A game ball having a cover formed from a crosslinkable thermoplastic polyurethane is disclosed. Various types of game balls are described, including golf balls and softballs. By selective exposure to radiation, the thermoplastic polyurethane cover is crosslinked and its hardness is increased. Typically, increases in hardness values of at least 2 units on the Shore D scale are realized upon exposure to 3.5 Mrads of gamma radiation.

The present invention generally relates to game balls, and more particularly to game balls having covers containing crosslinkable thermoplastic polyurethane. The ball preferably is a molded game ball such as a golf ball, basketball, baseball, softball, football, soccer ball, volleyball, tennis ball, lacrosse ball or the like.
There are generally, three types of golf balls. The first type is a wound ball wherein a vulcanized rubber thread is wound under tension around a solid or semi-solid core, and thereafter is enclosed in a single or multi-layer covering of tough, protective material.
A second type of golf ball is a one-piece ball formed from a solid mass of moldable resilient material which has been cured to develop the necessary degree of hardness. One-piece molded balls do not have an enclosing cover.
A third type of ball is a multi-piece (two or more pieces) non-wound ball which includes a solid or liquid core of one or more layers and a cover having one or more layers formed over the core.
Multi-piece non-wound golf balls typically have a cover which contains a substantial quantity of ionomer. Useful ionomers include those sold by E. I. Dupont de Nemours and Company under the name Surlyn(copyright) as well as those sold by Exxon under the name Iotek(copyright). Ionomers impart toughness and cut resistance to the covers. It would be useful to develop golf ball covers which contain substantial quantities of non-ionomeric materials and which have the durability, scuff resistance, cut resistance and other playability properties of ionomeric golf ball covers.
Polyurethanes are polymers which are used to form a broad range of products. They are generally formed by mixing two primary ingredients during processing. For the most commonly used polyurethanes, the two primary ingredients are a polyisocyanate (for example, diphenylmethane diisocyanate monomer (xe2x80x9cMDIxe2x80x9d) and toluene diisocyanate (xe2x80x9cTDIxe2x80x9d) and their derivatives) and a polyol (for example, a polyester polyol or a polyether polyol).
A wide range of combinations of polyisocyanates and polyols, as well as other ingredients, are available. Furthermore, the end-use properties of polyurethanes can be controlled by the type of polyurethane utilized, i.e., whether the material is thermoset (crosslinked molecular structure) or thermoplastic (linear molecular structure).
Crosslinking occurs between the isocyanate groups (xe2x80x94NCO) and the polyol""s hydroxyl end-groups (xe2x80x94OH). Additionally, the end-use characteristics of polyurethanes can also be controlled by different types of reactive chemicals and processing parameters. For example, catalysts are utilized to control polymerization rates. Depending upon the processing method, reaction rates can be very quick (as in the case for some reaction injection molding systemsxe2x80x94xe2x80x9cRIMxe2x80x9d) or may be on the order of several hours or longer (as in several coating systems). Consequently, a great variety of polyurethanes are suitable for different end-uses.
Polyurethane has been used for golf balls and other game balls as a cover material. Commercially available polyurethane golf balls have been made of thermoset polyurethanes. A polyurethane becomes irreversibly xe2x80x9csetxe2x80x9d when a polyurethane prepolymer is crosslinked with a polyfunctional curing agent, such as polyamine and polyol. The prepolymer typically is made from polyether or polyester. Diisocyanate polyethers are preferred because of their water resistance.
The physical properties of thermoset polyurethanes are controlled substantially by the degree of crosslinking. Tightly crosslinked polyurethanes are fairly rigid and strong. A lower amount of crosslinking results in materials that are flexible and resilient. Thermoplastic polyurethanes have some crosslinking, but purely by physical means. The crosslinking bonds can be reversibly broken by increasing temperature, as occurs during molding or extrusion. In this regard, thermoplastic polyurethanes can be injection molded, and extruded as sheet and blown film. They can be used to up to about 350xc2x0 F. and are available in a wide range of hardnesses.
U.S. Pat. No. 5,006,297 indicates that while thermoplastic and thermosetting polyurethanes are known, thermosets have been found to produce better cover stocks for golf balls. Additionally, while thermoplastic polyurethanes can be used to form game balls, they lack the scuff and cut resistance of a crosslinked polyurethane. Similarly, thermoplastic polyurethanes do not readily crosslink.
A further disadvantage of using thermosetting polyurethanes to form game ball covers is that scrap material (i.e. sprues, runners and/or reject parts) and cover stock from off-spec balls cannot be reused without substantial processing. It would be useful to develop a high quality game ball utilizing a polyurethane cover material which is subject to thermal degradation prior to final processing. In such a case, the scraps formed in the cover molding stage could be conveniently re-used to form additional game ball covers. A further advantage would be to produce a polyurethane based game ball which, when molded and then crosslinked, is resistant to thermal degradation. This would produce an improved game ball which could also withstand prolonged exposure to heat during use or storage.
The present invention relates to new and improved game balls which overcome the above-referenced problems and others. An object of the invention is to form a durable, scuff resistant game ball. The invention includes unitary, wound, two-piece, three-piece and multi-layer golf balls, but is not limited solely to golf balls.
Another object of the invention is to provide a game ball cover in which scrap cover material can be readily reused prior to final processing.
Yet another object of the invention is to provide a golf ball having a scuff resistant polyurethane cover which is also resistant to heat elongation at high temperatures.
Yet another object of the invention is to provide an improved method for making a thermoplastic polyurethane covered game ball
Yet another object of the invention is to provide a method for making a scuff resistant and cut resistant polyurethane game ball.
Another object of the invention is to provide a method of making a polyurethane covered golf ball having high heat resistance.
An additional object is to produce a thermoplastic polyurethane game ball which is readily crosslinked via high energy electrons or gamma rays. Such a thermoplastic polyurethane would be easily processable and could be directly molded into or around a core to form a game ball. Alternatively, the thermoplastic polyurethane could be injection molded into half shells that could be compression molded around a core or a mantle to form a multi-piece game ball. The runners and scraps from the molding process would not be crosslinked and could then be recycled with the virgin cover material. After molding, the game ball could then be subjected to electron beam or gamma irradiation.
Other objects will be pointed out more particularly in detail hereafter.
The present invention addresses and remedies all of the foregoing objectives. In a first aspect, the present invention provides a game ball comprising a central portion and a first cover layer formed over the central portion. The first cover layer is formed from a particular type of crosslinkable thermoplastic polyurethane.
In another aspect, the present invention provides a core and a cover layer disposed about the core. The cover layer comprises a thermoplastic polyurethane that is capable of undergoing crosslinking upon exposure to about 3.5 Mrads of radiation, thereby causing an increase in the hardness of the cover by at least 2 units on the Shore D hardness scale.
In yet another aspect, the present invention provides a method of forming a game ball comprising providing a game ball center and then forming a cover layer over the game ball center. The cover layer includes a crosslinkable thermoplastic polyurethane.
In a further aspect, the present invention provides a method of making a golf ball comprising providing a core of a particular composition, forming a cover layer about the core, and then irradiating the cover layer under conditions sufficient to increase the Shore D hardness of the cover layer by at least 3 units. The cover layer comprises a resin composition that includes at least 95 parts by weight of a crosslinkable thermoplastic polyurethane and has a hardness prior to crosslinking, of 35 to about 72 on the Shore D hardness range.

Game balls with cover containing post crosslinkable thermoplastic polyurethane and method of making same


Low viscosity methacrylic-urethane oligomers useful as a styrene monomer substitute in unsaturated resin compositions, are prepared by reacting a hydroxy ethyl or propyl methyl methacrylate monomer with an elastomeric urethane prepolymer having free NCO groups.

