CN114164058A

CN114164058A - Solid rinse aid composition and method of making same

Info

Publication number: CN114164058A
Application number: CN202111545735.9A
Authority: CN
Inventors: 孙昕; D·安德森; K·韦斯特; J·M·基弗; V·F-P·曼; M·亨特
Original assignee: Ecolab USA Inc
Current assignee: Ecolab USA Inc
Priority date: 2013-08-27
Filing date: 2013-09-10
Publication date: 2022-03-11
Also published as: AU2017201539B2; MX2016002237A; AU2013399081B2; BR112016004119A2; EP3039107A4; WO2015030836A1; EP3039107B1; AU2017201539A1; EP3039107A1; JP6599944B2; JP6208873B2; AU2019201156A1; CN105324473A; JP2017210627A; AU2013399081A1; BR112016004119B1; JP2016534204A; AU2019201156B2; ES2759203T3

Abstract

The invention comprises a solid rinse aid designed especially for pressed or extruded solid forms and effective for spot-free surfaces after rinsing, especially rinsing of metals without corrosion. According to the invention, solid acids are combined with short-chain alkylbenzenes and alkylnaphthalene sulfonates. Short chain alkyl benzene and alkyl naphthalene sulfonates act as hardeners as well as hydrotropes, and Total Dissolved Solids (TDS) active ingredients, and are combined with at least one nonionic low foaming surfactant.

Description

Solid rinse aid composition and method of making same

The application is a divisional application with the same name as the parent invention, the Chinese application number of the parent is 201380077663.7, the international application number is PCT/US2013/059013, and the application date is 9 months and 10 days in 2013.

Technical Field

The present invention relates to solid rinse aid compositions, and methods of making and using the same. Rinse aid compositions typically include a novel hardening system and a surfactant designed for use in pressed or extruded solid forms. The rinse aid can be used in aqueous use solutions on articles including, for example, cookware, dishware, dishes, glasses, cups, hard surfaces, healthcare surfaces, glass surfaces, vehicle surfaces, and the like, but is particularly useful on metal surfaces.

Background

Mechanical warewashing machines have been common in institutional and domestic environments for many years. Such automatic warewashers clean ware using two or more cycles, which may include an initial wash cycle followed by a rinse cycle, but may also utilize a soak, pre-wash, scrape, sanitize, dry, and additional wash cycles. Rinse agents are routinely used in warewashing applications to promote drying and prevent spotting.

Rinse agents may also be used in a healthcare environment, typically for cleaning medical carts, cages, instruments or devices. Typically, cleaning the cart, cage, instrument or device comprises contacting the cart, cage, instrument or device with an aqueous cleaning composition and rinsing or contacting it with a rinse solution containing a dissolved rinse aid. The method can also involve antimicrobially treating the medical vehicle, cage, instrument or device by contacting with an aqueous antimicrobial composition formed by dissolving or suspending a solid antimicrobial composition, preferably a solid quaternary ammonium or solid halogen antimicrobial composition.

In a domestic, institutional or healthcare environment, rinse agents are often added to the water to reduce the formation of spots, forming an aqueous rinse that is sprayed on the hard surface after cleaning is complete. The precise mechanism by which the rinse agent acts has not yet been established. One theory holds that at temperatures at or above its cloud point, the surfactant in the rinse agent is absorbed onto the surface, thereby lowering the solid-liquid interfacial energy and contact angle. This results in the formation of a continuous peel that drains uniformly from the surface and minimizes spot formation. Generally, a high foaming surfactant has a cloud point higher than the temperature of the rinse water and, according to this theory, will not promote peel formation, resulting in spotting. Also, highly foamed materials are known to interfere with the operation of warewashers.

Many rinse aids are currently known, each of which has some advantages and disadvantages. There continues to be a need for alternative rinse aid compositions, particularly alternative rinse aid compositions that are environmentally friendly (e.g., biodegradable), non-corrosive to metals, can handle high total dissolved solids, can handle high water hardness, and are easily prepared as solids.

Summary of The Invention

The present invention includes a solid rinse aid designed specifically for pressed or extruded solid forms and effective to leave a spot-free surface after rinsing (particularly rinsing metals without corrosion). According to the invention, the solid acid is combined with a hydrotrope of the short-chain alkylbenzene and alkylnaphthalene sulfonate type, such as sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkylnaphthalene sulfonate, and/or sodium butylnaphthalene sulfonate. Short chain alkyl benzene and alkyl naphthalene sulfonic acid hydrotropes act as a hardening agent as well as a surfactant and are combined with at least one nonionic low foaming surfactant.

The solid rinse agent compositions of the present invention thus include a solid acid for hardness control, a short chain alkylbenzene and/or alkylnaphthalene sulfonate, preferably Sodium Xylene Sulfonate (SXS), and a surfactant system. The surfactant is preferably a nonionic low foaming surfactant.

The compositions of the present invention are particularly beneficial for use with hard water and high Total Dissolved Solids (TDS) conditions.

Rinse aid concentrates are typically provided in solid form. It is typically prepared by the following steps: the solid materials are combined and then any liquid components are added. The material is then pressed or extruded to form a solid. Typically, it is contemplated to dilute the solid concentrate with water to provide a use solution, which is then applied to the substrate surface. The use solution preferably contains an effective amount of active material to provide a spot-free surface by rinsing the water. It should be understood that the term "active material" refers to the non-aqueous portion of the use solution that acts to reduce spotting and filming.

Some example methods of using a rinse aid generally include the steps of: providing a rinse aid, mixing the rinse aid into an aqueous use solution, and applying the aqueous use solution to a substrate surface.

In some embodiments, the solid acid is present in an amount of about 5 wt% to about 40 wt%. The short chain alkylbenzene or alkylnaphthalene sulfonate is present in an amount of from 50 wt% to 80 wt%, and the nonionic surfactant is present in an amount of from about 5 wt% to about 20 wt% for pressed solids, and from about 5 wt% to about 30 wt% for extruded solids. In some embodiments and as exemplified below, the solid rinse aid may also include additional surfactants, processing aids such as polyethylene glycol or urea, and other components such as chelating agents, preservatives, perfumes, or dyes.

In some aspects, the present invention relates to methods of rinsing surfaces in warewashing applications or on surfaces involved in health care. The method includes providing an aqueous rinse aid composition, diluting the rinse aid composition with water to form an aqueous use solution, and applying the aqueous use solution to a surface.

Drawings

FIG. 1 is a graph showing the hardness properties of compositions A and B of the present invention and various commercial rinse aids A-D.

FIG. 2 is a graph showing the Total Dissolved Solids (TDS) performance of compositions A and B of the present invention and various commercial rinse aids A-D.

FIG. 3 is a graph showing metal compatibility data for compositions A and B of the present invention and various commercial rinse aids A-D.

FIG. 4 is a graph showing the foam height at dispenser sump (pump) concentration for compositions A and B of the present invention and different commercial rinse aids D using a Glewwe foam unit.

FIG. 5 is a graph showing the foam height at RTU concentrations for compositions A and B of the present invention and various commercial rinse aids A-D.

Detailed Description

The present invention relates to rinse aid compositions, and methods of making and using rinse aid compositions. In some aspects, the present invention provides rinse aid compositions comprising a solid acid, a short chain alkylbenzene and an alkylnaphthalene sulfonate, such as sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkylnaphthalene sulfonate, and/or sodium butylnaphthalene sulfonate, and at least one additional surfactant, preferably a nonionic low foaming surfactant.

The compositions of the present invention can be used to reduce spotting and filming on a variety of surfaces including, but not limited to, glassware, cookware, tableware, dish, glass, cups, hard surfaces, glass surfaces, healthcare surfaces, and vehicle surfaces.

In order that the invention may be more clearly understood, certain terms are first defined.

The term "ware" as used herein refers to items such as eating, cooking and using utensils. Exemplary items of vessels include, but are not limited to: tableware, such as plates and bowls; silver vessels, such as forks, knives and spoons; cups and glasses, such as drinking cups and glasses; dishes, e.g. glass fibre trays, insulating tray covers. The term "warewashing" as used herein refers to washing, cleaning or rinsing ware. Articles of ware that may be contacted, e.g., washed or rinsed, with the compositions of the present invention may be prepared from any material. For example, vessels include articles made of wood, metal, ceramic, glass, and the like. Vessel also refers to an item made of plastic. Types of plastics that can be cleaned or rinsed with the compositions of the present invention include, but are not limited to, those containing polycarbonate Polymers (PC), acrylonitrile-butadiene-styrene polymers (ABS), and polysulfone Polymers (PS). Another exemplary plastic that can be cleaned using the methods and compositions of the present invention includes polyethylene terephthalate (PET).

The term "hard surface" as used herein includes showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, floors and the like.

The term "health care surface" as used herein refers to the surface of an instrument, device, cart, cage, furniture, structure, building or the like used as part of a health care activity. Examples of health care surfaces include surfaces of medical or dental instruments, surfaces of autoclaves and sterilizers, surfaces of electronic devices used to monitor the health of patients, and surfaces of fixtures in floors, walls or structures in which health care takes place. There are health care surfaces in hospitals, surgeries, wards, delivery rooms, mortises and clinical diagnostic rooms. These surfaces may be those typically referred to as "hard surfaces" (e.g., walls, floors, bed pans, etc.) or textile surfaces, such as knitted fabrics, woven and non-woven surfaces (e.g., surgical gowns, drapes, sheets and pillowcases, bandages, etc.), or patient-care equipment (e.g., ventilators, diagnostic equipment, shunts, body observation equipment, wheelchairs, beds, etc.), or surgical and diagnostic equipment. Health care surfaces include articles and surfaces used in animal health care.

The term "instrument" as used herein refers to various medical or dental instruments or devices that may benefit from the cleaning of water treated using the method according to the present invention.

As used herein, the terms "medical instrument," "dental instrument," "medical device," "dental device," "medical apparatus" or "dental apparatus" refer to instruments, devices, tools, kits, devices and equipment used in medicine or dentistry. Such instruments, devices and equipment may be cold sterilized, soaked or washed, and then heat sterilized, or benefit from being cleaned using water treated according to the present invention. These various instruments, devices and apparatuses include, but are not limited to: diagnostic instruments, trays, dishes, holders, racks, pliers, scissors, shears, saws (e.g., bone saws and their blades), hemostats, cutters, chisels, rongeurs, files, forceps, electric drills, drill bits, rasps, dental drills, spreaders, crushers, elevators, clamps, needle holders, carriers, clips, hooks, semicircular chisel, curette, retractors, straighteners, punches, extractors, buckets, keratomes, spatula, squeezers, trocars, dilators, cages, glassware, tubing, catheters, cannulas, plugs, stents, viewing instruments (e.g., endoscopes, stethoscopes, and arthroscopes) and related equipment, and the like or combinations thereof.

The term "solid" as used in relation to the compositions of the present invention means that the hardened composition does not appreciably flow and substantially retains its shape under appropriate stress or pressure or simply gravity, as for example the shape of a die when removed from the die, the shape of an article formed when extruded from an extruder and the like. The degree of hardening of the solid composition may range from a relatively dense and hard fused solid block (e.g., concrete) to a consistency characterized as malleable and spongy like an underfill.

The "cloud point" of a surfactant rinse or stripping agent (sheeting agent) is defined as the temperature at which a 1 wt% aqueous solution of the surfactant becomes cloudy when warmed.

The term "health care surface" as used herein refers to the surface of an instrument, device, cart, cage, furniture, structure, building or the like used as part of a health care activity. Examples of health care surfaces include surfaces of medical or dental instruments, surfaces of electronic devices used to monitor the health of patients, and surfaces of fixtures in floors, walls, or structures in which health care occurs. There are health care surfaces in hospitals, surgeries, wards, delivery rooms, mortises and clinical diagnostic rooms. These surfaces may be those typically referred to as "hard surfaces" (e.g., walls, floors, bed pans, etc.), or textile surfaces, such as knitted fabrics, woven and non-woven surfaces (e.g., surgical gowns, drapes, sheets and pillowcases, bandages, etc.), or patient-care devices (e.g., ventilators, diagnostic devices, shunts, body mirrors, wheelchairs, beds, etc.), or surgical and diagnostic devices. Health care surfaces include articles and surfaces used in animal health care.

The phrase "medical cart" as used herein refers to a cart for use in a healthcare environment to transport one or more medical instruments, devices or equipment and which may benefit from cleaning with a use composition of a solid cleaning composition, rinsing with a use composition of a solid rinsing composition, and/or antimicrobial treatment with a use composition of a solid antimicrobial composition. Medical carts include carts that transport medical or dental instruments or other medical or dental equipment in a healthcare environment, such as a hospital, clinic, dental or doctor room, nursing home, extended care facility, or the like.

