Patent Grant
8293699
This invention relates to a hard surface cleaning composition containing a hydrophilizing agent and a method for cleaning hard surfaces, such as ceramic, tiling, metal, melamine, formica, plastic, glass, mirror, and other industrial, kitchen and bathroom surfaces, with a hard surface cleaning composition containing a hydrophilizing agent. More particularly, the present invention employs mono-, di-, and polyol phosphate esters (like PEG phosphate esters, PPG phosphate esters, glycerine phosphate esters) to clean the surface properties of hard surfaces by applying the phosphate esters onto these surfaces. Also, the invention relates to providing long-lasting anti-adhesion and/or anti-deposition properties to hard surfaces.
The present application for patent for the claimed invention the claimed invention was made by or on behalf of parties to a joint research agreement between The Proctor & Gamble Co. along with its affiliates and Rhodia HPCII S.A. along with its affiliates
Detergent or cleaning compositions make it possible to clean industrial and domestic hard surfaces. Cleaning compositions generally contain surfactants; solvents, for example alcohol, to possibly facilitate drying; sequestering agents; and bases or acids to adjust the pH. The surfactants are generally nonionic and anionic combinations, or nonionic and cationic combinations. A frequent disadvantage of these cleaning compositions is that the subsequent contact of the hard surface with water leads to the formation of hard water deposits when the surface dries. Moreover, conventional cleaning compositions merely clean the surface, but do little to prevent future soiling.
A solution to this problem was proposed in EP-A-1 196 527, EP-A-1 196 528 and EP-A-1 196 523. These patents propose to deposit on the hard surface a cleaning composition containing a water-soluble amphoteric organic copolymer derived from a cation monomer and an anion or potentially anionic monomer in a sufficient quantity to make the surface absorbent or to improve the hydrophilicity of the surface. This is done to obtain the smallest possible contact angle between the treated surface and a water drop and to ensure the water retention in the vicinity of the treated surface lasts after treatment.
US Patent Application Publication No. 2006/0217286, incorporated herein by reference, discloses compositions for cleaning or rinsing hard surfaces in an aqueous or aqueous/alcoholic medium comprising at least one polybetaine for contributing to the surfaces antideposition and/or antiadhesion properties with regard to soiling substances capable of being deposited on said surfaces.
Many different approaches can be used to change the surface energy (hydrophilicity/hydrophobicity) and thus the adhesion properties of a given material. For example chemical treatments like plasma or ozone for polyethylene and polypropylene surfaces to increase hydrophilicity. Or physico-chemical treatments like the adhesion of surfactant molecules onto hydrophobic surfaces can alter them hydrophilic. Also the adhesion of polymers onto surfaces is used to change surface properties. One specific example would be the adsorption of polyethylene oxide (PEG). In all cases specific chemical groups are attached to the initial surface. These chemical groups change the surface energy and thus the adhesion properties and/or other surface properties like tendency of fouling or slip.
Two of the main disadvantages of the above mentioned treatments are poor durability and/or they are expensive/technically sophisticated. One example of the former is surfactants. They get easily washed away from the surface upon rinsing with e.g. water. An example for the latter is plasma or ozone treatment. Further, for some applications no satisfying solution is found up to date.
Materials that have a low surface energy, such as, for example, polyolefin polymers, have hydrophobic surfaces. The hydrophobic properties of such materials are not desirable in some applications and methods for hydrophilizing low surface energy substrates, including treatment with surfactants and/or high energy treatment, are known. Each of these methods has significant limitations. Surfactant treatments tend to wash off when a treated substrate is exposed to water and the charges imparted to the surface of a treated substrate by high energy treatment tend, particularly in the case of a thermoplastic polymer substrate, to dissipate. The hydrophilic properties of such surfactant treated substrates and high energy treated substrates thus tend to exhibit limited durability. Furthermore, the surfactants that are rinsed off of a treated substrate by exposure to water alter the properties of the water, such as lowering the surface tension, which may also be undesirable.
It would be advantageous to provide a cleaning composition for hard surfaces which imparts improved anti-deposition and/or anti-adhesion properties to a hard surface, particularly anti-soil deposition and anti-soil adhesion properties. It would also be advantageous to provide a cleaning composition for hard surfaces which prevents or minimizes hard water deposits, soap scum, and other mineral deposits. Accordingly, there is a need for more durably hydrophilizing low surface energy hard substrates.