Unsaturated resin compositions typically have used styrene monomers, like styrene as a reactive diluent, to adjust and reduce the viscosity of the resin compositions, generally in amount of up to 50% by weight, e.g., 5 to 40%. The unsaturated resin compositions include unsaturated polyester resin compositions prepared by the reaction of unsaturated acids with alcohols, such as dicarboxylic acids and dihydroxy alcohols.
Ethylenic unsaturation is usually realized by the use of maleic and fumaric acids or anhydrides; however, such compositions may also contain saturated acids, like phthalic and adipic acids to adjust resin properties. The dihydroxy alcohols used in the preparation may include: ethylene; propylene; diethylene; dipropylene glycols; and neopentyl glycol. These resin compositions contain cross-linking agents, like styrene and diallyl phthalate, and are peroxide curable to provide thermosetting resins.
The vinyl ester resin compositions comprise the vinyl esters of various acids, typically, short chain aliphatic and dicyclic acids, like C2-C6 acids, such as acetic acid. These vinyl ester resin compositions, such as polyvinyl acetate, contain cross-linking agents and styrene monomers and are subject to peroxide cure to produce a thermosetting vinyl ester resin.
While the use of styrene monomers provides a satisfactory product, the Environmental Protection Agency (EPA) requires that such cross-linkable resin compositions meet EPA regulations for volatile organic compounds (VOC).
The search for styrene monomer substitutes to meet VOC regulations is directed to low VOC compounds which are not flammable. Such substitutes are usually limited to: acrylic monomers; oligomers; methyl methacrylates; and allyl alcohol ethers. However, the acrylic monomers are usually associated with strong odor, low viscosity, strong skin irritation, and slow peroxide cure.
Acrylic oligomers are typically too high in viscosity and do not lend themselves to reduction in viscosity like the styrene monomers do. The allyl alcohol compounds tend to be very slow curing, and like the acrylics, are inhibited by air to cure with peroxides. Further, methyl methacrylate monomers are classified, like styrene monomers, by the EPA and have a strong objectionable odor.
It is desirable to provide a substitute for styrene monomers in resin compositions, which substitute provides a reactive diluent which overcomes the prior objections of other proposed prior art substitutes.
The invention relates to methyl methacrylate-urethane oligomers, the method of preparation of the same, polymers produced therefrom, and resin compositions wherein the oligomers are employed in whole or in part as styrene monomer substitutes.
The invention comprises a low viscosity methyl methacrylic-urethane oligomer prepared by the reaction of a hydroxyalkyl methacrylate monomer with an elastomeric urethane prepolymer having free NCO groups, and the oligomer is typically characterized by a viscosity of less than about 500 centipoise (cP).
The invention relates to a polymer prepared by the polymerization of the oligomer, typically by peroxide cure, free radical cure, or radiation cure of the oligomer alone or with other monomers or oligomers. The invention also comprises a low viscosity alkyl methacrylic-urethane oligomer prepared by the reaction of and in the presence of a catalyst of a hydroxyl ethyl or hydroxyl propyl methacrylate monomer with a flexible elastomeric urethane prepolymer, and generally having about 5 to 15% free NCO groups in about a stoichiometric amount or very minor excess of 0.1 to 0.2%, or in an excess of the methacrylate monomer, such as up to about 2 to 5 percent.
While the oligomer may be prepared with an excess of free NCO groups, the reaction preparation is not preferred, since the free NCO groups in the oligomer tend to react with moisture in the air and to cause foaming of the oligomer. The preferred reaction is to employ a stoichiometric amount or a slight excess of the methyl methacrylate monomer.
The resin composition, with the oligomer, may include: stabilizers; catalysts; promoters; curing agents; various filler materials; and other additives and components used in and with oligomers and resin compositions to prepare oligomer resin compositions suitable for use as: paint coatings; industrial floor coatings; gel coat replacement in laminates, such as rigid urethane foam-polyester composite laminate structures; marble coatings; and/or other industrial applications.
It has been discovered that the oligomers of the invention are characterized by low viscosity, such as less than 500 cP at 25xc2x0 C., and preferably, less than 200 cP, e.g., about 100 cP and are suitable as styrene monomer substitutes in resin compositions, without sacrifice time or properties, and most important, the oligomers reduce VOC""s to lower and acceptable levels.
The oligomers may be used in whole or in part as styrene monomer substitutes and may be used alone or with styrene monomers or other polymerizable monomers.
The oligomers, particularly those aliphatic or alicyclic urethane oligomers, may be used to produce UV stable coatings and polymers without VOC""s for a number of novel and useful applications.
The hydroxyalkyl methacrylates employed are preferably: hydroxyethyl methacrylate (HEMA); hydroxypropyl methacrylate (HPMA); or mixtures thereof. The hydroxymethyl methacrylate (HEMA), when used by itself, produces a brittle polymer which can still be a skin irritant, and HEMA is also quite sensitive to air inhibition.
The oligomers of the invention are low viscosity oligomers and may be employed as a reactive diluent, i.e., as a styrene or methyl methacrylate monomer substitute with unsaturated resin compositions, generally peroxide-curable resin compositions in amounts of 5 to 90% by weight, such as about 10 to 30% by weight.
The oligomers are prepared generally in the presence of a catalyst, and optionally but preferably, in the presence of a promoter to provide the methyl methacrylate urethane oligomers. The catalyst and promoter materials and amounts used may vary but organo-metallic catalyst, such a tin salts as a catalyst, and cobalt salts, like DMAA and DMA and various amines as promoters are satisfactory.
The reactants are mixed and heated, e.g., 120 to 180xc2x0 F., for a time of about 2 to 8 hours. The reactants may be used in varying amounts, but generally in about stoichiometric amounts. It is desirable to add a stabilizer or inhibitor to the reaction mixture to stabilize and prevent premature polymerization of the resulting oligomer, such as quinones and hydroquinones and derivatives.
The oligomers are cross-linkable with other monomers, such as in the resin composition or by itself, by the use of organic peroxides and promoters, like methyl ethyl ketone peroxide (MEKP), benzyl peroxide with amine promoters, like dimethylamine (DMA), diethylamine, and diethanolamine (DEA).
The solution and preparation of the elastomeric urethane prepolymer is important, due to the normal brittle nature of the methyl methacrylate monomers used in the reaction. The urethane prepolymer should be an elastomeric flexible prepolymer with free NCO groups for reaction with the selected amount of the methyl methacrylate monomer, generally greater than 50% by weight of the methyl methacrylate, e.g., 70 to 80% by weight with a prepolymer of 8 to 12% free NCO groups.
The elastomeric urethane prepolymers may be prepared with aromatic, aliphatic, or alicyclic polyisocyanates, typically diisocyanates reacted with polyols or amines which produce elastomeric urethanes.
Elastomeric urethane prepolymers, with about 10% free NCO for the best results, may be prepared employing primary linear diols and triols to include ethylene:oxide capped diols and triols, as well as linear polyesters and polyesters with free hydroxyl groups and aliphatic amines. Suitable polyisocyanates to prepare the prepolymers include: NCO uretedimine MDI; aliphatic dimer NCO; and isophorone diisocyante. Aliphatic urethane oligomers of low viscosity, e.g., 100 to 500 cP, are prepared from aliphatic diisocyanates and aliphatic amines of about 2000 MW and 5 to 10 NCO groups with HEM or HPMA in the presence of a tin catalyst and inhibitor.
The oligomer and oligomer resin composition may contain varying amounts of filler material, such as, but not limited to 5 to 50% by weight of: glass fibers; stone dust; calcium carbonate; metal oxides; and flame retardants, like aluminum trihydrites to provide marble-simulated resin coatings.
The oligomer of the invention may be schematically represented generally by the formula:
wherein R is an alkyl radical, such as C2-C4, such as a ethyl or propyl, the oligomer having a molecular weight of less than about 5000 and greater than 1200.

Methacrylic-urethane oligomers, method of preparation and oligomer-containing resin compositions


A replaceable handle for side loading the proximal end of a medical device therein, which is typically inserted with the operating lumen of an endoscope. The replaceable handle can side-load the proximal end of the device into the handle for added manipulation of the distal end such as in removing a stone from the kidney or ureter leading therefrom. An inner housing is rotatable within an outer housing of the handle to secure the medical device in the housing passageway, and is spring biased to then move proximally with respect to the outer housing, moving the inner control rod of the medical device proximally to withdraw the stone basket mostly into the outer cannula and capture the stone for removal from the patient. A push button in the proximal end portion of the inner housing is depressible to permit insertion or withdrawal of the proximal end of the inner control rod of the stone retriever within the inner housing, and is releasable to secure the inner control rod in the handle.

