mentioned negative stress profile, but on the other hand, no fan action is achieved either.


The invention is to provide a process for effectively removing impurities contained in an amide compound-containing solution by making an amide compound-containing solution, particularly an amide compound-containing solution produced by a hydration reaction of a nitrile compound by using a microorganism fungus body containing nitrile hydratase or a processed product of the microorganism fungus body, in contact with activated carbon under acidic conditions.

In a production liquid of an amide compound, particularly an amide compound obtained by hydration of a nitrile compound, impurities, such as a polymeric compound, a surfactant, a coloring component, an eluted component and the like, are generally present while the species thereof are different depending on the production process thereof. In order to remove them, for example, a purification process using activated carbon is described in JP-A-61-115495 and JP-A-61-122253 (EP-A-182578), a purification process using an ion exchange membrane is disclosed in JP-A-61-115058, and a purification process by a porous hollow fiber film is disclosed in JP-A-61-122227 (EP-A-188068).
However, the purification processes using an ion exchange membrane and a porous hollow fiber film cannot avoid economical demerits upon practice, such as necessity of a special purification equipment and the like.
In the purification process using activated carbon, while no special equipment is required, impurities are still present in the resulting product, and the process is insufficient from the standpoint of efficiency. Particularly, in the case where an amide compound is produced by directly hydrating a nitrile compound by using a nitrile hydratase, which is an enzyme having an ability of hydrating a nitrile, or the like, protein originated from microorganisms mixed in the reaction solution is insufficiently removed by the purification process by activated carbon according to the conventional technique, and as a result, the reaction solution is liable to be foamed when it is a trace amount, or the reaction solution becomes clouded when the amount is large, whereby the quality of the product is adversely affected.
Therefore, an object of the invention is to provide a process for effectively removing impurities contained in a solution containing an amide compound. More specifically, an object of the invention is to provide a simple and effective purification process in the case where an amide compound-containing solution obtained upon producing a corresponding amide compound from a nitrile compound is processed with activated carbon.


An exhaust circulation apparatus that can improve fuel combustion and suppress discharged NOx by expanding an operating region in which homogeneous lean combustion is possible. The exhaust circulation apparatus includes a homogeneous lean combustion unit for performing homogeneous lean combustion in a predetermined lean-burn region, and an EGR apparatus for performing EGR that recirculates a portion of gas that flows through an exhaust system of the internal combustion engine to an intake system. When performing homogeneous lean combustion, the exhaust circulation apparatus controls the EGR apparatus to perform EGR. An LPL-EGR apparatus that recirculates gas flowing through an exhaust passage on a downstream side of a turbine to an intake passage on an upstream side of a compressor is used as the EGR apparatus. Preferably, an air-fuel ratio is controlled so as to be 22:1 and an EGR rate is controlled so as to be between 10% and 20%.

An exhaust circulation apparatus for an engine with a supercharger that performs EGR that recirculates a portion of exhaust gas to an intake system is already known, as disclosed, for example, in Japanese Patent Laid-Open No. 2003-129874. According to this apparatus, EGR is performed when performing stratified lean combustion in which a gaseous mixture of fuel and air is stratified and a comparatively dense gaseous mixture in the vicinity of a spark plug is ignited, and a flame is propagated to a lean gaseous mixture inside the combustion chambers by a fire source that was ignited. Since it is thereby possible to reduce the combustion temperature, the amount of discharged NOx is suppressed.

Exhaust circulation apparatus for internal combustion engine