The term "medical cage" as used herein refers to a cage used in a health care environment to contain and/or transport one or more animals used in experiments, in clinical or toxicological tests, or in diagnostics, etc. Such animals include rodents (e.g., mice or rats), rabbits, dogs, cats, or the like. Medical cages typically include an animal cage that actually contains the animal and may be mounted on a cogged belt. The medical cage may also include one or more containers or dispensers for animal food, one or more containers or dispensers for water, and/or one or more systems for identifying the cart or animal. Medical cages may benefit from cleaning with the use composition of the solid alkaline cleaning composition, rinsing with the use composition of the solid rinsing composition, and/or antimicrobial treatment with the use composition of the solid antimicrobial composition.

The term "instrument" as used herein refers to various medical or dental instruments or devices that may benefit from cleaning with the use composition of the solid alkaline cleaning composition, rinsing with the use composition of the solid rinsing composition, and/or antimicrobial treatment with the use composition of the solid antimicrobial composition.

As used herein, the terms "medical instrument," "dental instrument," "medical device," "dental device," "medical apparatus" or "dental apparatus" refer to instruments, devices, tools, kits, devices and equipment used in medicine or dentistry. Such instruments, devices and equipment may be cold sterilized, soaked or washed, and then heat sterilized, or benefit from cleaning in the compositions of the present invention. These various instruments, devices and apparatuses include, but are not limited to: diagnostic instruments, trays, dishes, holders, racks, forceps, scissors, shears, saws (e.g., bone saws and their blades), hemostats, knives, semicircular chisels, rongeurs, files, forceps, electric drills, drill bits, rasps, dental drills, spreaders, crushers, elevators, clamps, needle holders, carriers, clips, hooks, semicircular chisels, curettes, retractors, straighteners, punches, extractors, buckets, keratomes, tongue depressors, squeezers, trocars, dilators, cages, glassware, tubing, catheters, cannulas, plugs, stents, viewing instruments (e.g., endoscopes, stethoscopes, and arthroscopes) and related equipment, and the like or combinations thereof.

The term "alkyl" as used herein refers to a straight or branched chain monovalent hydrocarbon radical optionally containing one or more heteroatom substituents independently selected from S, O, Si or N. Alkyl groups generally include those having 1 to 20 atoms. Alkyl groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include, for example, alkoxy, hydroxy, mercapto, amino, alkyl-substituted amino, or halogen. Examples of "alkyl" as used herein include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, and isopropyl and the like. In addition, "alkyl" may include "alkylene", "alkenylene", or "alkynylene".

The term "alkylene" as used herein refers to a straight or branched chain divalent hydrocarbon radical optionally containing one or more heteroatom substituents independently selected from S, O, Si or N. Alkylene groups generally include those having 1 to 20 atoms. The alkylene groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include, for example, alkoxy, hydroxy, mercapto, amino, alkyl-substituted amino, or halogen. Examples of "alkylene" as used herein include, but are not limited to, methylene, ethylene, prop-1, 3-diyl, prop-1, 2-diyl, and the like.

The term "alkenylene" as used herein refers to a straight or branched chain divalent hydrocarbon radical having one or more carbon-carbon double bonds and optionally containing one or more heteroatom substituents independently selected from S, O, Si or N. Alkenylene groups generally include those having 1 to 20 atoms. Alkenylene groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include, for example, alkoxy, hydroxy, mercapto, amino, alkyl-substituted amino, or halogen. Examples of "alkenylene" as used herein include, but are not limited to, ethylene-l, 2-diyl, propylene-1, 3-diyl, and the like.

The term "alkynylene" as used herein refers to a straight or branched chain divalent hydrocarbon radical having one or more carbon-carbon triple bonds and optionally containing one or more heteroatom substituents independently selected from S, O, Si or N. Alkynylene groups generally include those having 1 to 20 atoms. Alkynylene groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include, for example, alkoxy, hydroxy, mercapto, amino, alkyl-substituted amino or halogen.

The term "alkoxy" as used herein refers to an-O-alkyl group, wherein alkyl is as defined above.

The term "halogen" or "halo" as used herein shall include iodine, bromine, chlorine and fluorine.

As used herein, the terms "mercapto" and "mercapto" refer to the substituent-SH.

The term "hydroxy" as used herein refers to the substituent-OH.

The term "amino" as used herein refers to the substituent-NH₂。

The methods and compositions of the present invention may comprise, consist of, or consist essentially of the listed steps or ingredients. The term "consisting essentially of …" as used herein should be interpreted to mean that it includes the listed ingredients or steps and additional ingredients or steps that do not materially affect the basic and novel properties of the composition or method. In some embodiments, a composition "consisting essentially of the recited ingredients" according to embodiments of the present invention does not include any additional ingredients that would alter the basic and novel properties of the composition, such as the drying time, film-forming ability, spotting or film-forming properties of the composition.

As used herein, "weight percent (wt%)", "wt%" and the like are synonymous and refer to the concentration of a substance expressed as the weight of the substance divided by the total weight of the composition and multiplied by 100.

Modifying the amount of an ingredient in a composition of the invention or used in a method of the invention the term "about" as used herein refers to variations in the amount of a numerical value that may occur, for example, through typical measurement and liquid handling procedures used in the preparation of concentrates or use solutions in the real world, through inadvertent errors in such procedures, through differences in the preparation, source or purity of the ingredients used in preparing the composition or practicing the method, and the like. The term "about" also encompasses that for a composition resulting from a particular starting mixture, different amounts result from different equilibrium conditions. Whether or not modified by the term "about," the claims include equivalents to these amounts.

As used in this specification and the appended claims, the singular forms "a," "an," and "the" may include plural referents unless the content clearly dictates otherwise. The term "or" as used in this specification and the appended claims is generally employed in its sense including "and/or" unless the content clearly dictates otherwise.

Solid rinse aid composition

The solid rinse aid compositions of the present invention comprise a solid acid, a short chain alkylbenzene or alkylnaphthalene sulfonate such as sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkylnaphthalene sulfonate, and/or sodium butylnaphthalene sulfonate, and one or more surfactants, preferably at least one of which is a nonionic low foaming surfactant.

The solid rinse aid composition is advantageously formulated to give a spot-free surface after rinsing, particularly at high hardness and high Total Dissolved Solids (TDS). The rinse aid is also particularly useful for metal surfaces and to avoid corrosion of metal surfaces.

Solid acid

The present invention includes one or more solid acids. The solid acid in the composition includes any acid that is natural or treated to be in solid form at room temperature. The term "solid" herein includes forms such as powdered, granular or particulate solid forms. Acidic materials (hereinafter "acids") include, but are not limited to, pharmaceutically acceptable organic or inorganic acids, hydroxy acids, amino acids, lewis acids, mono-or di-alkali metal or ammonium salts of molecules containing two or more acid groups, and monomeric or polymeric molecules containing at least one acid group. Examples of suitable acid groups include carboxylic acid groups, hydroxamic acid groups, amide groups, phosphate groups (e.g., mono-and di-hydrogen phosphate groups), sulfate groups, and bisulfite groups.

In particular, the acid is an organic acid having 2 to 18 carbon atoms, including but not limited to short, medium or long chain fatty acids, hydroxy acids, mineral acids, amino acids and mixtures thereof. Preferably, the acid is selected from the group consisting of lactic acid, gluconic acid, citric acid, tartaric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, maleic acid, monosodium citrate, disodium citrate, potassium citrate, monosodium tartrate, disodium tartrate, potassium tartrate, aspartic acid, carboxymethylcellulose, acrylic polymers, methacrylic polymers, and mixtures thereof.

For example, many organic acids are crystalline solids in pure form (and at room temperature), such as citric acid, oxalic acid, benzoic acid. Sulfamic acid is an example of an inorganic acid that is solid at room temperature.

The solid acid or combination of one or more solid acids is present in the rinse aid composition of the present invention in an amount of from about 5 wt% to about 40 wt%, preferably from about 7.5 wt% to about 27.5 wt%, and more preferably from about 10 wt% to about 25 wt%.

Short-chain alkyl benzene or alkyl naphthalene sulfonate

The short chain alkyl benzene or alkyl naphthalene sulfonate group functions as a hardening agent within the composition and as a hydrotrope and TDS control active. The group includes alkylbenzene sulfonates based on toluene, xylene and cumene, and alkylnaphthalene sulfonates. Sodium toluene sulfonate and sodium xylene sulfonate are the best known hydrotropes. These have the following general formula:

this group includes, but is not limited to, sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkyl naphthalene sulfonate, and sodium butyl naphthalene sulfonate. In a preferred embodiment, the hardener is SXS.

The present invention provides solid rinse aid compositions comprising an effective amount of one or more short chain alkylbenzene or alkylnaphthalene sulfonates. Surprisingly, it has been found that such hydrotropes increase the performance of the solid rinse aid as well as act as a hardening agent. Short chain alkyl benzene or alkyl naphthalene sulfonates may also serve as builders. Solid rinse aid compositions typically have melting points greater than 110 ° F and are dimensionally stable. In some embodiments, the short chain alkylbenzene or alkylnaphthalene sulfonate hardener is present in an amount of from about 40 wt% to about 90 wt%, preferably from about 45 wt% to about 85 wt%, and more preferably from about 50 wt% to about 80 wt%.

In some embodiments and as exemplified below, the solid rinse aid may also include additional processing aids, such as polyethylene glycol or urea. If used, the additional processing aid is present in an amount of about 0.1 wt% to about 10 wt%.

Nonionic surfactant

Nonionic surfactants useful in the present invention are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by condensing an organic aliphatic, alkylaromatic or polyoxyalkylene hydrophobic compound with a hydrophilic basic oxide moiety, which in common practice is ethylene oxide or its polyhydration product, polyethylene glycol. In practice, any hydrophobic compound having a hydroxyl, carboxyl, amino or amide group with a reactive hydrogen atom may be condensed with ethylene oxide or its polyhydrated adduct or its mixture with alkyleneoxy groups (e.g., propylene oxide) to form a nonionic surfactant. The length of the hydrophilic polyoxyalkylene moiety condensed with any particular hydrophobic compound can be readily adjusted to provide a water-dispersible or water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic energy. In the present invention, useful nonionic surfactants include the following.

Examples of suitable nonionic surfactants include alkoxylated surfactants, such as Dehypon LS-54(R- (EO)₅(PO)₄) And Dehypon LS-36(R- (EO)₃(PO)₆) (ii) a And blocked alcohol alkoxylates such as Plurafac LF221 and Genepol available from Clariant, Tegoten EC 11; mixtures thereof or the like. ))

Other nonionic surfactants that can be used include:

1. based on propylene glycol, ethylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiatorBlock polyoxypropylene-polyoxyethylene polymer compounds of reactive hydrogen compounds. Examples of polymer compounds prepared from sequential propylene and ethylene oxidation initiators are under the trade name

And

commercially available, prepared from BASF Corp.

The compound is a difunctional (two reactive hydrogens) compound formed by the condensation of ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to the two hydroxyl groups of propylene glycol. The molecular weight of this hydrophobic moiety is 1,000-4,000. Ethylene oxide is then added to sandwich this hydrophobic moiety between hydrophilic groups, controlled by length to account for about 10% to about 80% by weight of the final molecule.

The compounds are tetrafunctional block copolymers derived from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The molecular weight range of the propylene oxide hydrotrope is 500-7,000; and adding hydrophilic ethylene oxide to constitute from about 10 wt% to about 80 wt% of the molecule.

Condensation products of 2.1mol of alkylphenols, in which the alkyl chain in the alkylphenol has 8 to 18 carbon atoms in the linear or branched configuration or in the mono-or dibasic alkyl component, with 3 to 50mol of ethylene oxide. The alkyl group may be represented by, for example, a di-isobutylene group, a di-pentyl group, a polymerized propylene group, an isooctyl group, a nonyl group and a dinonyl group. These surfactants may be polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkyl phenols. An example of a commercial compound of this chemistry is marketed under the trade name prepared by Rhone-Poulenc

And prepared from Dow

And (4) obtaining.

Condensation products of 3.1mol of saturated or unsaturated, linear or branched alcohols having from 6 to 24 carbon atoms with from 3 to 50mol of ethylene oxide. The alcohol moiety may consist of a mixture of alcohols in the carbon atom range listed above, or it may consist of an alcohol having a specific number of carbon atoms within this range. An example of a similar commercial surfactant is under the trade name manufactured by Shell Chemical Co

And prepared from Vista Chemical co

And (4) obtaining.