This invention relates generally to medical devices and, in particular, to a handle for positioning thereinto the proximal end of a medical device for controlled movement with respect thereto.
Extractors or baskets have been used for the removal of stones and other foreign objects from the urinary or biliary system. Often, the distal portion of these devices consist of a series of wires or strips that can be manipulated by the handle and actuating wire to expand to form an open basket. By further manipulating the handle of the extractor, the target object is captured within the basket, and the device is withdrawn from the body.
The procedure for extraction of a kidney stone usually requires that an endoscope be introduced to locate the obstruction. Once the stone is visualized, the basket or extractor is introduced through an operating lumen in the scope to complete the procedure. Occasionally, the extractor with the stone are too large to be safely withdrawn and further instrumentation such as forceps or an ultrasonic wire must be introduced that aid in fragmenting the object for removal. Without an additional operating lumen through which these instruments may be introduced, the endoscope must be withdrawn over the extractor. To accomplish this, the handle of the extractor must first be removed.
Handles for many current extractors are end loaded with a hub or expanded portion at the proximal end of the actuating wires. The hubs locks into place with the handle mechanism. Unfortunately, however, they must be cut off the proximal end of the wire before the endoscope can be slid off the end of the extractor. This prevents reattachment and reuse of the handle to complete the procedure once the basket has been freed. The ideal handle for a stone extractor must be able to be removed on a temporary basis and be easily reattached without the loss of handle function.
One such handle for a stone extractor or retriever is disclosed in U.S. Pat. No. 6,053,934 issued to Andrews, et al., the disclosure of which is hereby incorporated by reference. The handle is disclosed for side loading the proximal end of a medical device therein, which is typically inserted within the operative lumen of an endoscope. The handle is easily removed from the proximal end of the medical device for removing the endoscope over the device. With the endoscope removed, the replaceable handle can side-load the proximal end of the device for added manipulation of the distal end such as in removing a stone from the kidney or ureter leading therefrom. Having an inner housing therewithin, the outer housing also includes a first attachment mechanism disposed about the distal end for receipt of the first device while the inner housing includes a second attachment mechanism in communication with an inner passageway for receipt of a second device adjacent to the first member. The outer housing also includes a projection positionable into the positioning channel of the inner elongated member to control longitudinal and rotational movement therebetween. The inner housing is longitudinally slidable in the handle passage when the projection is positioned in a longitudinal component of the positioning channel. The inner housing is also rotatable in the handle passage when the projection is positioned in a transverse or circumferential component of the positioning channel. Removing a stone with the retriever requires holding the inner housing firmly in the proximal-most position along the outer housing with one hand, while simultaneously pulling the retriever proximally from the patient with the other hand, or by another person assisting the procedure.
It is desired to provide a handle that facilitates manipulation of the inner device to perform a work step, such as grasping a stone prior to removal, by applying tension in only one direction needing only one hand.
It is also desired to provide a handle that enables easy removal and insertion of a medical device with respect to the handle.
The foregoing problems are solved and a technical advance is achieved in an illustrative replaceable or removable handle for a medical device that is typically inserted through the operating lumen of an endoscope, where the medical device includes an outer member and an inner member that is to be operable axially with respect to the outer member. The replaceable handle includes an outer elongated housing with a passage having external or lateral communication extending longitudinally at least partially therealong from the distal end thereof. The distal end portion of the handle assembly defines an arrangement for securing an outer member of the medical device against lateral and axial movement. The handle also includes an inner elongated housing positioned in the outer housing central passageway and preferably extending proximally therefrom and preferably having a positioning cam channel arrangement for cooperating with a cam follower of the outer housing, for advantageously controlling the longitudinal and the rotational or circumferential movement of the inner housing with respect to the outer housing. The inner housing also includes a locking arrangement disposed therein and communicating with an inner passageway for receipt therein of the inner medical device member in a manner that controls axial movement thereof and also is manually actuatable to release the inner member for removal from the handle assembly.
One aspect of the invention is a replaceable, medical device handle for loading the proximal end of a medical device including first and second coaxial members and for controlling relative axial movement of the first and second coaxial members. The replaceable, medical device handle comprises an outer elongated housing having a distal end, a passage extending longitudinally therealong and having external communication thereto, and also a first attachment mechanism associated with the outer elongated housing for attaching the outer elongated housing to one of the first and second coaxial members when the proximal end of the medical device is in the passage for constraining the one of the first and second coaxial members against axial movement relative to the outer elongated housing. The medical device also comprises an inner elongated member position in said passage and extending therealong supported for axial movement relative to the outer elongated housing, and a second attachment mechanism associated with the inner elongate member for attaching the inner elongate member to the other of the first and second coaxial members when the proximal end of the medical device is in the passage for constraining the other of the first and second coaxial members against axial movement relative to the inner elongated member. The outer housing and the inner member include a projection positionable in an associated channel arrangement to achieve relative rotational and longitudinal movement of the first and second device members. The medical device also includes a spring operably coupled between the outer elongated housing and the inner elongated member for biasing the outer elongated housing and the inner elongated member toward a particular relative longitudinal position.
In one aspect of the invention, the locking arrangement includes a push button that is depressible to align a wide slot portion with the inner passageway to permit the proximal end of the inner medical device member to be inserted therethrough; release of the push button permits the button to be biased outwardly to align a narrow slot portion with the inner passagway, thus trapping an enlarged end of the inner medical device member proximally of the push button and permitting manipulation of the inner housing of the handle to move the inner medical device member.
In another aspect, a slotted end cap is affixed at the distal end of the outer housing, and a slotted insert is positioned inwardly from the end cap, with the outer medical device member insertable through a wide slot entrance along the side of the outer housing to be disposed in and along the slots to be aligned with the inner passageway of the inner housing. Rotation of the inner housing at its proximal end in turn rotates the insert within the outer housing, which misaligns a narrow portion of the slot of the insert with respect to the narrow slot of the end cap, thus trapping the outer medical device member against lateral movement, while the misaligning of the slots also defines stops for the outer medical device member against axial movement thereof when larger diameter portions thereof outside of the slots abut orthogonal faces of the end cap and insert at ends of the narrow slots.
In a further aspect of the present invention, the handle assembly includes a biasing arrangement to urge the inner housing proximally with respect to the outer housing, and thus urge the inner medical device member proximally with respect to the outer medical device member. This enables the inner member to be biased proximally with respect to the outer member without manual assistance. Where the medical device is a stone retriever, after the stone is captured by a stone basket of an inner control rod, the stone is securely held during withdrawal of the medical device from the patient without manual assistance to maintain the inner control rod biased proximally with respect to the outer cannula, thus allowing stone retrieval using only one hand to generally hold the handle assembly.


A water soluble container having disposed therein a liquid cleaning composition containing at least one nonionic surfactant, a perfume and a fatty acid.