In a first aspect, the present invention is directed a composition for the cleaning in an aqueous or aqueous/alcoholic medium of hard surfaces comprising at least one surface-active agent and at least one mono-, di-, and polyol phosphate ester (for example PEG phosphate esters, PPG phosphate esters, glycerine phosphate esters). For purposes of this specification a compositions for cleaning includes compositions for cleaning and compositions for rinsing.
More particularly in this first aspect, the present invention is directed to a hard surface cleaning composition, comprising:
If desired the composition may further comprise:
In a second aspect, the present invention is directed to a method for hydrophilizing a hard surface having a hydrophobic surface, comprising treating at least a portion of such hydrophobic surface with a treatment composition comprising an organophosphorus material, a surface-active agent and optionally a vinyl alcohol, as described above to deposit a hydrophilizing layer on such portion of such hydrophobic surface.
In a third aspect the present invention is directed to a cleaning composition for pre-treating a hard surface of an article. Consistent with this, the present invention is directed to a pre-treated article, comprising:
If desired the layer may further comprise:
The treatment of surfaces with the phosphate esters results in changed surface properties. The reduced adsorption of oil (like octadecane) onto calcium carbonate facilitates the extraction of grease or oil from porous stone materials. Treated facades or statues made from, for example, calcium carbonate stone can be more easily cleaned or show a self-cleaning effect due to a reduced adsorption of soil from rain and the air onto the facade or statue.
The invention has a number of advantages. The phosphate esters are relatively inexpensive and easy to manufacture in comparison to many polymers used for surface treatments. The treatment is easy and fast (usually from aqueous solution), especially compared to, for example, plasma, ozone, or other chemical treatments. The coating is significantly more durable compared to surfactant systems. While not wishing to be limited by theory, it is theorized this is due to a specific binding of the phosphate group onto the surface. For example, surfaces with calcium ions show a durable adsorption of phosphate groups. Further, surfactants can not be used for surfaces which are not sufficiently hydrophobic. The hydrophobic surfactant groups cannot adsorb onto such surfaces. Then, for example, polyethylene glycol (PEG) or polypropylene glycol (PPG) might be used instead of surfactants. But coatings with PEG or PPG are not durable either. Again, the durability of the phosphate esters is significantly improved compared to, e.g., PEG or PPG homopolymers. The phosphate esters are considered non-toxic, non-irritant to skin and biodegradable.
In a first aspect, the present invention is directed a composition for the cleaning in a solvent medium for hard surfaces comprising at least one surface-active agent and at least one mono-, di-, and polyol phosphate ester (for example PEG phosphate esters, PPG phosphate esters, glycerine phosphate esters). For purposes of this specification a compositions for cleaning includes compositions for cleaning and compositions for rinsing.
The present invention is directed to a hard surface cleaning composition, comprising:
If desired the composition may further comprise:
According to the present invention, deposition on a hard surface, via a cleaning formulation, of mono-, di-, and polyol phosphate esters (like PEG phosphate esters, PPG phosphate esters, glycerine phosphate esters) makes it possible to confer, on the surface thus treated, persistent antideposition and/or antiadhesion properties with regard to soiling substances; in addition, the presence of mono-, di-, and polyol phosphate esters (like PEG phosphate esters, PPG phosphate esters, glycerine phosphate esters) makes it possible to improve the cleaning ability of the formulation.
Use of mono-, di-, and polyol phosphate esters (like PEG phosphate esters, PPG phosphate esters, glycerine phosphate esters) changes the surface properties of several surfaces by adsorption of the phosphate esters onto these surfaces. The treatment of the surfaces in most cases is simply by adsorption from aqueous solutions. For example, the treatment of calcium carbonate crystal is done by immersing the crystal in an aqueous solution of e.g. PEG400 phosphate ester (e.g. 1 wt %, pH 6-7). A successful adsorption onto the crystal and a respective change of the surface properties is shown by measuring the contact angle of octadecane droplets under water. A low contact angle is observed for the untreated crystal (i.e. good adsorption of the oil onto the crystal) and a high contact angle is observed for the treated crystal (i.e. poor adsorption of the oil onto the crystal).
As used herein, the terminology “hydrophobic surface” means a surface that exhibits a tendency to repel water and to thus resist being wetted by water, as evidenced by a water contact angle of greater than or equal to 70°, more typically greater than or equal to 90°, and/or a surface free energy of less than or equal to about 40 dynes/cm.
As used herein, the terminology “hydrophilic surface” means a surface that exhibits an affinity for water and to thus be wettable by water, as evidenced by a water contact angle of less than 70°, more typically less than 60° and/or a surface energy of greater than about 40 dynes/cm, more typically greater than or equal to about 50 dynes/cm.