Condensation products of 4.1mol of saturated or unsaturated, linear or branched carboxylic acids having from 8 to 18 carbon atoms with from 6 to 50mol of ethylene oxide. The acid moiety may consist of a mixture of acids in the carbon atom range defined above or it may consist of an acid having a specific number of carbon atoms within this range. Examples of commercial compounds of this chemistry are commercially available from Henkel Corporation

And prepared by Lipo Chemicals, Inc

And (4) obtaining.

In addition to ethoxylated carboxylic acids (often referred to as polyethylene glycol esters), other alkanoic acid esters formed by reaction with glycerides, glycerols, and poly (saccharide or sorbitan/sorbitol) alcohols may be used in the present invention. All of these ester moieties have one or more reactive hydrogen sites on their molecule that can undergo further acylation or ethylene oxide (alkoxide) addition to control the hydrophilicity of these materials. When adding these fatty esters or acylated carbohydrates to the compositions of the present invention containing amylase and/or lipase care must be taken because of potential incompatibility.

In a preferred embodiment, the nonionic surfactant is a low foaming nonionic surfactant. Examples of the low-foaming nonionic surfactant include:

5. by addition of ethylene oxide to ethylene glycol to provide a hydrophile of a specified molecular weight; and then adding propylene oxide on the outside (end) of the molecule to obtain a hydrophobic block modified, substantially reversed compound from (1). The molecular weight of the hydrophobic portion of the molecule is 1,000-3,100, and the central hydrophilic species accounts for 10-80 wt% of the final molecule. These being in opposite directions

Under the trade name of BASF Corporation

And preparing the R surfactant.

Also, in the same manner as above,

the R surfactant was produced by BASF Corporation by sequential addition of ethylene oxide and propylene oxide to ethylenediamine. The molecular weight of the hydrophobic portion of the molecule is 2,100-6,700, and the central hydrophilic species accounts for 10-80 wt% of the final molecule.

6. Compounds from groups (1), (2), (3) and (4) modified to reduce foaming by "capping" or "endcapping" (of the polyfunctional moiety) one or more terminal hydroxyl groups by reaction with small hydrophobic molecules (e.g. propylene oxide, butylene oxide, benzyl chloride) and short chain fatty acids containing 1-5 carbon atoms, alcohols or alkyl halides and mixtures thereof. Also included are reactants such as thionyl chloride which converts the terminal hydroxyl group to a chloro group. This modification of the terminal hydroxyl groups can result in all-block, block-hetero, hetero-block, or all-hetero nonionic surfactants.

Additional examples of effective low-foaming nonionic surfactants include:

alkylphenoxypolyethoxyalkanols of the formula, in U.S. Pat. No.2,903,486 to Brown et al, 8.9. 7.1959:

wherein R is an alkyl group of 8 to 9 carbon atoms, A is an alkylene chain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is an integer of 1 to 10.

U.S. Pat. No.3,048,548 issued to Martin et al on 8/7/1962 has a polyalkylene glycol condensate having alternating hydrophilic oxyethylene chains and hydrophobic oxypropylene chains wherein the weight of the terminal hydrophobic chains, the weight of the intermediate hydrophobic units and the weight of the attached hydrophilic units each comprise about 1/3 of the condensate.

Defoaming nonionic surfactants disclosed in U.S. Pat. No.3,382,178 issued to Lissant et al on 5/7/1968 and having the general formula Z [ (OR)_nOH]_zWherein Z is an oxyalkylatable material, R is a group derived from a basic oxide, which may be ethylene and propylene, and n is an integer, for example, from 10 to 2,000 or more and Z is an integer determined by the number of reactive oxyalkylatable groups.

Conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,677,700 to Jackson et al, 5/4/1954, which corresponds to formula Y (C)₃H₆O)_n(C₂H₄O)_mH, wherein Y is the residue of an organic compound having 1 to 6 carbon atoms and 1 reactive hydrogen atom, n is an average value of at least 6.4 as determined by the number of hydroxyl groups, and m has a value such that the oxyethylene moieties constitute 10% to 90% by weight of the molecule.

A conjugated polyoxyalkylene compound described in U.S. Pat. No.2,674,619 issued to Lundsted et al on 6.4.4.1954 and having the formula Y [ (C)₃H₆O_n(C₂H₄O)_mH]_xWherein Y is the residue of an organic compound having 2 to 6 carbon atoms and containing x reactive hydrogen atoms, wherein x is a number of at least 2The value of n is such that the molecular weight of the polyoxypropylene hydrophobe is at least 900 and the value of m is such that the oxyethylene content of the molecule is between 10% and 90% by weight. Compounds falling within the definition of Y include, for example, propylene glycol, glycerol, pentaerythritol, trimethylolpropane, ethylenediamine and the like. The oxypropylene chains optionally but advantageously contain a small amount of ethylene oxide, and the oxyethylene chains also optionally but advantageously contain a small amount of propylene oxide.

The additional conjugated polyoxyalkylene surface-active agents advantageously used in the compositions of the present invention correspond to the formula: p [ (C)₃H₆O)_n(C₂H₄O)_mH]_xWherein P is the residue of an organic compound having 8 to 18 carbon atoms and containing x reactive hydrogen atoms, wherein x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxyethylene moiety is at least 44 and m has a value such that the oxypropylene content of the molecule is between 10% and 90% by weight. In either case, the oxypropylene chains may optionally but advantageously contain small amounts of ethylene oxide, and the oxyethylene chains may also optionally but advantageously contain small amounts of propylene oxide.

8. Polyhydroxy fatty acid amide surfactants suitable for use in the compositions of the present invention include those having the formula R²CONR¹Those of Z wherein R¹Is H, C₁-C₄A hydrocarbyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, an ethoxy group, a propoxy group, or a mixture thereof; r²Is C₅-C₃₁A hydrocarbon group, which may be linear; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain and having at least three hydroxyl groups directly attached to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z may be derived from a reducing sugar in a reductive amination reaction, for example a glycidyl moiety.

9. Alkyl ethoxylate condensation products of aliphatic alcohols with from 0 to 25mol of ethylene oxide are suitable for use in the compositions of the present invention. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and typically contains from 6 to 22 carbon atoms.

10. Ethoxylated C₆-C₁₈Fatty alcoholsAnd C₆-C₁₈Mixed ethoxylated and propoxylated fatty alcohols are suitable surfactants for use in the compositions of the present invention, especially those that are water soluble. Suitable ethoxylated fatty alcohols include C with a degree of ethoxylation of from 3 to 50₁₀-C₁₈An ethoxylated fatty alcohol.

11. Suitable nonionic alkyl polysaccharide surfactants particularly suitable for use in the compositions of the present invention include those disclosed in U.S. Pat. No.4,565,647 to Llenado on 21.1.1986. These surfactants include hydrophobic groups containing 6 to 30 carbon atoms and hydrophilic groups of polysaccharides (e.g., polyglycosides) containing 1.3 to 10 saccharide units. Any reducing sugar containing 5 or 6 carbon atoms may be used, for example glucose, galactose and the galactosyl moiety may be substituted with the glucosyl moiety. (optionally, the hydrophobic groups are attached at the 2-,3-,4-, etc. positions, thereby yielding a glucose or galactose, as opposed to a glucoside or galactoside.) the intersugar (intersaccharide) linkage may for example be between one position of the additional sugar unit and the 2-,3-, 4-and/or 6-position of the preceding sugar unit.

12. Fatty acid amide surfactants suitable for use in the compositions of the present invention include those having the formula R⁶CON(R⁷)₂Wherein R is⁶Is an alkyl group having 7 to 21 carbon atoms, and each R⁷Independently of one another is hydrogen, C₁-C₄Alkyl radical, C₁-C₄Hydroxyalkyl or- - (C)₂H₄O)_XH, wherein x ranges from 1 to 3.

13. One class of useful nonionic surfactants includes those defined as alkoxylated amines or most particularly alcohol alkoxylated/aminated/alkoxylated surfactants. These nonionic surfactants may be represented, at least in part, by the general formula:

R²⁰-(PO)_sN-(EO)_tH，

R²⁰-(PO)_sN-(EO)_tH(EO)_th, and

R²⁰-N(EO)_tH；

wherein R is²⁰Is an alkyl, alkenyl or other aliphatic group, orAlkyl-aryl of 8 to 20 and preferably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2 to 5, t is 1 to 10, preferably 2 to 5, and u is 1 to 10, preferably 2 to 5. Other variations within the scope of these compounds may be represented by the following alternative formulae:

R²⁰-(PO)_v-N[(EO)_wH][(EO)_zH]

wherein R is²⁰As defined above, v is 1 to 20 (e.g., 1,2,3 or 4 (preferably 2)), w and z are independently 1 to 10, preferably 2 to 5.

These compounds are commercially represented by a series of products sold by Huntsman Chemicals as nonionic surfactants. Preferred such chemicals include Surfonic PEA 25Amine alkoxlyate.

The linear nonionics Surfactants, first volume of Surfactant Science Series, Marcel Dekker, inc., New York,1983, edited by Schick, m.j., is an excellent reference for a wide variety of Nonionic compounds commonly used in The practice of The present invention. A typical list of the classes and species of the nonionic surfactants is given in U.S. Pat. No.3,929,678 to Laughlin and Heuring, 12/30/1975. Further examples are given in Surface Active Agents and Detergents, volumes I and II, Schwartz, Perry and Berch.

Water (W)

In some embodiments, the solid rinse aid composition comprises water. Water may be added separately to the solid rinse aid composition or may be provided to the solid rinse aid composition as a result of its presence in the material added to the solid rinse aid composition. For example, materials added to the solid rinse aid composition include water or are prepared in an aqueous premix that is available for reaction with the hardener component. Typically, water is introduced into the solid rinse aid composition to provide a composition having a desired viscosity prior to hardening, and to provide a desired cure rate.

Generally, it is contemplated that water is present as a processing aid and may be removed or become water of hydration. It is contemplated that water may be present in the solid composition. In solid compositions, it is contemplated that water will be present in the solid rinse aid composition in the range of 0 wt.% to 5 wt.%. For example, water is present in the range of 0.1 wt% to about 5 wt% in embodiments of the solid rinse aid composition, or in the range of 0.5 wt% to about 4 wt% in further embodiments of the solid rinse aid composition, or in the range of 1 wt% to 3 wt% in still further embodiments of the solid rinse aid composition. It should also be understood that the water may be provided in the form of deionized or demineralized water.

The components used to form the solid composition may include water as a hydrate or hydrated form of the binder, a hydrate or hydrated form of any other ingredient, and/or an aqueous medium added as an aid in processing. It is expected that the aqueous medium will help provide the components with the viscosity required for processing. Additionally, it is contemplated that the aqueous medium may aid the hardening process when it is desired to form a concentrate in solid form.

Additional functional materials

As noted above, the solid rinse aid may contain other functional materials that provide the desired properties and functionality to the solid composition.

Functional materials include materials that provide beneficial properties in a particular application when dispersed or dissolved in a use solution. Examples of such functional materials include preservatives, chelating/sequestering agents; a bleaching or activating agent; disinfectants/antimicrobials; an activator; builders or fillers; an anti-redeposition agent; a fluorescent whitening agent; a dye; a flavoring or fragrance; a stabilizer; a processing aid; a corrosion inhibitor; a filler; a hardening agent; an additional hardener; additional surfactants, solubility modifiers; a pH adjusting agent; a humectant; a hydrotrope; or numerous other functional materials. In the context of some embodiments disclosed herein, functional materials or ingredients are optionally included within the hardening matrix due to their functionality.

Some more specific examples of functional materials will be discussed in more detail below, but those skilled in the art and others will appreciate that the specific materials discussed are given by way of example only, and that a wide variety of other functional materials may be used.

Preservative

The solid rinse aid composition may also include an effective amount of a preservative. Often, the total acidity and/or acid of the solid rinse aid composition and use solution serves as a preservative and stabilizing effect.

Some embodiments of the solid rinse aid compositions of the present invention also include a preservative system for acidification of the solid rinse aid, including sodium bisulfate and an organic acid. In at least some embodiments, the solid rinse aid has a pH of 2.0 or less and the use solution of the solid rinse aid has a pH of at least pH 4.0. Typically, sodium bisulfate is included in the solid rinse aid composition as an acid source. In certain embodiments, an effective amount of sodium bisulfate and one or more other acids are included in the solid rinse aid composition as a preservative system. Suitable acids include, for example, inorganic acids such as HCl, and organic acids. In certain further embodiments, effective amounts of sodium bisulfate and one or more organic acids are included in the solid rinse aid composition as a preservative system. Suitable organic acids include sorbic acid, benzoic acid, ascorbic acid, erythorbic acid, citric acid, and the like. Preferred organic acids include benzoic acid and ascorbic acid. Typically, an effective amount of sodium bisulfate is included, with or without additional acid, such that the use solution of the solid rinse aid composition has a pH value that should be less than pH 4.0, often less than pH 3.0, and may even be less than pH 2.0.