This invention relates to a water soluble sachet containing a concentrate of a cleaning composition having excellent foam collapse properties and excellent grease cutting properties designed in particular for cleaning hard surfaces and which is effective in removing grease soil and/or bath soil and in leaving unrinsed surfaces with a shiny appearance.
In recent years all-purpose liquid detergents have become widely accepted for cleaning hard surfaces, e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc. Such all-purpose liquids comprise clear and opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent builder salts. In order to achieve comparable cleaning efficiency with granular or powdered all-purpose cleaning compositions, use of water-soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids. For example, such early phosphate-containing compositions are described in U.S. Pat. Nos. 2,560,839; 3,234,138; 3,350,319; and British Patent No.1,223,739.
In view of the environmentalist""s efforts to reduce phosphate levels in ground water, improved all-purpose liquids containing reduced concentrations of inorganic phosphate builder salts or non-phosphate builder salts have appeared. A particularly useful self-opacified liquid of the latter type is described in U.S. Pat. No. 4,244,840.
However, these prior art all-purpose liquid detergents containing detergent builder salts or other equivalent tend to leave films, spots or streaks on cleaned unrinsed surfaces, particularly shiny surfaces. Thus, such liquids require thorough rinsing of the cleaned surfaces which is a time-consuming chore for the user.
In order to overcome the foregoing disadvantage of the prior art all-purpose liquid, U.S. Pat. No. 4,017,409 teaches that a mixture of paraffin sulfonate and a reduced concentration of inorganic phosphate builder salt should be employed. However, such compositions are not completely acceptable from an environmental point of view based upon the phosphate content. On the other hand, another alternative to achieving phosphate-free all-purpose liquids has been to use a major proportion of a mixture of anionic and nonionic detergents with minor amounts of glycol ether solvent and organic amine as shown in U.S. Pat. No. 3,935,130. Again, this approach has not been completely satisfactory and the high levels of organic detergents necessary to achieve cleaning cause foaming which, in turn, leads to the need for thorough rinsing which has been found to be undesirable to today""s consumers.
Another approach to formulating hard surfaced or all-purpose liquid detergent composition where product homogeneity and clarity are important considerations involves the formation of oil-in-water (o/w) microemulsions which contain one or more surface-active detergent compounds, a water-immiscible solvent (typically a hydrocarbon solvent), water and a xe2x80x9ccosurfactantxe2x80x9d compound which provides product stability. By definition, an o/w microemulsion is a spontaneously forming colloidal dispersion of xe2x80x9coilxe2x80x9d phase particles having a particle size in the range of 25 to 800 xc3x85 in a continuous aqueous phase.
In view of the extremely fine particle size of the dispersed oil phase particles, microemulsions are transparent to light and are clear and usually highly stable against phase separation.
Patent disclosures relating to use of grease-removal solvents in o/w microemulsions include, for example, European Patent Applications EP 0137615 and EP 0137616xe2x80x94Herbots et al; European Patent Application EP 0160762xe2x80x94Johnston et al; and U.S. Pat. No. 4,561,991xe2x80x94Herbots et al. Each of these patent disclosures also teaches using at least 5% by weight of grease-removal solvent.
It also is known from British Patent Application GB 2144763A to Herbots et al, published Mar. 13, 1985, that magnesium salts enhance grease-removal performance of organic grease-removal solvents, such as the terpenes, in o/w microemulsion liquid detergent compositions. The compositions of this invention described by Herbots et al. require at least 5% of the mixture of grease-removal solvent and magnesium salt and preferably at least 5% of solvent (which may be a mixture of water-immiscible non-polar solvent with a sparingly soluble slightly polar solvent) and at least 0.1% magnesium salt.
However, since the amount of water immiscible and sparingly soluble components which can be present in an o/w microemulsion, with low total active ingredients without impairing the stability of the microemulsion is rather limited (for example, up to 18% by weight of the aqueous phase), the presence of such high quantities of grease-removal solvent tend to reduce the total amount of greasy or oily soils which can be taken up by and into the microemulsion without causing phase separation.
The following representative prior art patents also relate to liquid detergent cleaning compositions in the form of o/w microemulsions: U.S. Pat. Nos. 4,472,291xe2x80x94Rosario; U.S. Pat. No. 4,540,448xe2x80x94Gauteer et al; U.S. Pat. No. 3,723,330xe2x80x94Sheflin; etc.
Liquid detergent compositions which include terpenes, such as d-limonene, or other grease-removal solvent, although not disclosed to be in the form of o/w microemulsions, are the subject matter of the following representative patent 25 documents: European Patent Application 0080749; British Patent Specification 1,603,047; and U.S. Pat. Nos. 4,414,128 and 4,540,505. For example, U.S. Pat. No. 4,414,128 broadly discloses an aqueous liquid detergent composition characterized by, by weight:
(a) from 1% to 20% of a synthetic anionic, nonionic, amphoteric or zwitterionic surfactant or mixture thereof;
(b) from 0.5% to 10% of a mono- or sesquiterpene or mixture thereof, at a weight ratio of (a):(b) being in the range of 5:1 to 1:3; and
(c ) from 0.5% 10% of a polar solvent having a solubility in water at 15xc2x0 C. in the range of from 0.2% to 10%. Other ingredients present in the formulations disclosed in this patent include from 0.05% to 2% by weight of an alkali metal, ammonium or alkanolammonium soap of a C13xe2x80x94C24 fatty acid; a calcium sequestrant from 0.5% to 13% by weight; non-aqueous solvent, e.g., alcohols and glycol ethers, up to 10% by weight; and hydrotropes, e.g., urea, ethanolamines, salts of lower alkylaryl sulfonates, up to 10% by weight. All of the formulations shown in the Examples of this patent include relatively large amounts of detergent builder salts which are detrimental to surface shine.
U.S. Pat. No. 6,037,319 teaches a water soluble sachet containing a cleaning composition containing an alcohol and hexylene glycol.
U.S. Pat. No. 5,783,541 teaches a dishwashing composition disposed in a water soluble film, wherein the water soluble film is coated with a water dissolvable glue.
The present invention provides a cleaning system comprising a water soluble sachet containing a concentrate of a liquid cleaning composition having excellent foam collapse properties and excellent grease cutting property which, when diluted in a bucket, is suitable for cleaning hard surfaces such as plastic, vitreous and metal surfaces having a shiny finish, oil stained floors, automotive engines and other engines. More particularly, the improved cleaning compositions, with excellent foam collapse properties and excellent grease cutting property exhibit good grease soil removal properties due to the improved interfacial tensions, when used diluted and leave the cleaned surfaces shiny without the need of or requiring only minimal additional rinsing or wiping. The latter characteristic is evidenced by little or no visible residues on the unrinsed cleaned surfaces and, accordingly, overcomes one of the disadvantages of prior art products.
Surprisingly, these desirable results are accomplished even in the absence of polyphosphate or other inorganic or organic detergent builder salts and also in the complete absence or substantially complete absence of grease-removal solvent.
In one aspect, the invention generally provides a stable, water soluble sachet made of a water soluble thermoplastic wherein the sachet contains a liquid cleaning composition which comprises approximately by weight:
1% to 13%, more preferably 2% to 12% of an organic compound selected from the group consisting of a fatty acid, a water insoluble organic ester and a silicone fluid and mixtures thereof;
45% to 90%, more preferably 50% to 80% of a nonionic surfactant selected from the group consisting of an ethoxylated/propoxylated nonionic surfactant and an ethoxylated nonionic surfactant and mixtures thereof;
0 to 30%, more preferably 1% to 26% of a short chain amphiphile; and
1% to 10%, more preferably 2% to 9% of a perfume, essential oil or water insoluble saturated or unsaturated organic compound having 4 to 20 carbon atoms wherein the composition does not contain an anionic sulfate surfactant, an anionic sulfonate surfactant, hexylene glycol, an amine oxide surfactant, 2-butyl ethanol, isopropyl alcohol, or propylene glycol.
The present invention relates to a water soluble sachet containing a unit dose of a liquid cleaning composition wherein the water soluble sachet is formed from a single layer of film water soluble thermo plastic such as a polyvinyl alcohol, wherein the inner layer of the film is in contact with the liquid cleaning composition and the external layer of the film does not have a water soluble glue disposed thereon.
The liquid cleaning composition contained in the water soluble sachet comprises approximately by weight:
(a) 1% to 13%, more preferably 2% to 12% of an organic compound selected from the group consisting of a fatty acid, a water insoluble organic ester and a silicone fluid and mixtures thereof;
(b) 1% to 10%, more preferably 2% to 9% of a perfume, essential oil or water insoluble saturated or unsaturated organic compound having 4 to 20 carbon atoms, and a water insoluble mono or diorganic acid having about 6 to about 24 carbon atoms;
(c) 45% to 90%, more preferably 50% to 80% of an ethoxylated/propoxylated nonionic surfactant and an ethoxylated nonionic surfactant and mixtures thereof; and
(d) 0 to 30%, more preferably 1% to 26% of a short chain amphiphiles, wherein the composition does not contain an anionic sulfate surfactant, an anionic sulfonate surfactant, hexylene glycol or an amine oxide surfactant.