In other embodiments, the solid rinse aid composition comprises a disinfectant/antimicrobial agent in addition to or in lieu of the preservative system described above. Suitable disinfectants/antimicrobials will be described below.

If present, the preservative component is typically present in an amount of about 0.05 to 20 wt%, preferably 0.1 to 15 wt%, and most preferably 1 wt% to about 10 wt% of the solid rinse aid composition.

Chelating/sequestering agents

The solid rinse aid composition may also include an effective amount of a chelant/sequestrant, also known as a builder. In addition, the rinse aid may optionally comprise one or more additional builders as functional ingredients. In general, chelating agents are molecules capable of coordinating (i.e., binding) metal ions typically present in water sources to prevent the metal ions from interfering with the action of other ingredients in rinse aids or other cleaning compositions. The chelating/sequestering agent can also act as a threshold agent when included in an effective amount.

Typically, the solid rinse aid is also phosphate-free and/or aminocarboxylate-free. In embodiments of the phosphate-free solid rinse aid composition, additional functional materials, including builders, exclude phosphorus-containing compounds such as condensed phosphates and phosphonates.

Suitable additional builders include polycarboxylates. Some examples of polymeric polycarboxylates suitable for use as sequestering agents include those having pendant carboxylates (-CO)₂) And include, for example, polyacrylic acid, maleic acid/olefin copolymers, acrylic acid/maleic acid copolymers, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamides, hydrolyzed polymethacrylamides, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitriles, hydrolyzed polymethacrylonitriles, hydrolyzed acrylonitrile-methacrylonitrile copolymers, and the like.

In embodiments of the solid rinse aid composition that are not free of aminocarboxylate, an added chelant/sequestrant may be included as an aminocarboxylate. Some examples of aminocarboxylic acids include N-hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA) (in addition to the HEDTA used in the binder), diethylenetriaminepentaacetic acid (DTPA), and the like.

In embodiments of the solid rinse aid composition that are not phosphate-free, the added chelant/sequestrant may include, for example, condensed phosphates, phosphonates, and the like. Some examples of condensed phosphates include sodium and potassium orthophosphate, sodium and potassium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, and the like. Condensed phosphates may also contribute to the hardening of the composition to a limited extent by fixing the free water present in the composition to water of hydration.

In embodiments of the solid rinse aid composition that are not phosphate-free, the composition may comprise a phosphonate, such as 1-hydroxyethane-1, 1-diphosphonic acid CH₃C(OH)[PO(OH)₂]₂(ii) a Amino tri (methylene phosphonic acid) N [ CH₂PO(OH)₂]₃(ii) a Aminotris (methylenephosphonic acid) sodium salt

2-hydroxyethyliminodibis (methylenephosphonic acid) HOCH₂CH₂N[CH₂PO(OH)₂]₂(ii) a Diethylene triamine penta (methylene phosphonic acid) (HO)₂POCH₂N[CH₂CH₂N[CH₂PO(OH)₂]₂]₂(ii) a Diethylenetriamine penta (methylenephosphonic acid) sodium salt C₉H_(28-x)N₃Na_xO₁₅P₅(x ═ 7); potassium salt of hexamethylenediamine (tetramethylenephosphonic acid) C₁₀H_(28-x)N₂K_xO₁₂P₄(x ═ 6); bis (hexamethylene) triamine (pentamethylene phosphonic acid) (HO)₂)POCH₂N[(CH₂)₆N[CH₂PO(OH)₂]₂]₂(ii) a And phosphorous acid H₃PO₃. In some embodiments, a combination of phosphonates may be used, for example ATMP and DTPMP. Either a previously neutralized or alkaline phosphonate, or a combination of the phosphonate and an alkali source, can be used that is added to the mixture such that little or no heat or gas is generated by the neutralization reaction when the phosphonate is added.

For a further discussion of chelating/sequestering agents, see Kirk-Othmer, Encyclopedia of Chemical Technology, 3 rd edition, volume 5, pp.339-.

When present, the chelating/sequestering agent may be used in an amount of about 0.1 wt% to about 30 wt%, preferably about 1 wt% to about 25 wt%, and more preferably about 5 wt% to about 20 wt%. In some embodiments, the solid acid may also function as a chelating agent.

Processing aid

In some embodiments, the solid rinse aid composition may include additional processing aids. Examples of processing aids include amides, such as stearyl monoethanolamide or lauryl diethanolamide, or alkylamides, and the like; solid polyethylene glycol, or solid EO/PO block copolymers, urea and the like; starch which is changed into water-soluble starch by an acid or alkali treatment process; various inorganic substances that impart hardening properties to the heated composition upon cooling, and the like. Such compounds may also modify the solubility of the composition in aqueous media during use so that rinse aids and/or other active ingredients may be dispensed from the solid composition over an extended period of time. The composition may include an auxiliary hardener in an amount ranging up to about 10 weight percent. In some embodiments, the auxiliary hardener may be present in an amount in the range of from 0 to 10 weight percent, often in the range of from 0 to 5 weight percent, and sometimes in the range of from about 0 to about 0.5 weight percent.

Additional surfactants

In addition to the nonionic surfactants specified above, the compositions may also include other surfactants listed below.

Anionic surfactants

Certain embodiments of the present invention contemplate the use of one or more anionic surfactants that interact electrostatically or ionically with the positively charged polymer to enhance the stability of the foam. Anionic surfactants are surfactants classified as anionic because the charge on the hydrophobe is negative; or a surfactant, wherein the hydrophobic portion of the molecule is uncharged unless the pH is raised to neutral or above (e.g., carboxylic acids).

Carboxylates, sulfonates, sulfates and phosphates are polar (hydrophilic) solubilizing groups present in anionic surfactants. Among the cations (counter ions) bound to these polar groups, sodium, lithium and potassium impart water solubility; ammonium and substituted ammonium ions provide both water and oil solubility; calcium, barium and magnesium promote oil solubility.

It is understood by those skilled in the art that anionic surfactants are excellent detersive surfactants and are therefore routinely advantageously added to heavy duty detergent compositions as well as rinse aids. Generally, anionic surfactants have a high foam profile, which is useful in the foaming cleaning compositions of the present invention. Anionic surface active compounds can be used in compositions to impart specific chemical or physical properties in addition to cleaning.

Most of the large number of commercial anionic surfactants can be subdivided into 5 major chemical classes and additional subgroups known to those skilled in the art and are described in "Surfactant Encyclopedia," Cosmetics & Toiletries, volume 104(2) 71-86 (1989).

The first category includes acylamino acids (and salts), such as acylglutamates, acyl peptides, sarcosinates (e.g., N-acyl sarcosinates), taurates (e.g., N-acyl taurates and fatty acid amides of methyl tauride) and the like. The second class includes carboxylic acids (and salts), such as alkanoic acids (and alkanoates), ester carboxylic acids (e.g., alkyl succinates), ether carboxylic acids, and the like. The third class includes sulfonic acids (and salts), such as isethionates (e.g., acyl isethionates), alkylaryl sulfonates, alkylsulfonates, sulfosuccinates (e.g., mono-and diesters of sulfosuccinic acid), and the like. An especially preferred anionic surfactant is an alpha olefin sulfonate. The fourth class includes sulfonic acids (and salts), such as isethionates (e.g., acyl isethionates), alkylaryl sulfonates, alkylsulfonates, sulfosuccinates (e.g., mono-and diesters of sulfosuccinic acid), and the like. The fifth category includes sulfates, such as alkyl ether sulfates, alkyl sulfates, and the like. The fifth category includes sulfates, such as alkyl ether sulfates, alkyl sulfates, and the like. An especially preferred anionic surfactant is sodium lauryl ether sulfate.

Anionic sulfate surfactants suitable for use in the compositions of the present invention include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oil alkenyl glycerosulfatesOil sulfate, alkylphenol ethoxylate sulfate, C₅-C₁₇acyl-N- (C)₁-C₄Alkyl) and-N- (C)₁-C₂Hydroxyalkyl) glucosamine sulfate and sulfates of alkyl polysaccharides, such as alkyl polyglucoside sulfate (nonionic, non-sulfated compounds are described herein). Alkali metal (e.g., sodium, lithium and potassium) salts of ammonium and substituted ammonium (e.g., mono-, di-, and triethanolamine) and alkyl mononuclear aromatic sulfonates, such as alkyl benzene sulfonates containing 5 to 18 carbon atoms in the alkyl group, straight or branched, for example, alkyl benzene sulfonates or alkyltoluene, xylene, cumene and phenol sulfonates; alkyl naphthalene sulfonates, diamyl naphthalene sulfonates and dinonyl naphthalene sulfonates and alkoxylated derivatives.

Examples of suitable synthetic water-soluble anionic surfactant compounds include ammonium and substituted ammonium (e.g., mono-, di-, and triethanolamine) and alkali metal (e.g., sodium, lithium and potassium) salts of alkyl mononuclear aromatic sulfonates, such as alkyl benzene sulfonates containing from 5 to 18 carbon atoms in the alkyl group, straight or branched, for example, alkyl benzene sulfonates or alkyl toluene, xylene, cumene and phenol sulfonates; alkyl naphthalene sulfonates, diamyl naphthalene sulfonates and dinonyl naphthalene sulfonates and alkoxylated derivatives.

Anionic carboxylate surfactants suitable for use in the compositions of the present invention include alkyl ethoxy carboxylates, alkylpolyethoxy polycarboxylate surfactants, and soaps (e.g., alkyl carboxylates). Secondary soap surfactants (e.g., alkyl carboxyl surfactants) useful in the compositions of the present invention include those that contain a carboxyl unit attached to a secondary carbon. The secondary carbon may be within the ring structure, for example in p-octylbenzoic acid, or in an alkyl-substituted cyclohexyl carboxylate. Secondary soap surfactants typically contain no ether linkages, no ester linkages and no hydroxyl groups. Further, they typically lack a nitrogen atom in the head group (the amphiphilic moiety). Suitable secondary soap surfactants typically contain 11-13 total carbon atoms, but there may be more carbon atoms (e.g., up to 16).

Other anionic surfactants suitable for use in the compositions of the present invention include olefin sulfonates, such as long chain olefin sulfonates, long chain hydroxyalkane sulfonates, or mixtures of olefin sulfonates and hydroxyalkane sulfonates. Also included are alkyl sulfates, alkyl poly (ethyleneoxy) ether sulfates and aromatic poly (ethyleneoxy) sulfates, such as the sulfates or condensation products of ethylene oxide and nonylphenol (typically having 1 to 6 oxyethylene groups per molecule). Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow.

The particular salt is suitably selected depending on the particular formulation and requirements therein.

Further examples of suitable anionic surfactants are given in "Surface Active Agents and Detergents" (Vol.I and II, Schwartz, Perry and Berch). Various such surfactants are also generally disclosed in U.S. Pat. No.3,929,678 to Laughlin et al, 12/30 1975, at column 23, line 58 to column 29, line 23.

Zwitterionic surfactants

Zwitterionic surfactants can be considered as a subset of amphoteric surfactants. Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Typically, zwitterionic surfactants include positively charged quaternary ammonium, or in some cases sulfonium or phosphonium ions, negatively charged carboxy groups, and alkyl groups. Zwitterionic surfactants usually contain cationic and anionic groups that ionize to nearly equal degrees in the isoelectric region of the molecule and can produce strong "endo-salt" attraction between positive-negative charge centers. Examples of such zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain and wherein one of the aliphatic substituents contains 8-18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Betaine and sulfobetaine surfactants are exemplary zwitterionic surfactants for use herein.

These compounds have the general formula:

wherein R is¹An alkyl, alkenyl or hydroxyalkyl group of 8 to 18 carbon atoms containing 0 to 10 ethylene oxide moieties and 0 to 1 glyceryl moiety; y is selected from nitrogen, phosphorus and sulfur atoms; r²Is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfur atom, x is 2 when Y is a nitrogen or phosphorus atom, R³Is an alkylene or hydroxyalkylene of 1 to 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate and phosphate.