As used herein and in the appended claims the term xe2x80x9cperfumexe2x80x9d is used in its ordinary sense to refer to and include any non-water soluble fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flower, herb, blossom or plant), artificial (i.e., mixture of natural oils or oil constituents) and synthetically produced substance) odoriferous substances. Typically, perfumes are complex mixtures of blends of various organic compounds such as alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils (e.g., terpenes) such as from 0% to 80%, usually from 10% to 70% by weight, the essential oils themselves being volatile odoriferous compounds and also serving to dissolve the other components of the perfume.
In the present invention the precise composition of the perfume is of no particular consequence to cleaning performance so long as it meets the criteria of water immiscibility and having a pleasing odor. Naturally, of course, especially for cleaning compositions intended for use in the home, the perfume, as well as all other ingredients, should be cosmetically acceptable, i.e., non-toxic, hypoallergenic, etc.
The water insoluble saturated or unsaturated organic compounds contain 4 to 20 carbon atoms and up to 4 different or identical functional groups and is used at a concentration of about 1.0 wt. % to about 8 wt. %, more preferably about 2.0 wt. % to about 7 wt. %. Examples of acceptable water insoluble saturated or unsaturated organic compound include (but are not limited to) water insoluble hydrocarbons containing 0 to 4 different or identical functional groups, water insoluble aromatic hydrocarbons containing 0 to 4 different or identical functional groups, water insoluble heterocyclic compounds containing 0 to 4 different or identical functional groups, water insoluble ethers containing 0 to 3 different or identical functional groups, water insoluble alcohols containing 0 to 3 different or identical functional groups, water insoluble amines containing 0 to 3 different or identical functional groups, water insoluble carboxylic acids containing 0 to 3 different or identical functional groups, water insoluble amides containing 0 to 3 different or identical functional groups, water insoluble nitriles containing 0 to 3 different or identical functional group, water insoluble aldehydes containing 0 to 3 different or identical functional groups, water insoluble ketones containing 0 to 3 different or identical functional groups, water insoluble phenols containing 0 to 3 different or identical functional groups, water insoluble nitro compounds containing 0 to 3 different or identical functional groups, water insoluble halogens containing 0 to 3 different or identical functional groups, water insoluble sulfates or sulfonates containing 0 to 3 different or identical functional groups, limonene, dipentene, terpineol, essential oils, perfume s, water insoluble organic compounds containing up to 4 different or identical functional groups such as an alkyl cyclohexane having both three hydroxys and one ester group and mixture thereof.
Typical heterocyclic compounds are 2,5-dimethylhydrofuran,2-methyl-1,3-dioxolane, 2-ethyl 2-methyl 1,3 dioxolane, 3-ethyl 4-propyl tetrahydropyran, 3-morpholino-1,2-propanediol and N-isopropyl morpholine A typical amine is alpha-methyl benzyldimethylamine. Typical halogens are 4-bromotoluene, butyl chloroform and methyl perchloropropane. Typical hydrocarbons are 1,3-dimethylcyclohexane, cyclohexyl-1decane, methyl-3 cyclohexyl-9 nonane, methyl-3 cyclohexyl-6 nonane, dimethyl cycloheptane, trimethyl cyclopentane, ethyl-2 isopropyl-4 cyclohexane. Typical aromatic hydrocarbons are bromotoluene, diethyl benzene, cyclohexyl bromoxylene, ethyl-3 pentyl-4 toluene, tetrahydronaphthalene, nitrobenzene and methyl naphthalene. Typical water insoluble esters are benzyl acetate, dicyclopentadienylacetate, isononyl acetate, isobornyl acetate and isobutyl isobutyrate. Typical water insoluble ethers are di(alphamethyl benzyl) ether and diphenyl ether. Typical alcohols are phenoxyethanol and 3-morpholino-1,2-propanediol. Typical water insoluble nitro derivatives are nitro butane and nitrobenzene.
Suitable essential oils are selected from the group consisting of: Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Peru), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China), Camphor oil, White, Camphor powder synthetic technical, Cananga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Coumarin 69xc2x0 C. (China), Cyclamen Aldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun balsam, Heliotropin, Isobornyl acetate, Isolongifolene, Juniper berry oil, L-methyl acetate, Lavender oil, Lemon oil, Lemongrass oil, Lime oil distilled, Litsea Cubeba oil, Longifolene, Menthol crystals, Methyl cedryl ketone, Methyl chavicol, Methyl salicylate, Musk ambrette, Musk ketone, Musk xylol, Nutmeg oil, Orange oil, Patchouli oil, Peppermint oil, Phenyl ethyl alcohol, Pimento berry oil, Pimento leaf oil, Rosalin, Sandalwood oil, Sandenol, Sage oil, Clary sage, Sassafras oil, Spearmint oil, Spike lavender, Tagetes, Tea tree oil, Vanilin, Vetyver oil (Java), Wintergreen, Allocimene, Arbanex(trademark), Arbanol(copyright)), Bergamot oils, Camphene, Alpha-Campholenic aldehyde, I-Carvone, Cineoles, Citral, Citronellol Terpenes, Alpha-Citronellol, Citronellyl Acetate, Citronellyl Nitrile, Para-Cymene, Dihydroanethole, Dihydrocarveol, d-Dihydrocarvone, Dihydrolinalool, Dihydromyrcene, Dihydromyrcenol, Dihydromyrcenyl Acetate, Dihydroterpineol, Dimethyloctanal, Dimethyloctanol, Dimethyloctanyl Acetate, Estragole, Ethyl-2 Methylbutyrate, Fenchol, Fernlo(trademark), Florilys(trademark), Geraniol, Geranyl Acetate, Geranyl Nitrile, Glidmint(trademark) Mint oils, Glidox(trademark), Grapefruit oils, trans-2-Hexenal, trans-2-Hexenol, cis-3-Hexenyl Isovalerate, cis-3-Hexanyl-2-methylbutyrate, Hexyl Isovalerate, Hexyl-2-methylbutyrate, Hydroxycitronellal, Ionone, Isobornyl Methylether, Linalool, Linalool Oxide, Linalyl Acetate, Menthane Hydroperoxide, I-Methyl Acetate, Methyl Hexyl Ether, Methyl-2-methylbutyrate, 2-Methylbutyl Isovalerate, Myrcene, Nerol, Neryl Acetate, 3-Octanol, 3-Octyl Acetate, Phenyl Ethyl-2-methylbutyrate, Petitgrain oil, cis-Pinane, Pinane Hydroperoxide, Pinanol, Pine Ester, Pine Needle oils, Pine oil, alpha-Pinene, beta-Pinene, alpha-Pinene Oxide, Plinol, Plinyl Acetate, Pseudo Ionone, Rhodinol, Rhodinyl Acetate, Spice oils, alpha-Terpinene, gamma-Terpinene, Terpinene-4-OL, Terpineol, Terpinolene, Terpinyl Acetate, Tetrahydrolinalool, Tetrahydrolinalyl Acetate, Tetrahydromyrcenol, Tetralol(copyright), Tomato oils, Vitalizair, Zestoral(trademark).
The at least one nonionic surfactant used in the instant cleaning composition is selected from the group of an aliphatic ethoxylated nonionic surfactant and an aliphatic ethoxylated/propoxylated nonionic surfactant and mixtures thereof.
The water soluble aliphatic ethoxylated nonionic surfactants utilized in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates and secondary aliphatic alcohol ethoxylates. The length of the polyethenoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.
The nonionic surfactant class includes the condensation products of a higher alcohol (e.g., an alkanol containing about 8 to 16 carbon atoms in a straight or branched chain configuration) condensed with about 4 to 20 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 to 15 moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
A preferred group of the foregoing nonionic surfactants are the Neodol ethoxylates (Shell Co.), which are higher aliphatic, primary alcohol containing about 9-15 carbon atoms, such as C9-C11 alkanol condensed with 4 to 10 moles of ethylene oxide (Neodol 91-8 or Neodol 91-5), C12-13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12-15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12), C14-15 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13), and the like. Such ethoxamers have an HLB (hydrophobic lipophilic balance) value of about 8 to 15 and give good O/W emulsification, whereas ethoxamers with HLB values below 7 contain less than 4 ethyleneoxide groups and tend to be poor emulsifiers and poor detergents.
Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available nonionic detergents of the foregoing type are C11-C15 secondary alkanol condensed with either 9 EO (Tergitol 15-S-9) or 12 EO (Tergitol 15-S-12) marketed by Union Carbide.
One of the water soluble nonionic surfactants which can be utilized in this invention are an aliphatic ethoxylated/propoxylated nonionic surfactants which are depicted by the formula:
Rxe2x80x94Oxe2x80x94(CH2CH2O)xe2x80x94xxe2x80x94(CH2CH2CH2O)yxe2x80x94H
or
wherein R is a branched chain alkyl group having about 10 to about 16 carbon atoms, preferably an isotridecyl group and x and y are independently numbered from 1 to 20. A preferred ethoxylated/propoxylated nonionic surfactant is Plurafac(copyright) 300 manufactured by BASF.
A C6-C14 alkylene carbonate can be used optionally in the instant composition at a concentration of 0 to 10 wt. %, more preferably 1.0 wt. % to 5 wt. % and is depicted by the structure:
wherein R1 is a Cn alkyl group, R2 is H or is a Cm alkyl group, with n+m being a number from 4 to 12, more preferably from 6 to 10, such as 1-octene carbonate or 1-dodecene carbonate. The C6-C14 alkylene carbonate is prepared by the reaction of alkane alpha-diol with phosgene as depicted by the following:
wherein R1 is a Cn alkyl group, with n being a number from 4 to 12 and R2 is a Cm alkyl group, with n+m being a number from 4 to 12. The alkane alpha-diols are prepared from the epoxidation of an internal or an alpha-olefin and the subsequent hydrolysis of the epoxide. The C6-C14 alkylene carbonate can also be prepared by a another synthesis route by the reaction of molecular oxygen O2 on the said internal or alpha-olefin to form the epoxide as intermediate product, followed by the direct reaction of carbon dioxide CO2 on the epoxide in appropriate conditions, as depicted by the following:
The C6-C14 alkylene carbonates are nitrogen-free amphiphiles having a high dipole moment.
The short chain amphiphile which is optionally used in the instant cleaning composition is not a surfactant and is characterized by the formula:
R1O(CH2CH2O)nH