Examples of zwitterionic surfactants having the structure listed above include: 4- [ N, N-bis (2-hydroxyethyl) -N-octadecylammonio ] -butane-1-carboxylic acid salt; 5- [ S-3-hydroxypropyl-S-hexadecylsulfo (sulfonio) ] -3-hydroxypentane-1-sulfate; 3- [ P, P-diethyl-P-3, 6, 9-trioxadotetracosylphosphonium (phosphonio) ] -2-hydroxypropane-1-phosphate; 3- [ N, N-dipropyl-N-3-dodecyloxy-2-hydroxypropyl-ammonio ] -propane-1-phosphonate; 3- (N, N-dimethyl-N-hexadecylammonium) -propane-1-sulfonate; 3- (N, N-dimethyl-N-hexadecylammonio) -2-hydroxypropane-1-sulfonate; 4- [ N, N-bis (2 (2-hydroxyethyl) -N (2-hydroxydodecyl) ammonio ] -butane-1-carboxylate; 3- [ S-ethyl-S- (3-dodecyloxy-2-hydroxypropyl) sulfo ] -propane-1-phosphate; 3- [ P, P-dimethyl-P-dodecylphosphonium ] -propane-1-phosphonate; and S- [ N, N-bis (3-hydroxypropyl) -N-hexadecylammonium ] -2-hydroxy-pentane-1-sulfate the alkyl groups contained in the detergent surfactant may be linear or branched and saturated or unsaturated.

Zwitterionic surfactants suitable for use in the compositions of the present invention include betaines of the general structure:

these surfactants betaine typicalAnd do not exhibit strong cationic or anionic character at pH extremes nor exhibit reduced water solubility in their isoelectric domain. Unlike "external" quaternary ammonium salts, betaines are compatible with anionic surfactants. Examples of suitable betaines include cocoacylamidopropyl dimethyl betaine; cetyl dimethyl betaine; c_12-14Acylamidopropyl betaine; c_8-14Acylamidohexyl diethylbetaine; 4-C_14-16Acylaminomethylaminodiethylammonium-1-carboxybutane; c_16-18Acylamidodimethylbetaine; c_12-16Acylamidopentane diethylbetaine; and C_12-16Acyl methyl amido dimethyl betaine.

Sultaines (sultaines) useful in the present invention include those having the general formula (R)¹)₂N⁺R²SO³-those compounds in which R is C₆-C₁₈A hydrocarbon radical, each R¹Is typically independently C₁-C₃Alkyl, e.g. methyl, and R²Is C₁-C₆Hydrocarbyl radicals, e.g. C₁-C₃Alkylene or hydroxyalkylene.

A typical list of zwitterionic classes and species of these surfactants is given in U.S. Pat. No.3,929,678 to Laughlin and Heuring, 12/30 in 1975. Further examples are given in Surface Active Agents and Detergents (Vol.I and II, Schwartz, Perry and Berch).

The betaines and sulfobetaines, as well as other such zwitterionic surfactants, are present in the composition in any cleaning amount which can typically range from about 0.01 wt.% to about 75 wt.% of the rinse aid composition. In preferred embodiments, from about 10 wt% to about 30 wt%, and more preferably from about 15 wt% to about 25 wt%.

Semi-polar nonionic surfactants

Semi-polar types of nonionic surfactants are another class of nonionic surfactants useful in the compositions of the present invention. Typically, semi-polar nonionic surfactants are high sudsing agents and foam stabilizers, which may limit their application within CIP systems. However, within the embodiments of the compositions of the present invention designed for high foam cleaning methods, semi-polar nonionic surfactants have immediate efficacy. Semi-polar nonionic surfactants include amine oxides, phosphine oxides, sulfoxides and their alkoxylated derivatives.

Amine oxides are tertiary amine oxides corresponding to the general formula:

wherein the arrow is a conventional representation of a semi-polar bond, and R¹，R²And R³May be aliphatic, aromatic, heterocyclic, alicyclic, or a combination thereof. In general, for amine oxides for detergent considerations, R¹Is an alkyl group of 8 to 24 carbon atoms; r²And R³Is an alkyl or hydroxyalkyl group of 1 to 3 carbon atoms or mixtures thereof; r²And R³May be linked to each other, for example through an oxygen or nitrogen atom, forming a ring structure; r⁴Is a basic or hydroxyalkylene group containing 2 to 3 carbon atoms; and n ranges from 0 to 20.

Useful water-soluble amine oxide surfactants are selected from coconut or tallow alkyl di- (lower alkyl) amine oxides, specific examples of which are dodecyl dimethylamine oxide, tridecyl dimethylamine oxide, tetradecyl dimethylamine oxide, pentadecyl dimethylamine oxide, hexadecyl dimethylamine oxide, heptadecyl dimethylamine oxide, octadecyl dimethylamine oxide, dodecyl dipropylamine oxide, tetradecyl dipropylamine oxide, hexadecyl dipropylamine oxide, tetradecyl dibutylamine oxide, octadecyl dibutylamine oxide, bis (2-hydroxyethyl) dodecylamine oxide, bis (2-hydroxyethyl) -3-dodecyloxy-1-hydroxypropylamine oxide, dimethyl- (2-hydroxydodecyl) amine oxide, 3,6, 9-trioctadecyl dimethylamine oxide and 3-dodecyloxy-2-hydroxypropyl bis- (2-hydroxyethyl) amine oxide.

Useful semi-polar nonionic surfactants also include water-soluble phosphine oxides having the structure:

wherein the arrow is a conventional representation of a semi-polar bond; and R¹Is an alkyl, alkenyl or hydroxyalkyl moiety having a chain length in the range of 10 to 24 carbon atoms; and R is²And R³Each is an alkyl moiety independently selected from alkyl or hydroxyalkyl groups containing 1 to 3 carbon atoms.

Examples of useful phosphine oxides include dimethyldecylphosphine oxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphine oxide, dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosphine oxide, bis (2-hydroxyethyl) dodecylphosphine oxide and bis (hydroxymethyl) tetradecylphosphine oxide.

Semi-polar nonionic surfactants useful herein also include water-soluble sulfoxide compounds having the structure:

wherein the arrow is a conventional representation of a semi-polar bond; and R¹An alkyl or hydroxyalkyl moiety of 8 to 28 carbon atoms, 0 to 5 ether linkages and 0 to 2 hydroxy substituents; and R is²Is an alkyl moiety consisting of an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group.

Useful examples of such sulfoxides include dodecyl methyl sulfoxide; 3-hydroxytridecyl methyl sulfoxide; 3-methoxytridecylmethyl sulfoxide; and 3-hydroxy-4-dodecyloxybutylmethylsulfoxide.

Further examples of suitable anionic surfactants are given in "Surface Active Agents and Detergents" (Vol.I and II, Schwartz, Perry and Berch). Various such surfactants are also generally disclosed in U.S. Pat. No.3,929,678 at column 23, line 58 to column 29, line 23 to Laughlin et al, 12/30 1975.

Cationic surfactant

If the charge on the water-soluble portion of the molecule is positive, the surfactant is classified as a cationic surfactant. Surfactants (e.g., alkylamines) in which the aqueous solution is uncharged unless the pH drops to near neutral or below, and which are cationic at this time, are also included in this group. In theory, it is possible to use compounds containing the "onium" structure R_nX⁺Any combination of elements of Y — synthesizes a cationic surfactant, and it may also include compounds other than nitrogen (ammonium), such as phosphorus (phosphonium) and sulfur (sulfonium). In practice, the field of cationic surfactants is dominated by nitrogen-containing compounds, probably because the synthetic route of nitrogen-containing cationic surfactants is simple and straightforward and results in high yields of products, which can make them less expensive.

Cationic surfactants preferably include and more preferably refer to compounds containing at least one long carbon chain hydrophobic group and at least one positively charged nitrogen. The long carbon chain groups may be directly attached to the nitrogen atom by simple substitution or more preferably indirectly attached to the nitrogen atom through one or more bridging functional groups in so-called interrupted alkylamines and amidoamines. These functional groups may make the molecule more hydrophilic and/or more water dispersible, more readily solubilized by water of the co-surfactant mixture, and/or made water soluble. Additional primary, secondary or tertiary amino groups may be introduced for increased water solubility, or the amino nitrogen may be quaternized with low molecular weight alkyl groups. Further, the nitrogen may be part of a linear or branched moiety of variable unsaturation, or part of a saturated or unsaturated heterocyclic ring. Additionally, the cationic surfactant may contain a complex bond having more than one cationic nitrogen atom.

Surfactant compounds classified as amine oxides, amphoteric surfactants, and zwitterions are typically cationic in nature in solutions of near neutral to acidic pH, and may overlap the classification of surfactants. Polyoxyethoxylated cationic surfactants generally behave like nonionic surfactants in alkaline solutions and cationic surfactants in acidic solutions.

The simplest cationic amines, amine salts and quaternary ammonium compounds can thus be illustrated graphically:

wherein R represents a long alkyl chain, R ', R "and R'" can be long alkyl chains or smaller alkyl or aryl groups or hydrogen, and X represents an anion. For the practical application of the present invention, amine salts and quaternary ammonium compounds are preferred because of their high degree of water solubility.

Most of the large number of commercial cationic surfactants can be subdivided into four major classes and additional subgroups known to those skilled in the art and are described in "Surfactant Encyclopedia," Cosmetics & Toiletries, volume 104(2), pages 86-96 (1989). The first class includes alkylamines and salts thereof. The second class includes alkyl imidazolines. The third class includes ethoxylated amines. The fourth class includes quaternary ammonium salts such as alkylbenzyldimethylammonium salts, alkylbenzene salts, heterocyclic ammonium salts, tetraalkylammonium salts, and the like. Cationic surfactants are known to have various properties that may be beneficial in the compositions of the present invention. These desirable properties may include detergency in compositions at, or below, neutral pH, antimicrobial efficacy, thickening or gelling in conjunction with other agents, and the like.

Cationic surfactants useful in the compositions of the present invention include those having the formula R¹ _mR² _xYLZ, wherein each R is¹Is an organic group containing a linear or branched alkyl or alkenyl group, optionally substituted with up to three phenyl or hydroxyl groups and optionally spaced apart by up to 4 of the following structures or isomers or mixtures of these structures and which contains from 8 to 22 carbon atoms:

R¹the radicals may additionally contain up to 12 ethoxy groups, m being the number 1-3. Preferably, when m is 2, not more than 1R is present in the molecule¹The group has greater than or equal to 16 carbon atoms, or greater than 12 carbon atoms when m is 3. Each R²Is an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms, or a benzyl radical, and has no more than 1R in the molecule²Is benzyl, x has a value of from 0 to 11, preferably from 0 to 6. The remainder of any carbon atom position on the Y group is filled with hydrogen.

Y may be a group including, but not limited to:

or mixtures thereof.

Preferably, L is 1 or 2, and when L is 2, the Y group is selected from R having 1 to 22 carbon atoms and two free carbon single bonds¹And R²Preferably alkylene or alkenylene. Z is a water-soluble anion, for example a sulfate, methylsulfate, hydroxide or nitrate anion, particularly preferably a sulfate or methylsulfate anion, in an amount such that the cationic component is rendered electrically neutral.

Amphoteric surfactant

Amphoteric surfactants contain both basic and acidic hydrophilic groups and organic hydrophobic groups. These ionic entities may be any of the anionic or cationic groups described herein for other types of surfactants. Basic nitrogen and acidic carboxylate groups are typical functional groups employed as the basic and acidic hydrophilic groups. In some surfactants, the sulfonate, sulfate, phosphonate, or phosphate provides a negative charge.

Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains 8 to 18 carbon atoms and one of the aliphatic substituents contains an anionic water-solubilizing group, e.g., carboxy, sulfo, sulfate, phosphate, or phosphono. Amphoteric surfactants are subdivided into two main classes known to the person skilled in the art and are described in "Surfactant Encyclopedia," Cosmetics & Toiletries, Vol.104 (2), pp.69-71 (1989). The first class includes acyl/dialkyl ethylenediamine derivatives (e.g., 2-alkyl hydroxyethyl imidazoline derivatives) and their salts. The second class includes N-alkyl amino acids and their salts. It is envisioned that some amphoteric surfactants are classified into both classes.

Amphoteric surfactants can be synthesized by methods known to those skilled in the art. For example, 2-alkylhydroxyethylimidazolines are synthesized by condensing and ring-closing long-chain carboxylic acids (or derivatives) with dialkylethylenediamine. Commercial amphoteric surfactants are derived by subsequent hydrolysis and ring opening of the imidazoline ring, for example, by alkylation with ethyl acetate. During alkylation, one or both carboxy-alkyl groups are reacted with different alkylating agents to form tertiary amines and ether linkages, thereby producing different tertiary amines.