wherein R1 is a straight or branched chain alkyl group having 2 to 6 carbon atoms and n is a number from 2 to 8, more preferably 3 to 6 and the amphiphile has an HLB of about 6 to about 9, preferably about 7 to about 8. Preferred amphiphiles have a C6 alkyl group and 2 to 5 EO such as hexanol 5EO.
Another short chain amphiphile which can be used in the instant cleaning composition is not a surfactant and is characterized by the formula:
or
R2Oxe2x80x94(CH2CH2O)wxe2x80x94(CH2CH2CH2O)zH
wherein R1 or R2 are a straight or branched chain alkyl group having 2 to 6 carbon atoms and x or w is a number from 2 to 5, more preferably 2 to 4 and y or z is a number from 1 to 4, more preferably 1 to 3 and the amphiphile has an HLB of about 6 to about 9, preferably about 7 to about 8. Preferred amphiphiles have a C6 alkyl group and 2 to 5 EO such as hexanol 5 EO such as Emulan(trademark) HE50).
The instant cleaning composition can contain a fatty acid. As example of the fatty acids which can be used as such or in the form of soap, mention can be made of distilled coconut oil fatty acids, xe2x80x9cmixed vegetablexe2x80x9d type fatty acids (e.g. high percent of saturated, mono-and/or polyunsaturated C18 chains); oleic acid, stearic acid, palmitic acid, eiocosanoic acid, and the like, generally those fatty acids having from 8 to 22 carbon atoms being acceptable.
The silicone fluids are selected from the group consisting of decamethyl cyclopentasiloxane, dodecanmethyl cyclohexasiloxane, and a mixture of dodecamethyl cyclohexasiloxane and decamethyl cyclopenta silioxane in a weight ratio of 9:1 to 19:1, more preferably 11:1 to 17:1 and a weight ratio of 8:1 to 1:1, more preferably 2:1 to 1.5:1. These chemicals are manufactured by Dow Chemical and sold as Silicone Fluids 245, 246 and 345.
The structure of decamethyl cyclopentasiloxane is:
The structure of dodecamethylcyclohexasiloxane is:
The water insoluble organic ester is either an organic mono ester having 6 to 24 carbon atoms or an organic diester having 6 to 24 carbon atoms.
The liquid cleaning composition of this invention may, if desired, also contain other components either to provide additional effect or to make the product more attractive to the consumer. The following are mentioned by way of example: Colors or dyes in amounts up to 0.5% by weight; bactericides in amounts up to 1% by weight; preservatives or antioxidizing agents, such as formalin, 5-bromo-5-nitro-dioxan-1,3; 5-chloro-2-methyl-4-isothaliazolin-3-one, 2,6-di-tert.butyl-p-cresol, etc., in amounts up to 2% by weight.
In final form, the cleaning compositions which contain less than 2 wt. % of water exhibit stability at reduced and increased temperatures. More specifically, such compositions remain clear and stable in the range of 4xc2x0 C. to 50xc2x0 C., especially 2xc2x0 C. to 43xc2x0 C. Such compositions exhibit a pH, at 1% solution, in the acid or neutral range depending on intended end use. The liquids are readily pourable and exhibit a viscosity in the range of 6 to 60 millipascal second (mPas.) as measured at 25xc2x0 C. with a Brookfield RVT Viscometer using a #1 spindle rotating at 20 RPM. Preferably, the viscosity is maintained in the range of 10 to 40 mPas.
The compositions are easily prepared simply by combining all the ingredients in a suitable vessel or container. The order of mixing the ingredients is not particularly important and generally the various ingredients can be added sequentially.
The water soluble container which can be in the form of a sachet, a blow molded capsule or other blow molded shapes, an injected molded ampoule or other injection molded shapes, or rotationally molded spheres or capsules are formed from a water soluble thermoplastic resin. Water soluble plastics which may be considered for forming the container include low molecular weight and/or chemically modified polylactides; such polymers have been produced by Chronopol, Inc. and sold under the Heplon trademark. Also included in the water soluble polymer family are melt processable poly(vinyl) alcohol resins (PVA); such resins are produced by Texas Polymer Services, Inc., tradenamed Vinex, and are produced under license from Air Products and Chemicals, Inc. and Monosol film produced by Chris Craft Film. Other suitable resins include poly (ethylene oxide) and cellulose derived water soluble carbohydrates. The former are produced by Union Carbide, Inc. and sold under the tradename Polyox; the latter are produced by Dow Chemical, Inc. and sold under the Methocel trademark. Typically, the cellulose derived water soluble polymers are not readily melt processable. The preferred water soluble thermoplastic resin for this application is Chris Craft Film. Any number or combination of PVA resins can be used. The preferred grade, considering resin processability, container durability, water solubility characteristics, and commercial viability is Monosol film having a weight average molecular weight range of about 55,000 to 65,000 and a number average molecular weight range of about 27,000 to 33,000.
The sachet may be formed from poly(vinyl) alcohol film. The pelletized, pre-dried, melt processable polyvinyl alcohol (PVA) resin, is feed to a film extruder. The feed material may also contain pre-dried color concentrate which uses a PVA carrier resin. Other additives, similarly prepared, such as antioxidants, UV stabilizers, anti-blocking additives, etc. may also be added to the extruder. The resin and concentrate are melt blended in the extruder. The extruder die may consist of a circular die for producing blown film or a coat hanger die for producing cast film. Circular dies may have rotating die lips and/or mandrels to modify visual appearance and/or properties.
Typical film properties are:
1. Tensile strength (125 mil, break, 50% RH)=4,700 to 5,700 psi
2. Tensile modulus (125 mil, 50% RH)=47,000 to 243,000 psi; preferred range is 140,000 to 150,000 psi
3. Tear resistance (mean) (ASTM-D-199gm/ml)=900-1500
4. Impact strength (mean) (ASTM-D-1709, gm)=600-1,000
5. 100% Elongation (mean) (ASTM-D-882, psi)=300-600
6. Oygen transmission (1.5 mil, 0% RH, 1 atm)=0.0350 to 0.450 cc/100 sq. in./24 h
7. Oxygen transmission (1.5 mil, 50% RH, 1 atm)=1.20 to 1.50 cc/100 sq. in./24 h
8. 100% modulus (mean) (ASTM-D-882, psi)=1000-3000
9. Solubility (sec) (MSTM-205,75xc2x0 F.) disintegration=1-15; dissolution=10-30
Typical resin properties are:
1. Glass Transition Temperature (xc2x0 C.)=28 to 38; preferred is 28 to 33,
2. Weight Average Molecular Weight (Mw)=15,000 to 95,000; preferred is 55,000-65,000
3. Number Average Molecular Weight (Mn)=7,500 to 60,000; preferred is 27,000 to 33,000. Preferred poly(vinyl) alcohol film is formed from Monosol 7030 or Monosol 8630
The extruded film is slit to the appropriate width and wound on cores. Each core holds one reel of film. The reels of slit film are fed to either a vertical form, fill, seal machine (VFFS) or a horizontal form, fill, seal machine (HFFS). The Form, Fill, Seal machine (FFS) makes the appropriate sachet shape (cylinder, square, pillow, oval, etc.) from the film and seals the edges longitudinally (machine direction seal). The FFS machine also makes an end seal (transverse direction seal) and fills the appropriate volume of non-aqueous liquid above the initial transverse seal. The FFS machine then applies another end seal. The liquid is contained in the volume between the two end seals.
Blow molded capsules are formed from the poly(vinyl) alcohol resin having a molecular weight of about 50,000 to about 70,000 and a glass transition temperature of about 28 to 33xc2x0 C. Pelletized resin and concentrate(s) are feed into an extruder. The extruder into which they are fed has a circular, oval, square or rectangular die and an appropriate mandrel. The molten polymer mass exits the die and assumes the shape of the die/mandrel combination. Air is blown into the interior volume of the extrudate (parison) while the extrudate contacts a pair of split molds. The molds control the final shape of the package. While in the mold, the package is filled with the appropriate volume of liquid. The mold quenches the plastic. The liquid is contained within the interior volume of the blow molded package.
An injection molded ampoule or capsule is formed from the poly(vinyl) alcohol resin having a molecular weight of about 50,000 to about 70,000 and a glass transition temperature of about 28 to 38xc2x0 C. Pelletized resin and concentrate(s) are fed to the throat of an reciprocating screw, injection molding machine. The rotation of the screw pushes the pelletized mass forward while the increasing diameter of the screw compresses the pellets and forces them to contact the machine""s heated barrel. The combination of heat, conducted to the pellets by the barrel and frictional heat, generated by the contact of the pellets with the rotating screw, melts the pellets as they are pushed forward. The molten polymer mass collects in front of the screw as the screw rotates and begins to retract to the rear of the machine. At the appropriate time, the screw moves forward forcing the melt through the nozzle at the tip of the machine and into a mold or hot runner system which feeds several molds. The molds control the shape of the finished package. The package may be filled with liquid either while in the mold or after ejection from the mold. The filling port of the package is heat sealed after filling is completed. This process may be conducted either in-line or off-line.
A rotationally molded sphere or capsule is formed from the poly(vinyl) alcohol resin having a molecular weight of about 50,000 to about 70,000 and a glass transition temperature of about 28 to 38xc2x0 C. Pelletized resin and concentrate are pulverized to an appropriate mesh size, typically 35 mesh. A specific weight of the pulverized resin is fed to a cold mold having the desired shape and volume. The mold is sealed and heated while simultaneously rotating in three directions. The powder melts and coats the entire inside surface of the mold. While continuously rotating, the mold is cooled so that the resin solidifies into a shape which replicates the size and texture of the mold. After rejection of the finished package, the liquid is injected into the hollow package using a heated needle or probe after filling, the injection port of the package is heat sealed.