The long chain imidazole derivatives that may be employed in the present invention generally have the following general formula:

wherein R is an acyclic hydrophobic group containing 8 to 18 carbon atoms and M is a cation to neutralize the charge of an anion, typically sodium. Commercially outstanding imidazoline derived amphoteric surfactants that can be used in the compositions of the present invention include, for example: cocoamphopropionate (Cocoamphopropionate), cocoamphocarboxy-propionate, cocoamphoglycinate, cocoamphocarboxy-glycinate, cocoamphopropyl-sulfonate and cocoamphocarboxy-propionic acid. Preferred amphocarboxylic acids are produced from fatty imidazolines, wherein the functional groups of the dicarboxylic acids in the amphodicarboxylic acid are diacetic acid and/or dipropionic acid.

The carboxy-methylated compounds (glycinates) described several times herein above are referred to as betaines. Betaines are a particular class of amphoteric surfactants discussed herein in the section entitled zwitterionic surfactants.

By making RNH₂Fatty amines with halogenated carboxylic acids to readily prepare long chain N-alkyl amino acids wherein R is C₈-C₁₈Straight chainOr a branched alkyl group. Alkylation of the primary amino group in an amino acid results in secondary and tertiary amines. The alkyl substituent may have an additional amino group that provides more than one reactive nitrogen center. Most commercial N-alkyl amino acids are alkyl derivatives of beta-alanine or beta-N (2-carboxyethyl) alanine. Examples of commercial N-alkyl amino acid amphiphiles useful in the present invention include alkyl beta-amino dipropionate, RN (C)₂H₄COOM)₂And RNHC₂H₄And (4) COOM. Of these, R is preferably an acyclic hydrophobic group containing 8 to 18 carbon atoms, and M is a cation to neutralize the charge of the anion.

Preferred amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acid. More preferred such coconut derived surfactants include an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety (preferably glycine), or combinations thereof as part of their structure; and aliphatic substituents of 8 to 18, preferably 12, carbon atoms. The surfactant may also be considered to be an alkyl amphoteric dicarboxylic acid. Disodium cocoamphodipropionate is one of the most preferred amphoteric surfactants and may be sold under the tradename Miranol^MFBS is commercially available from Rhodia inc. Another most preferred coconut derived amphoteric surfactant having the chemical name disodium cocoamphodiacetate is also sold under the trade name Miranol C2M-SF conc, by Rhodia inc.

A typical list of the amphoteric class and species of these surfactants is given in U.S. Pat. No.3,929,678 to Laughlin and Heuring, 12/30/1975. Further examples are given in "Surface Active Agents and Detergents" (Vol.I and II, Schwartz, Perry and Berch).

The additional surfactants may be present in any detersive amount so long as they do not interfere with the electrostatic, ionic interactions that provide foam stability.

Bleaching agent

The rinse aid may optionally comprise a bleaching agent. Bleaching agents may be used to lighten or whiten the substrate, and may include species that release active halogen, such as Cl, under conditions typically encountered during cleaning₂、Br₂、-OCl^-and/or-OBr^-And the like. Bleaching agents suitable for use may include, for example, chlorine-containing compounds, such as chlorine, hypochlorites, chloramines, or the like. Some examples of halogen-releasing compounds include alkali metal dichloroisocyanurates, chlorinated trisodium phosphate, alkali metal hypochlorates, monochloramine, dichloramine, and the like. Encapsulated chlorine sources can also be used to improve the stability of the chlorine source within the composition (see, e.g., U.S. patents 4618914 and 4830773, the disclosures of which are incorporated herein by reference). The bleaching agent may also include an agent that contains or acts as a source of active oxygen. The active oxygen compound functions to provide a source of active oxygen, for example, active oxygen may be released in an aqueous solution. The active oxygen compound may be inorganic or organic, or may be a mixture thereof. Some examples of active oxygen compounds include peroxy compounds or peroxy compound adducts. Some examples of active oxygen compounds or active oxygen sources include hydrogen peroxide, perborates, sodium carbonate peroxyhydrate, phosphate peroxyhydrate, potassium peroxymonosulfate, and sodium perborate monohydrate and tetrahydrate, with and without activators such as tetraacetylethylenediamine. The rinse aid composition may contain a minor but effective amount of bleach, for example, in some embodiments in the range of up to about 10 wt%, and in some embodiments in the range of from about 0.1 to about 6 wt%.

Activating agent

In some embodiments, the antimicrobial or bleaching activity of the rinse aid can be enhanced by the addition of materials that react with active oxygen to form an activated component when the composition is used. For example, in some embodiments, a peracid or a peracid salt is formed. For example, in some embodiments, tetraacetylethylenediamine may be included in the composition to react with active oxygen and form a peracid or persalt that acts as an antimicrobial agent. Other examples of active oxygen activators include transition metals and compounds thereof, compounds containing carboxylic acid, nitrile, or ester moieties, or other such compounds known in the art. In one embodiment, the activator comprises tetraacetylethylenediamine; a transition metal; a compound containing a carboxylic acid, nitrile, amine or ester moiety; or mixtures thereof.

In some embodiments, the activator component may comprise up to about 75 wt% of the composition, in some embodiments in the range of about 0.01 to about 20 wt%, or in some embodiments in the range of about 0.05 to 10 wt% of the composition. In some embodiments, an activator for an active oxygen compound is combined with active oxygen to form an antimicrobial agent.

In some embodiments, the rinse aid composition includes a solid, such as a solid flake, pellet, or block, and the activator material for active oxygen is combined with the solid. The activator can be incorporated onto the solid by any of a variety of methods for incorporating one solid composition onto another. For example, the activator can be in a solid form that is bound, fixed, glued, or adhered to the solids of the rinse aid composition. Alternatively, a solid activator can be formed around and entrap a solid rinse aid composition. As a further example, the solid activator may be combined with the solid rinse aid composition by a container or package for the composition, such as by a plastic or shrink wrap or film.

Filler material

The rinse aid may optionally contain a minor but effective amount of one or more fillers that do not necessarily function as a rinse and/or cleaning agent by themselves, but may cooperate with the rinse agent to enhance the overall performance of the composition. Some examples of suitable fillers may include sodium chloride, starch, sugars, C₁-C₁₀Alkylene glycols such as propylene glycol and the like. In some embodiments, fillers may be included in amounts up to about 20 wt%, and in some embodiments, in the range of about 1 to 15 wt%. Sodium sulfate is conventionally used as an inert filler.

Anti-redeposition agent

The rinse aid composition may optionally include an anti-redeposition agent that can promote the continued suspension of soils in the rinse solution and prevent the removed soils from redepositing onto the substrate being rinsed. Some examples of suitable anti-redeposition agents may include fatty acid amides, fluorocarbon surfactants, complexed phosphate esters, styrene maleic anhydride copolymers, and cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and the like. The rinse aid composition may comprise up to about 10 wt%, in some embodiments, in the range of about 1 to about 5 wt%, of an anti-redeposition agent.

Dye/odorant

Various dyes, odorants including perfumes, and other aesthetic enhancers may also be included in the rinse aid. Dyes may be included to alter the appearance of the composition, such as FD & C Blue1(Sigma Chemical), FD & C Yellow 5(Sigma Chemical), Direct Blue 86(Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange7(American Cyanamid), Basic Violet 10(Sandoz), Acid Yellow 23(GAF), Acid Yellow 17(Sigma Chemical), Sap Green (Keyston alkali and Chemical), Metalanil Yellow (Keyston alkali and Chemical), Acid 9(Hilton Davis), Sandolan Blue/Acid Blue 182(Sandoz), Hisol Fast Red (Capitol or and Color), fluorpigment Color and 25 (Gedry Color and Green), and the like.

Fragrances or perfumes that may be included in the composition include, for example, terpenoids such as citronellol, aldehydes such as amyl cinnamaldehyde, jasmine perfumes such as C1S-jasmine or benzyl acetate, vanillin, and the like.

Functional polydimethylsiloxane

The composition may also optionally comprise one or more functional polydimethylsiloxanes. For example, in some embodiments, polyoxyalkylene modified polydimethylsiloxanes, nonionic surfactants, or polybetaine modified polysiloxane amphoteric surfactants can be used as additives. In some embodiments, both are linear polysiloxane copolymers to which polyethers or polybetaines have been grafted by a hydrosilation reaction. Some examples of specific siloxane surfactants are known from Union Carbide

Surfactant or from Goldschmidt Chemical Corp

Polyether or polybetaine polysiloxane copolymers and are described in U.S. Pat. No.4,654,161, which is incorporated herein by reference. In some embodiments, the particular silicone used may be described as having, for example, low surface tension, high wetting ability, and excellent lubricity. For example, these surfactants are said to be a few surfactants that are capable of wetting polytetrafluoroethylene surfaces. The siloxane surfactant used as an additive may be used alone or in combination with a fluorochemical surfactant. In some embodiments, fluorochemical surfactants used as additives, optionally in combination with silanes, can be, for example, nonionic fluorinated hydrocarbons such as fluorinated alkyl polyoxyethylene alcohols, fluorinated alkyl alkoxylates, and fluorinated alkyl esters.

Further descriptions of such functional polydimethylsiloxanes and/or fluorochemical surfactants are described in U.S. Pat. Nos. 5,880,088, 5,880,089 and 5,603,776, all of which are incorporated herein by reference. We have found, for example, that the use of certain polysiloxane copolymers in admixture with hydrocarbon surfactants provides excellent rinse aids for glassware. We have also found that certain silicone polysiloxane copolymers and fluorocarbon surfactants in combination with conventional hydrocarbon surfactants also provide excellent rinse aids for glassware. In addition to certain polyoxyalkylene modified polydimethylsiloxane and polybetaine polysiloxane copolymers which are about equally effective, such combinations have been found to be superior to the individual components. Thus, some embodiments include polysiloxane copolymers alone, and the combination with fluorocarbon surfactants can involve polyether polysiloxanes, nonionic siloxane surfactants. The amphoteric silicone surfactant, the polybetaine polysiloxane copolymer, can be used alone as an additive in a rinse aid to provide the same results.

In some embodiments, the composition may comprise up to about 10 wt% of the functional polydimethylsiloxane. For example, some embodiments may comprise a range of about 0.1 to 10 weight percent of a polyoxyalkylene modified polydimethylsiloxane or polybetaine modified polysiloxane, optionally in combination with about 0.1 to 10 weight percent of a fluorinated hydrocarbon nonionic surfactant.

Wetting agent

The composition may also optionally comprise one or more humectants. Humectants are substances that have an affinity for water. The humectant may be provided in an amount sufficient to help reduce the visibility of the film on the surface of the substrate. The visibility of films on the substrate surface is a particular concern when the rinse water contains more than 200ppm total dissolved solids. Thus, in some embodiments, when the rinse water contains more than 200ppm total dissolved solids, the humectant is provided in an amount sufficient to reduce the visibility of the film on the surface of the substrate compared to a rinse agent composition that does not contain the humectant. The term "aqueous solid film-forming" or "film-forming" refers to the presence of a visible, continuous layer of a substance on the surface of a substrate that gives the appearance that the surface of the substrate is not clean.

Some exemplary humectants that can be used include those materials that contain greater than 5 wt% water (based on dry humectant) equilibrated at 50% relative humidity and room temperature. Exemplary humectants that can be used include glycerin, propylene glycol, sorbitol, alkyl polyglycosides, polybetaine polysiloxanes, and mixtures thereof. In some embodiments, the rinse agent composition may comprise up to about 75% of a humectant, based on the total composition, and in some embodiments, in the range of about 5 wt% to about 75 wt%, based on the weight of the composition.

Other ingredients

A wide variety of other ingredients may also be included for providing a particular composition being formulated to include a desired property or functionality. For example, the rinse aid may include other active ingredients, such as pH modifiers, buffers, cleaning enzymes, carriers, processing aids, or the like.

In addition, the rinse aid can be formulated such that the rinse water will have a desired pH during use in an aqueous operation, such as an aqueous cleaning operation. For example, compositions designed for use in rinsing may be formulated such that the rinse water will have a pH in the range of from about 3 to about 5 or in the range of from about 5 to about 9 during use in an aqueous rinsing operation. In some embodiments, the liquid product formulation has a pH (10% dilution) ranging from about 2 to about 4. Techniques for controlling the pH at the recommended usage level include the use of buffers, bases, acids, and the like, and are well known to those skilled in the art.