Cleaning system including a liquid cleaning composition disposed in a water soluble container


A structure of a micro electro mechanical system and a manufacturing method are provided, the structure and manufacturing method is adapted for an optical interference display cell. The structure of the optical interference display cell includes a first electrode, a second electrode and posts. The second electrode comprises a conductive layer covered by a material layer and is arranged about parallel with the first electrode. The support is located between the first plate and the second plate and a cavity is formed. In the release etch process of manufacturing the structure, the material layer protects the conductive layer from the damage by an etching reagent. The material layer also protects the conductive layer from the damage from the oxygen and moisture in the air.

In a micro electro mechanical system (MEMS), the development of a sacrificial layer technique has become a key factor for manufacturing a suspended structure, such as a cantilever, a beam, a membrane, a channel, a cavity, a joint or hinge, a link, a crank, a gear or a rack, to name a few. A structure release etching process is adapted for removing a sacrificial layer, so a structure of a structure release in a micro electro mechanical system has a critical influence on the process of removing the sacrificial layer.
A conventional structure release etching process is first introduced with an optical interference display cell as an example. The optical interference display cell, a kind of a micro electro mechanical system, is used to fabricate a planar display. Planar displays are popular for portable displays and displays with space limits because they are light and small in size. To date, planar displays in addition to liquid crystal displays (LCD), organic electro-luminescent displays (OLED), plasma display panels (PDP), a mode of optical interference displays is another option for planar displays.
U.S. Pat. No. 5,835,255 discloses an array of display units of visible light that can be used in a planar display. Please refer to FIG. 1, which depicts a cross-sectional view of a display unit in the prior art. Every optical interference display unit 100 comprises two walls, 102 and 104. Posts 106 support these two walls 102 and 104, and a cavity 108 is subsequently formed. The distance between these two walls 102 and 104, that is, the length of the cavity 108, is D. One of the walls 102 and 104 is a hemi-transmissible/hemi-reflective layer with an absorption rate that partially absorbs visible light, and the other is a light reflective layer that is deformable when voltage is applied. When the incident light passes through the wall 102 or 104 and arrives in the cavity 108, in all visible light spectra, only the visible light with the wavelength corresponding to the formula 1.1 can generate a constructive interference and can be emitted, that is,2D=Nλ  (1.1)
, where N is a natural number.
When the length D of cavity 108 is equal to half of the wavelength times any natural number, a constructive interference is generated and a sharp light wave is emitted. In the meantime, if the observer follows the direction of the incident light, a reflected light with wavelength λ1 can be observed. Therefore, the display unit 100 is "open".
FIG. 2 depicts a cross-sectional view of a display unit in the prior art after applying a voltage. As shown in FIG. 2, while driven by the voltage, the wall 104 is deformed and falls down towards the wall 102 due to the attraction of static electricity. At this time, the distance between wall 102 and 104, that is, the length of the cavity 108 is not exactly zero, but is d, which can be zero. If we use d instead of D in formula 1.1, only the visible light with a wavelength satisfying formula 1.1, which is λ2, can generate a constructive interference, and be reflected by the wall 104, and pass through the wall 102. Because wall 102 has a high light absorption rate for light with wavelength λ2, all the incident light in the visible light spectrum is filtered out and an observer who follows the direction of the incident light cannot observe any reflected light in the visible light spectrum. The display unit 100 is now "closed".
FIG. 3A to FIG. 3B illustrate a method for manufacturing a conventional display cell. Referring to FIG. 3A, a first electrode 110 and a sacrificial layer 111 are formed in sequence on a transparent substrate 109, and opening 112, which is suitable for forming a supporter therein, is formed in the first electrode 110 and the sacrificial layer 111. Then, a supporter 106 is formed in the opening 112. Next, an electrode 114 is formed on the sacrificial layer 111 and the supporter 106. Subsequently, referring to FIG. 3B, the sacrificial layer 111 shown in FIG. 3A is removed by a release etching process to form a cavity 116, which is located in the position of the sacrificial layer 111, and the length D of the cavity 116 is the thickness of the sacrificial layer 111.
In a micro electro mechanical process, a micro suspended structure is fabricated by using a sacrificial layer. A suspended movable microstructure is fabricated by a selective etching between a device structure layer and the sacrificial layer to remove the sacrificial layer and leave the structure layer, and this process is called a structure release etching. The difference between the structure release etching process and an IC process is that in the structure release etching process, the selective etching is an isotropic etching, so that an undercut or an under etching is formed in the structure layer for smooth separation of the structure layer and the substrate.
No matter the wet structure release process or the dry structure release process is used, the choices of the material of the sacrificial layer and the micro suspended structure should be restricted, that is, the material used should have high etching-selectivity in the etching process or else the goal of removing the sacrificial layer without etching the micro suspended structure can not be achieved. Therefore, it is impossible to use the same material in both sacrificial layer and the micro suspended structure in the present process.
In the process of the optical interference display cell, some materials, such as molybdenum, are very suitable to form the sacrificial layer and the movable electrodes. However, in the structure and the process of the conventional optical interference display cell, molybdenum cannot be the material of forming both sacrificial layer and the micro suspended structure at the same time. Thus results in enormous limits in choosing the materials.
Furthermore, the aforementioned movable electrode is generally a membrane that is usually metal. The thickness of the movable electrode is so small that the quality of the metal membrane is easily worsen because of the oxidation caused by the contact with air or moisture. Thus would affect the optical interference display cell. Accordingly, how to provide a new structure and the manufacturing method thereof of an optical interference display cell to broaden the choices of process materials and to protect the movable electrode from the oxidation caused by the air or moisture has become a very important issue.

Structure of a micro electro mechanical system and the manufacturing method thereof


Method and apparatus for treatment of air conditioning systems and the like provides an air treatment element (18) comprising a microbial control medium and an entrainment medium therefor. The air treatment element (18) is adapted to be placed on the upstream side of the air cooling element (14) of an air conditioning system so that the air stream (16) thereto has entrained therein droplets of entrainment medium (32) containing the microbial treatment medium which are then condensed on the cooling surfaces, thereby removed from the air stream (16) and effectively applied to all relevant surfaces for exerting an effective microbial control action.