Processing and/or preparation of compositions

The solid composition of the present invention can be prepared by an advantageous method of compressing the solid composition. Specifically, in the forming process, the liquid and solid components are introduced into the final mixing system and continuously mixed until the components form a substantially homogeneous semi-solid mixture with the components distributed throughout the mass thereof. In an exemplary embodiment, the components are mixed in the mixing system for at least about 5 seconds. The mixture is then discharged from the mixing system into or through a die, press or other forming device. The product is then packaged. In an exemplary embodiment, the solid shaped composition begins to harden in about 1 minute to about 3 hours. In particular, the formed composition begins to harden in about 1 minute to about 2 hours. More particularly, the formed composition begins to harden in about 1 minute to about 20 minutes.

The process of the present invention produces a stable solid without the use of melting and hardening melts as in conventional casting. Forming a melt requires heating the composition to melt it. Heat may be applied externally or may be generated by a chemical exotherm, for example from mixing caustic (sodium hydroxide) and water. Heating the composition consumes energy. Handling hot melts requires safety precautions and equipment. Further, hardening the melt requires cooling the melt within a vessel to harden the melt and form a cast solid. Cooling requires time and/or energy. In contrast, the method of the present invention may utilize ambient temperature and humidity during hardening or curing of the composition of the present invention. The solids of the invention are held together not by melt hardening but by a binder that is produced within the mixed particles and is effective for producing a stable solid.

Although the present invention can be advantageously formed into a solid by pressing, other methods of solid formation, such as extrusion, casting, and the like, can also be used.

In exemplary embodiments, one or more component agents may be combined and mixed under high shear using a single or twin screw extruder to form a homogeneous mixture. In some embodiments, the processing temperature is at or below the melting temperature of each component. The processed mixture may be dispensed from the mixer by pressing, shaping, extruding or other suitable means whereby the composition hardens into a solid form. The matrix structure may be characterized according to methods known in the art in terms of its hardness, melting point, material distribution, crystal structure, and other similar properties. In general, the solid compositions processed according to the methods of the present invention are substantially uniform and dimensionally stable with respect to the distribution of the ingredients throughout their mass.

The resulting solid composition may have various forms including, but not limited to: extruded, molded or formed solid pellets, blocks, tablets, powders, granules, flakes; or the formed solid, may then be comminuted or formed into a powder, granule or flake. In an exemplary embodiment, the extruded pellet formed weighs between about 50g and about 250g, the extruded solid weighs greater than or equal to about 100g, and the solid block formed weighs between about 1 and about 10 kg. The solid composition provides a stable source of functional material. In preferred embodiments, the solid composition may be dissolved, for example, in an aqueous or other medium to produce a concentrated and/or use solution. The solution may be directed to a storage container for subsequent use and/or dilution, or may be applied directly to a point of use.

In certain embodiments, the solid rinse aid composition is provided in unit dosage form. Unit dose refers to a unit of solid rinse composition sized such that the entire unit is used in a single wash cycle. When the solid cleaning composition is provided as a unit dose, it may have a mass of from about 1g to about 50 g. In other embodiments, the composition may be a solid, pellet, or tablet having a size of about 50g to 250g, greater than or equal to about 100g, or about 40g to about 11,000 g.

In other embodiments, the solid rinse aid composition is provided in the form of a multi-use solid, such as a block or a plurality of pellets, and can be used repeatedly to produce an aqueous rinse composition for multiple wash cycles. In certain embodiments, the solid rinse aid composition is provided as a solid having a mass of about 5g to 10 kg. In certain embodiments, the solid rinse aid composition in a multiple use form has a mass of about 1-10 kg. In a further embodiment, the solid rinse aid composition in multiple use form has a mass of from about 5kg to about 8 kg. In other embodiments, the solid rinse aid composition in a multiple use form has a mass of from about 5g to about 1kg or from about 5g to 500 g.

Packaging system

The solid rinse aid composition may, but need not, be incorporated into a packaging system. The packaging container produced may be rigid or flexible and comprises any material suitable for containing the produced composition, such as glass, metal, plastic film or sheet, cardboard composites, paper and the like. The rinse aid composition may be allowed to harden in a package or may be packaged in a commonly available package after the solids are formed and sent to a distribution center before shipment to the consumer.

For solids, advantageously, in at least some embodiments, because the rinse agent is processed at or near ambient temperature, the temperature of the processed mixture is sufficiently low that the mixture can be cast or extruded directly into a container or other packaging system without structurally damaging the material. As a result, a wider variety of materials can be used to make the container than those of the compositions used for processing and dispensing in the molten state. In some embodiments, the package for containing the rinse aid is made from a flexible, easily openable film material.

Dispensing/use of rinse aid

The rinse aid may be dispensed as a concentrate or as a use solution. Additionally, the rinse aid concentrate may be provided in solid form or in liquid form. Typically, it is contemplated that the concentrate will be diluted with water to provide a use solution that is then applied to the surface of a substrate. In some embodiments, the aqueous use solution may contain less than or equal to about 2,000ppm of active material, or less than or equal to about 1,000ppm of active material, or from about 10ppm to about 500ppm of active material, or from about 10 to about 300ppm, or from about 10-200ppm of active material.

The application solution may be applied to the substrate during a rinse application, such as during a rinse cycle, such as in a warewasher, car wash application, institutional healthcare surface cleaning, or the like. In some embodiments, the use solution may be formed from a rinse agent contained within the cleaning machine, for example, on a dish rack. The rinse agent may be diluted and dispensed from a dispenser mounted on or within the machine, or by a separate dispenser mounted separately but in cooperation with the washing machine.

For example, in some embodiments, a liquid rinse agent can be dispensed by introducing a compatible package containing a liquid material into a dispenser adapted to dilute the liquid with water to an end-use concentration. Some examples of dispensers for liquid rinses of the present invention are DRYMASTER-P sold by Ecolab inc.

In other exemplary embodiments, the solid product can be conveniently dispensed by placing the solid material in a container or contained without a housing into a spray-type dispenser, such as the ECOTEMP Ring Injection Cylinder system controlled by volumetric SOL-ET manufactured by Ecolab Inc., St.Paul, Minn. Such dispensers cooperate with warewashers during the rinse cycle. When required by the machine, the dispenser directs water onto the solid block of rinse agent, which water is effective to dissolve a portion of the block, thereby producing a concentrated aqueous rinse solution, which is then fed directly into the rinse water to form the aqueous rinse agent. An aqueous rinse agent is then contacted with the surface to effect a thorough rinse. This dispenser and other similar dispensers can control the effective concentration of the active portion in the aqueous rinse agent by measuring the volume of material dispensed, the actual concentration of material in the rinse water (electrolyte measured with electrodes), or by measuring the spray time on the casting block. In general, the concentration of the active portion in the aqueous rinse agent is preferably the same as described above for the liquid rinse agent. Some other embodiments of spray-type dispensers are disclosed in U.S. Pat. Nos. 4,826,661, 4,690,305, 4,687,121, 4,426,362 and in U.S. Pat. Nos. Re 32,763 and 32,818, the disclosures of which are incorporated herein by reference. One example of a particular product shape is shown in FIG. 9 of U.S. patent application No.6,258,765, which is incorporated herein by reference.

The compositions of the present invention are particularly beneficial for use with hard water. The composition can provide good rinsing and levels of up to 20gpg water hardness.

In some embodiments, it is believed that the rinse aid compositions of the present invention can be used in an aqueous environment containing high solids in order to reduce the appearance of visible films resulting from the level of dissolved solids provided in the water. Generally, water containing high solids is considered to be water having a Total Dissolved Solids (TDS) content of over 200 ppm. In some places, industrial water contains over 400ppm total dissolved solids, and even over 800 ppm. Applications where the presence of a visible film after washing a substrate is a particular problem include the restaurant or warewashing industry, the car wash industry, the health care instrument reprocessing and cart wash sectors, and general cleaning of hard surfaces.

When used in such automated washing applications as warewashing machines and health care instruments and hand cart washing machines, the rinse aid should provide effective stripping and low sudsing performance. It is believed that the rinse aid compositions of the present invention are formulated to control the above-mentioned problems at risk.

Method and composition for cleaning, rinsing and antimicrobial treatment of medical carts, cages, instruments or devices

The methods and solid rinse aid compositions of the present invention can be used to clean medical carts, cages, instruments or devices in a medical or healthcare environment. Typically, cleaning a medical cart, cage, instrument or device comprises contacting the medical cart, cage, instrument or device with an aqueous cleaning composition, and then rinsing or contacting it with a rinse solution containing a solubilized rinse aid of the present invention, in accordance with the present invention. The method can also involve antimicrobially treating the medical vehicle, cage, instrument or device by contacting with an aqueous antimicrobial composition formed by dissolving or suspending a solid antimicrobial composition, preferably a solid quaternary ammonium or solid halogen antimicrobial composition.

Contact with the cleaning composition may occur by manual application in a wash area or compartment or by application via a cart, cage, instrument or device washing apparatus. In a manual process, rinsing and/or antimicrobial treatment may also take place within the washing zone or compartment or within a separate zone or compartment. A typical cart, cage, instrument or device washing apparatus includes a washing station that applies a cleaning composition. Typically, such washing devices also include a rinse station that can rinse the cart, cage, instrument or device with water or other suitable rinse compositions, such as solid neutral or neutral rinse compositions. This washing device may also optionally include an antimicrobial treatment station that contacts the cart, cage, instrument or device with a dissolved solid antimicrobial composition, such as a solid quaternary ammonium salt or a solid halogen antimicrobial composition. The washing device may perform one or more of the washing, rinsing and/or antimicrobial treatment steps at one, two, three or more stations.

The methods and compositions of the present invention for rinsing medical carts, cages, instruments or devices can be used to rinse medical carts, cages, instruments or devices made of various materials within a medical or healthcare environment.

Typically, rinsing the medical cart, cage, instrument, or device comprises rinsing the medical cart, cage, instrument, or device with an aqueous rinse composition formed by dissolving or suspending the solid rinse composition of the present invention.

Contact with the rinse composition may occur by manual application in a wash area or compartment or by application through a cart, cage, instrument or device wash and/or rinse apparatus. In a manual approach, the cleaning and/or antimicrobial treatment may also take place within the rinse zone or compartment or within a separate zone or compartment. A typical cart, cage, instrument or device washing apparatus includes a rinse station that can rinse the cart, cage, instrument or device with a liquid rinse composition formed from a solid neutral or neutral rinse composition. This washing device may also optionally include washing and/or antimicrobial treatment stations.

The antimicrobial composition used for antimicrobial treatment of an artificial or mechanical medical cart, cage, instrument or device can be a solid antimicrobial composition, preferably a solid quaternary ammonium or solid halogen antimicrobial composition, as described in more detail herein below.

Method for cleaning medical vehicle

The cleaning of the medical vehicle can be realized manually or by adopting a machine. Manual medical cart cleaning may include preparing an application composition of the solid cleaning composition, and applying it to the medical cart. Application typically involves wiping or scraping the medical cart with a brush, towel or sponge soaked with the cleaning composition. Applying may also include spraying the cart with the application composition. Artificial medical cart cleaning may also include preparing an application composition of a rinse composition, preferably a neutral rinse composition, and applying it to the medical cart. Applying the rinse composition may include spraying, pouring, or wiping the application composition onto a cart. Artificial medical cart cleaning may also include preparing a solid antimicrobial composition and an application composition, preferably a solid quaternary ammonium or solid halogen antimicrobial composition, and applying it to the medical cart. Applying the antimicrobial composition may comprise spraying, pouring or wiping the application composition on a cart. The medical cart is typically dried after rinsing, either manually or by air drying.

Machine cleaning the medical cart any of a variety of configurations of medical cart cleaning devices may be used. Such devices may be modified to dispense solid detergents, rinse aid compositions of the present invention and/or antimicrobial compositions. The medical cart cleaning apparatus typically includes at least one chamber for housing the medical cart during washing, rinsing and/or antimicrobial treatment.

Smaller medical cart cleaning apparatuses typically include a single chamber sized to accommodate, for example, 1-3 medical carts. The medical cart may be introduced into the smaller device by an operator through a door or other coverable opening in the chamber. The device then performs one or more wash, rinse, antimicrobial treatment, and/or drying cycles on the cart within the chamber. Washing is typically carried out by spraying the medical vehicle with the application detergent composition. Rinsing is typically performed by spraying the medical vehicle with an application rinse composition. Optionally, the antimicrobial treatment may be performed by spraying the medical vehicle with the applied antimicrobial composition. Drying can be carried out by blowing ambient or heated air, or by treatment with steam. The medical cart may be removed from the chamber by the operator through the same door or other coverable opening or through an exit door or other coverable opening on the opposite side of the device.

Larger medical cart cleaning apparatuses typically include a transport apparatus that transports one or several carts through one or more chambers including washing, rinsing, optionally antimicrobial treatment and/or drying stages. Such a medical vehicle cleaning device may resemble an auto-induction car wash that is sized and configured for cleaning medical vehicles other than automobiles. Typically, the cart is transported by rail or rail means through the washing, rinsing, optional antimicrobial treatment and/or drying sections while being inclined at an acute angle to the horizontal with its doors (if any) open. This tilting keeps the door open and allows liquid to drain from any normal horizontal surface of the cart. The access opening of the larger medical cart cleaning device may be covered, for example, by a door or with a suspended plastic strip that allows the cart to enter, but keeps the application composition within the device. The washing station typically sprays the medical vehicle with the application wash composition. Rinse stations typically spray the medical cart with a rinse composition. The optional antimicrobial treatment station typically sprays the medical vehicle with the antimicrobial composition. At the drying section, a blower blows ambient or heated air over the cart, or the cart is steamed. Alternatively, the cart can be removed from the device and towel dried. One or more stations may be at different, overlapping or the same location. The outlet from the device may be covered in the same way as the inlet.

The robotic cart washer may use an apply composition/wash cycle of up to about 30 to about 40 gallons of cleaning composition, an apply composition/rinse cycle of up to about 30 to about 40 gallons of rinse composition, and optionally an apply antimicrobial composition/antimicrobial treatment cycle of up to about 30 to about 40 gallons. The actual amount of cleaning, rinsing or antimicrobial composition used will be based on the judgment of the user and will depend on factors such as the particular product formulation of the composition, the concentration of the composition, the number of soiled carts to be cleaned and the degree of soiling of the carts.

Other wheeled medical devices or utensils may also be washed using the machine for washing medical carts, such as wheelchairs, wheel carriers, such as those holding IV bags, tubing and pumps, wheeled racks and the like.

The foregoing description provides a basis for understanding the broad satisfaction of conditions and boundaries of the present invention. The following examples and test data provide an understanding of certain specific embodiments of the present invention. These examples do not limit the scope of the invention. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are by weight, and all reagents used in the examples were obtained or obtainable from the chemical suppliers described below, or may be synthesized by conventional techniques.

Examples

The following materials were used in the examples that follow:

plurafac SLF-180: fatty alcohol alkoxylates

Dehypon GRA: fatty alcohol alkoxylates

Preservative from Dow Chemical by Kathon, having active ingredients 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one

Sodium xylene sulfonate

Citric acid

The control was water (0 or 17gpg, depending on the purpose of the experiment)

Commercial rinse aid a is a rinse aid commercially available from Steris.

Commercial rinse aid B is a phosphoric acid-containing rinse aid commercially available from Getinge.

Commercial rinse aid C is a liquid rinse aid commercially available from Ecolab.

Commercial rinse aid D is a solid rinse aid commercially available from Ecolab that does not contain any hardness or TDS components.

The compositions of the present invention were formulated and tested according to the following table.

Example 1

Hardness tests were performed according to the following method using commercially available rinse aids and compositions of the present invention.

Hardness test (17 grain water)

Stainless steel 304 and glass microscope slide

1. 15 samples were obtained for each: stainless steel 304#4 face (finish) and glass (microscope slide).

2. With soft sponges and

each sample was thoroughly washed. Rinse with 5 grains of water and DI water. Lay flat and dry overnight.

3. A 308 oz glass french square vial was obtained.

4. Each vial was rinsed with 5 grains of water and DI water. Lay flat and dry overnight.

5. The following chemicals were prepared.

Sample (I)	Description of the invention		Water condition
				1	Control		17gpg
2	Commercial rinse aid A	2000ppm	17gpg
				3	Commercial rinse aid B	2000ppm	17gpg
4	Commercial rinse aid C	500ppm	17gpg
				5	Commercial rinse aid C	1000ppm	17gpg
6	Commercial rinse aid C	2000ppm	17gpg
				7	Commercial rinse aid D	50ppm	17gpg
8	Commercial rinse aid D	125ppm	17gpg
				9	Commercial rinse aid D	200ppm	17gpg
10	Composition A of the invention	50ppm	17gpg
				11	Composition A of the invention	125ppm	17gpg
12	Composition A of the invention	200ppm	17gpg
				13	Composition B of the invention	50ppm	17gpg
14	Composition B of the invention	125ppm	17gpg
				15	Composition B of the invention	200ppm	17gpg

6. To 2 independent glass french square vials was added 200ml of control (17 grains of water) together with the surface. Stainless steel 304#4 side (finish) and glass (microscope slide) were in each individual vial. The vials were labeled.

7. Repeat step 6 with 17 grains of water for all chemicals.

8. All vials were placed in a 70 ℃ temperature controlled oven and allowed to incubate for 8 hours.

The results are shown in fig. 1. It can be seen that the compositions of the present invention perform better than other rinse aid products as observed by image analysis means.

Example 2

Next, the performance of the different rinse aids was tested at different levels of total dissolved solids according to the method described below.

Total dissolved solids (1000ppm NaCl in 0 grain water)

Stainless steel 304#4 surface

1. Before starting, the inclination tester was preheated to 150 ° F.

2. 15 samples were obtained for each: stainless steel 304#4 face (3x5 inches).

3. With soft sponges and

4. The following chemicals were prepared in a 1L flask:

5. add 1000mL of control (0 grain water +1000ppm NaCl) to a 1L beaker; the beaker was placed in a microwave oven and heated to 150 ° F. The beaker was then placed in a water bath of a tilt angle tester (water temperature set at 150 ° F).

6. The tilt tester was set to allow the sample in solution to soak statically for 1 minute.

7. After 1 minute, the sample was suspended in air for 2 minutes as it came out of solution and lifted the support plate (plank) all the way up.

8. After 2 minutes, the sample was taken out of the inclination tester and set on a stand in a vertical position to be cooled to room temperature.

9. Steps 4-7 were repeated with 0 grains of water for all chemicals.

The results are shown in fig. 2. It can be seen that the compositions of the present invention perform better than all other rinses at increasing levels of total dissolved solids in the rinse water.

Example 3

Material Corrosion/compatibility test (0 grain water)

1. A sample of the desired substrate material (aluminum) was obtained.

2. Each sample was thoroughly washed with soft sponge and a commercially available detergent. Rinse with 0 grain water and DI water. Lay flat and dry overnight.

3. 8oz glass French square vials were obtained.

4. Each vial was rinsed with 0 grains of water and DI water, laid flat and dried overnight.

5. The following chemicals were prepared:

6. to 2 independent glass french square vials, 200mL of control (0 grain water) was added along with the sample with the material to be studied; example (c): aluminum 6061 and aluminum 1100. Each vial was labeled.

7. Step 6 was repeated with 0 grain water for each chemical.

8. All vials were placed in a 160 ° F oven and allowed to incubate for 8 hours.

9. Samples were taken from each test solution with clean forceps.

10. In each test solution, Al concentration was analyzed using Inductively Coupled Plasma (ICP) spectroscopy, respectively.

Fig. 3 shows the results for the Al coupon, and it can be seen that the compositions of the present invention exhibit very little corrosion. Other metal samples tested showed that the formulations of the invention were compatible with all metals.

Example 4

The following tank solutions (Sump solution) were tested for foaming tendency in use.

Tank solution agitation was simulated using a reverse foam test. Rinse additive was added to the graduated cylinder and the resulting foam was measured after 10 180 degree reversals.

Device and material:

1. 250mL graduated cylinder with stopper

2. Room temperature 5 grains water.

The process comprises the following steps:

1. graduated cylinders were rinsed thoroughly with soft water, followed by DI water and air dried.

2. Simulated tank solutions of the desired 5% and/or 10% solids rinse aid were prepared and stirred until dissolved.

3. Pour 150mL of 5% or 10% commercial rinse aid solution or liquid into a graduated cylinder and cap with a bottle stopper.

4. By rotating the cylinder about 180 degrees from vertical⁰And back to the vertical position.

5. This action was repeated 10 times at a frequency of about 1 cycle/second.

6. When the cylinder was placed on a flat surface, the foam height was immediately recorded. The foam height was read as the difference between the top of the liquid level to the top of the foam level. The top of the foam level is the level at which the foam is opaque and cannot be viewed by the operator through the cylinder.

7. For each chemical, repetition was performed.

The results are shown in fig. 4 and again demonstrate that the formulation of the present invention is better than the foam control.

Other embodiments

It is to be understood that the invention has been described in conjunction with the detailed description thereof, which is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims.

In addition, the contents of all of the patent publications discussed above are incorporated by reference in their entirety.

It is to be understood that whenever values and ranges are provided herein, all values and ranges encompassed within that range are meant to be encompassed by the present invention. Moreover, all values falling within these ranges, as well as the upper and lower limits of the ranges of values, are also encompassed by the present application.

Example 5

Finally, the following procedure was used to evaluate the foaming tendency of the different rinse additives at the application concentration.

Evaluation of foam rinse additive

Device and material:

glewwe foam unit

Hot soft water

Boats of small and large weight (boats)

The process comprises the following steps:

the Glewwe unit was rinsed thoroughly by filling with soft water and running the pump. The device was discharged by opening the gate valve. If foam is generated during this cleaning process, the procedure is repeated until there is no foam.

Close the gate valve and remove the top cover.

Packing the column (chimney) with hot, soft water to the bottom of the ruler (base of the ruler), 0", 3L water

Open the pump switch and adjust the temperature to 100, 120, 140 or 160 ° F by adding either cold or hot soft water. The test was conducted at 160 ° F.

Adjust the pressure to 6psi by using a knob located below the pressure gauge.

Stop pumping.

Readjust the water level to 0 "if necessary.

Open the pump, allow the pressure to reach 6psi, and add the desired concentration of rinse additive or surfactant combination to be evaluated. Note the time.

After 1 minute, the pumping was stopped and the foam height, and the characteristics at times 0, 15 seconds and 1 minute were recorded.

Open the gate valve to drain the machine and repeat the cleaning process.

Instability-rapid collapse of the foam (less than 15 seconds)

Partial stabilization-slow collapse of foam (within 1 minute)

Stabilization-foam hold for several minutes

The results are shown in fig. 5. The graph shows that the foam condition at the pumped concentration of the dispenser is better than the control. Foam control is a very important aspect of rinse aids.

Claims

1. A solid rinse aid composition comprising:

a solid acid;

one or more short chain alkylbenzene and/or alkylnaphthalene sulfonates selected from sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkylnaphthalene sulfonate and sodium butylnaphthalene sulfonate; and

one or more nonionic surfactants.

2. The composition of claim 1, wherein the short-chain alkylbenzene and/or alkylnaphthalene sulfonate is sodium xylene sulfonate or sodium cumene sulfonate.

3. The composition of claim 1, wherein the short chain alkylbenzene and/or alkylnaphthalene sulfonate is present in an amount from about 50% to about 80% by weight.

4. The composition of claim 1, further comprising a preservative.

5. The composition of claim 1, further comprising a chelating agent.

6. The composition of claim 5, wherein the chelating agent is GLDA.

7. The composition of claim 1, wherein the acid is citric acid.

8. The composition of claim 1, wherein the nonionic surfactant is a low foaming surfactant.

9. The composition of claim 8, wherein the low foaming surfactant is present in an amount of about 5 wt% to about 30 wt%.

10. The composition of claim 1, wherein the solid acid is present in an amount of about 5 wt% to about 40 wt%.

11. A method of making a solid rinse aid composition, the method comprising:

a. mixing a solid acid, a nonionic surfactant and a short chain alkylbenzene and/or alkylnaphthalene sulfonate;

b. placing the mixture, and thereafter

c. Mixing, for example, preservatives, additional surfactants, water, dyes, and the like, within any liquid component of the rinse aid;

d. forming a solid with the rinse aid mixture.

12. The method of claim 11, wherein said forming a solid is by pressing.

13. The method of claim 11, wherein said forming a solid is by extrusion.

14. The method of claim 11, wherein the mixture is left for greater than or equal to 1 day.

15. A method of rinsing a hard surface in a cleaning application, the method comprising:

a. providing a solid rinse aid composition of claim 1;

b. contacting the rinse aid composition with water to form a use solution; and

c. applying the application solution to a hard surface.

16. The method of claim 15, wherein the use solution comprises less than or equal to 2,000ppm of active material.

17. The method of claim 15, wherein the contacting is by directing water onto a solid block of rinse aid.

18. The method of claim 15, wherein the solid rinse aid is dissolved into the use solution by the contacting.

19. The method of claim 15, wherein said hard surface comprises metal, glass, plastic, ceramic, or ceramic tile.