This invention relates to a method and apparatus for anti-microbial and related treatments. An example of the application of the invention is two systems for treating air conditioning systems with anti-microbial agents. Aspects of the invention are also applicable to systems for treatment of other equipment with anti-microbial and other agents, including for example the use of deodorant compositions and the like.
It is well known that there is a long standing requirement for systems for treating air conditioning systems in order to reduce the occurrence of such conditions as sick building syndrome and the like. Many proposals have been made. To the best of the applicants"" knowledge, no currently available system offers the combination of effective microbial control with at least moderate ease of use and an acceptable price.
One of the difficulties arising in the case of the treatment of air conditioning systems is that the hardware includes ducting and passages with heat exchange surfaces and other intricate structures which all need effective treatment in order to reduce the opportunity for microbial growth at times when conditions favour such growth. The use of simple systems for mechanical cleaning are rendered more or less impossible by the complexity of the structures and the inaccessibility of the interstices of the system.
An important aspect of the difficulties inherent in designing a system for effective treatment of air conditioning systems is the fact that many, if not all, microbial control reagents have the usage requirement attached to them that the user must not allow the reagent to become dispersed unacceptably within the breathable environment encountered by users of the building. In other words, the treatment system needs to be confined to the actual air treatment equipment itself so that the latter is clean and the microbial presence acceptably reduced while the remainder of the building is unaffected by the microbial treatment material in any direct way.
Accordingly, there is considerable difficulty in providing a system which is easy to use, cost-effective and does not contravene regulations relating to the use of microbial treatment agents.
With this requirement in mind, the embodiments of the present invention are based upon the discovery disclosed below, and there is provided according to the invention the method and apparatus defined in the accompanying claims.
In the embodiments of the invention described below there is provided a system in which provision is made for treatment of substantially the entire relevant air-contacting surfaces of the air conditioning equipment. Such treatment occurs over a significant period, for example from one to 24 hours, depending upon the parameters of the installed treatment element and on the extent of use of the air conditioning equipment. The treatment system is effective to limit the application of the microbial treatment material to just those relevant surfaces of the air conditioning plant. Moreover, this limitation of the treatment of the surfaces of the air conditioning plant alone, without affecting the remainder of the building, is effected by that equipment itself and without the need to instal any additional equipment to achieve this result.
Moreover, in the embodiments, the treatment process is effective for a defined period of time (dependent upon the factors mentioned above) and then ceases, substantially automatically, so that the operation is effective in a time-limited way and lends itself to repetitive use at suitably-chosen intervals in order to maintain a satisfactorily level of microbial removal.
In the embodiments of the invention the method and apparatus is based upon our discovery that the treatment of the relevant surfaces of the air conditioning plant and equipment can be effectively achieved by means of a system in which a biocide material is provided and is made available in association with a carrier medium, for example water, but other fluids may be feasible for certain applications, and the biocide or microbial treatment material is entrained from an air treatment element so as to be carried in the air and air stream entering the air conditioning plant and is thus dispersed by the air flow-producing systems (for example a fan), so as to become reasonably uniformly distributed around the entire air-flow paths of the apparatus.
Thus, in this way, the entrained biocide material and its carrier medium, for example water droplets, are dispersed around the system and thus are available for treatment of all the relevant hardware surfaces.
In accordance with another important aspect of the present invention, the system furthermore operates in accordance with the following. After the entrainment of the microbial treatment material and its dispersal with the entrainment medium and the air currents around the system, there is provided the means for effectively removing the treatment medium for the air, and this provided by the refrigerated or cooled surfaces of the air conditioning plant. Thus, the air conditioning plant itself serves to remove the biocide or microbial treatment medium from the air flow around the hardware, and it does this by effectively condensing the carrier medium, usually water, so that its associated biocide material is likewise condensed on the relevant cooled surfaces. Effectively, this means that all such surfaces become coated with droplets of water vapour containing or carrying the biocide material with the result that all such surfaces are very effectively treated with the biocide.
Thus, in the embodiments of the invention, the system utilises symbiotically and beneficially, purely the existing hardware apparatus of the air conditioning plant firstly to cause the biocide material to be entrained with its carrier medium into the air flow and thus to be widely dispersed, and secondly the air conditioning plant is caused to remove the entrained treatment material and carrier medium for a condensation step.
Accordingly, it can now be seen that the system of the present invention makes effective and convenient use of existing hardware systems and employs these to achieve not only effective dispersal of relatively small quantities of biocide material about the system, but also achieves likewise the effective removal of the treatment material or medium from the system by a condensation step. In this way, the embodiments of the present invention are able to achieve the indicated requirements of such a system, without the need to employ any additional hardware and by means which involves the employment merely of air treatment elements comprising sachets of the treatment medium and the carrier medium.
It will be understood that the embodiments of the invention do rely on the use of a carrier medium for the biocide material which is capable of being removed by condensation at the temperature occurring in the relevant surfaces of the air conditioning hardware. In most cases the carrier medium will be water. Care also needs to be exercised in order to ensure that the air conditioning plant is arranged to operate the air flow-producing fan, which causes entrainment of the biocide material, with the carrier medium, only when the air conditioning plant is operating and the refrigerated surfaces, which effect condensation of the biocide and carrier medium, are at their relevant refrigeration temperatures.
In other embodiments of the invention, the air treatment elements may be used in alternative systems in which the combination of a biocide or microbial treatment material and a carrier medium are also of benefit. For example, there may be provided light weight air conditioning or air treatment apparatus for use in relation to transport boxes for placement in lorries and trucks. Such equipment employs the air treatment elements described above in relation to air conditioning plant, in combination with an air dispersal system not incorporating any refrigerated surfaces as such.
Such an arrangement is of utility and convenience in relation to the road and rail transport of refrigerated goods in which the-dispersal of biocide-containing air around the stored goods is of benefit and the requirement for healthy breathability of the air in question is not in issue.
The invention provides, for use in association with air conditioning equipment, whether of the kind incorporating air circulation apparatus, an air treatment element comprising a microbial treatment medium together with a supply of an entrainment or carrier medium therefor, such as water. In an physical embodiment, the provision of the entrainment medium, for example water, is conveniently in the form of a material, for example a polymer such as silicone or silicagel particles, which holds (volume for volume) large amounts of water and makes such available for use over a period of time by slow release of water. Other such water-holding polymers and the like are known to the competent technician in this field.
A practical embodiment of an air treatment element in accordance with this aspect of the invention provides the combination of a anti-microbial agent or a deodorant agent or an odourant agent, with a freezable or condensable supply of a treatment medium, such a treatment element being thus adapted to be frozen or condensed prior to use and adapted likewise to be employed as a temperature-reducing xe2x80x9cice-packxe2x80x9d which effects either microbial control, or odour control, or both, and can be packed into storage containers in association with stored goods in order to carry out these functions during transport and after.
Aspects and features of the invention are described in the priority application GB 9927617.2 filed on Nov. 24, 2000 and entitled xe2x80x9cBiocide Air Delivery Systemxe2x80x9d the entire text of which is incorporated herein by reference.
As described in GB 9927617.2, an aspect of the invention is a biocide air delivery system as follows.
1) This invention is a means of releasing a proven chemical anti-microbial agent in water vapour from a water saturated biocide/polymer mixture into the air stream of a fan or other forced air distribution system to achieve microbial control.
2) The purpose of the invention is to disinfect areas where micro-organisms may accumulate creating a health hazard and/or other deleterious effects.
3) The anti-microbial agent such as a proven biocide of the type developed as a preservative for medicinal application is blended with a highly absorbent polymer powder. The mixture is sealed in a porous or perforated sachet or container which can be stored in a dry place.
3) When saturated fresh water, water droplets will progressively filter through the sheets of the sachets; they are then drawn into the air stream by the action of the fan in biocide-laden water vapour.
4) One of the obvious applications of the invention is in air-conditioning systems where micro-organisms build up and cause discomfort for people in these environments.
5) Because the air-conditioning industry must conform to the basic business principle of minimum running costs, most of the systems use filtered air. A controlled balance of temperature and humidity must be achieved for a comfortable environment; when recirculated air is filtered and cooled or heated without sufficient import of additional fresh air it can cause dry respiratory passage, dry skin and hair, runny noses and general discomfort. Such operating conditions provide a suitable environment for the growth of micro-organisms which when caught in the air stream circulate around the buildings posing significant health risks, such as Sick Building Syndrome and Legionelloses.
6) Microbial growth is a common problem in air-conditioning and refrigeration systems. However, an air-conditioning system in a continuous cycle creates condensate water which will flow away through the drip trays and drains; research by the authors of the present invention shows that the condensate water normally produced by an equipment correctly maintained and running efficiently is in sufficient quantity to flush away the micro-organisms which may contaminate the system. But the tests also show that when the air-conditioning system does not function correctly, due perhaps to faulty valves or loss of refrigerant, less condensate water is produced which is therefore insufficient to flush away the micro-organisms providing them with innoculum for further growth and proliferation. A similar scenario occurs when the air-conditioning refrigeration cycle is interrupted, for example during periods of cooler weather when the system is shut down, or even for short period of time like week-ends. During those periods, little or no condensate water is produced and micro-organisms will settle and as soon as conditions are favourable, grow and multiply very quickly, when the air-conditioning system is operated, micro-organisms then quickly contaminate the building carried around by the air current.
7) For air-conditioning systems, refrigeration and associated equipment, the sachets containing the mixture of acrylate polymer powder and biocide powder are hydrated then positioned close to the fan held in a plastic vented holding grill or other device according to size and situations, designed to ensure maximum air-flow. The biocide laden vapour is drawn or expelled out of the sachets through the fabric and introduced into air-conditioning, normally inaccessible areas of the equipment and reduce the microbial build-up. The biocide laden water vapour then condenses onto the surfaces such as the evaporators continuously washing and disinfecting internal surfaces of such equipment.
8) As a useful addition to the operation, the sachets can be placed directly into drip trays and troughs receiving condensate water. The compound will soak in any fluid which may gather for example in situations when there is insufficient flow of water to wash away the microorganisms; the biocidal activities of the sachets will achieve microbial control.
9) Another application for the invention by the use of frozen hydrated sachet. The mixture of water saturated acrylate polymer and biocide can be frozen and kept frozen for periods of times exceeding that of ice; tests have shown that in a closed container, the temperature can be maintained at below 8 deg C for periods of over 36 hours.
10) This property can be used for the transport of temperature sensitive produce in portable container, in adverse conditions. Containers made of polystyrene or other acceptable material are fitted with perforated baffle plates at one or two centimeters inside the lid, the floor and the walls; behind the plates are inserted one or more layers of sachets containing an appropriate mixture of acrylate polymer and biocide powder. The containers are also fitted with one or several battery operated fans. During transport, the main fan can be connected to the 12/24 volt battery of the vehicle another fan being served by a 5/6 volt support cell battery. An example will be a box with dual axial fans, one powered by the transporting vehicle or its battery, the other being a fan of low voltage operated by a rechargeable portable battery; when the embodiment is disconnected from the main battery, the back-up battery cuts in to maintain continuity of the fan action with no interruption to the cooling operation inside the container. When the fans operate, they disperse the chilled water vapour emanating from the sachets within the container providing both cooling and microbial control functions. Refrigeration temperatures can therefore be sustained for one to two days before the frozen biocide sachets need replacing. By adding an extra layer of frozen sachets, test have shown that freezing temperatures can be maintained for 12 hours or longer with suitable insulation.
11) Chilled foods are usually distributed in containers such as plastic or polystyrene boxes by refrigerated lorries or vans. During deliveries when the van door remain open for unloading or loading, air at the ambient temperature enters the van which affects the produce stored in the vehicle. The invention will keep the temperature inside the containers within the acceptable limits of food hygiene as prescribed by the Health Authorities; the produce is packed at the refrigerated premises of the manufacturer or distributor in the chilled container where the invention is fitted; it is then loaded into the carrier""s vehicles. The stored produce will not be affected by the opening of the vehicle""s doors; it will allow the transit of the refrigerated container from vehicle to vehicle and consequently will enable the transporter to cover a much wider range of delivery over a much longer period.
12) Another useful advantage of the invention is that the water content of the polymer inside the sachets is progressively discharged through the fabric and by the action of the fan drawn as water vapour and spread throughout the container. This will maintain a constant degree of humidity which will keep the produce fresh. However any trace of liquid which may deposit inside the container will be absorbed by the super polymer to prevent the produce becoming wet. The combination of these functions will ensure that the produce maintains a pleasant and appealing appearance enhancing its presentation and commercial value.
13) The biocidal action of the invention will prevent possible cross contamination within the produce stored in the container during transport. The particular property of the polymer to absorb and contain contaminated liquids including oils, blood and other biological fluids, mixed with a biocide will facilitate the transport of temperature sensitive goods for medical purposes for example in areas and for applications remote from conventional refrigeration facilities, for relief operations or mobile medical services civil and military.
14) The invention can be used to deliver and introduce any chemical in vapour form into a forced air distribution system. Applications include the use of re-odorants to mask unpleasant and anti-social smells and the use of odour-releasing chemicals to enhance olfactory perception in commercial and recreational activities such as conference rooms, restaurants, leisure and sport centres, cinema complexes and similar areas where people gather.
15) An embodiment of the invention is now described by way of example with reference to the accompanying drawings in which:
FIG. 1 shows a sheet 1 of perforated sachets 2 containing a mixture of absorbent polymer and biocide 3.
FIG. 2 shows the sheet 1 of perforated saturated sachets enclosed in a 2 mm nylon sachet holder 4 placed opposite the fan 5 of an air conditioning unit, the said sachet holder being held in position with clips on the air inlet grill 6 showing the direction 7 of the air current which draws the biocide-laden water vapour inside the air conditioning system.
FIG. 3 illustrates the basic working parts of a typical air conditioning system showing the passage of the air current 7 drawn by the fan 5 carrying with it with biocide laden water vapour flowing through the air inlet grill 6, the evaporator with cooling coil 8 and dispersing through the air outlet 9. FIG. 3 also shows the condensate water dripping from the evaporator surface into the drip tray 10 and flushed through the drains 11.
16) The efficacy of the invention has been demonstrated through tests carried out in laboratories and in commercial/industrial premises. Some of the tests are reproduced in the following schedules:

Method and apparatus for anti-microbial and related treatments