As used herein in reference to a hydrophobic surface, the term “hydrophilizing” means rendering such surface more hydrophilic and thus less hydrophobic, as indicated by a decreased water contact angle. One indication of increased hydrophilicity of a treated hydrophobic surface is a decreased water contact angle with a treated surface compared to the water contact angle with an untreated surface.
As used herein in reference to a substrate, the terminology “water contact angle” means the contact angle exhibited by a droplet of water on the surface as measured by a conventional image analysis method, that is, by disposing a droplet of water on the surface, typically a substantially flat surface, at 25° C., photographing the droplet, and measuring the contact angle shown in the photographic image.
Surface energy is estimated using the Young equation:
cos(θ)*γlv=γsv−γsl
with the contact angle θ, the interfacial energy ysv between the solid and the vapor phase, the interfacial energy γsl between the solid and the liquid phase, and the interfacial energy γlv between the liquid and the vapor phase, and γsv represents the surface energy of the solid.
As used herein, “molecular weight” in reference to a polymer or any portion thereof, means to the weight-average molecular weight (“Mw”) of the polymer or portion, wherein Mw of a polymer is a value measured by gel permeation chromatography and Mw of a portion of a polymer is a value calculated according to known techniques from the amounts of monomers, polymers, initiators and/or transfer agents used to make the said portion.
As used herein, the notation “(Cn-Cm)” in reference to an organic group or compound, wherein n and m are integers, means that the group or compound contains from n to m carbon atoms per such group or compound.
The term “persistent antideposition and/or antiadhesion properties” is understood to mean that the treated surface retains these properties over time, including after subsequent contacts with a soiling substance (for example rainwater, water from the distribution network, rinsing water to which rinsing products have or have not been added, spattered fats, soaps, and the like). This property of persistence can be observed beyond approximately 10 rinsing cycles, indeed even, in some specific cases where numerous rinsings are carried out (case of toilets, for example), beyond 100 rinsing cycles.
The expression of “conferring, on the surface thus treated, antideposition properties” means more particularly that the treated surface, brought into contact with a soiling substance in a predominantly aqueous medium, will not have a tendency to “capture” said soiling substance, which thus significantly reduces the deposition of the soiling substance on the surface.
The expression of “conferring, on the surface thus treated, antiadhesion properties” means more particularly that the treated surface is capable of interacting only very slightly with the soiling substance which has been deposited thereon, which makes possible easy removal of the soiling substances from the soiled treated surface; this is because, during the drying of the soiling substance brought into contact with the treated surface, the bonds developed between the soiling substance and the surface are very weak; thus, to break these bonds requires less energy (thus less effort) during the cleaning operation.
When it is said that the presence of mono-, di-, and polyol phosphate esters (like PEG phosphate esters, PPG phosphate esters, glycerine phosphate esters) makes it possible “to improve the cleaning ability” of a formulation, this means that, for the same amount of cleaning formulation (in particular a formulation for washing dishes by hand), the formulation comprising polybetaine zwitterions makes it possible to clean a greater number of soiled objects than a formulation which is devoid thereof.
In addition, the deposition on a hard surface of mono-, di-, and polyol phosphate esters (like PEG phosphate esters, PPG phosphate esters, glycerine phosphate esters) makes it possible to contribute antistatic properties to this surface; this property is particularly advantageous in the case of synthetic surfaces.
The presence of mono-, di-, and polyol phosphate esters (like PEG phosphate esters, PPG phosphate esters, glycerine phosphate esters) in formulations for the treatment of a hard surface makes it possible to render the surface hydrophilic or to improve its hydrophilicity.
The property of hydrophilization of the surface makes it possible in addition to reduce the formation of condensation on the surface; this advantage can be made use of in cleaning formulations for windows and mirrors, in particular in bathrooms. Furthermore, the rate of drying of the surface, immediately after treatment thereof by the application of the polymer but also after subsequent and repeated contacts with an aqueous medium, is very significantly improved.
The term “hard surfaces” is to be taken in the broad sense; it refers to nontextile surfaces which can equally well be domestic, communal or industrial surfaces.
They can be made of any material, in particular of the following types:
The “hard surfaces” according to the invention are surfaces which are not very porous and which are non-fibrillate; they are thus to be distinguished from textile surfaces (fabrics, fitted carpets, clothes, and the like, made of natural, artificial or synthetic materials).
The composition according to the invention, capable of contributing, to the hard surfaces to be treated, antideposition and/or antiadhesion properties with regard to soiling substances, can be a cleaning (or rinsing) composition for domestic use.
It can be universal or can be more specific, such as a composition for cleaning or rinsing any of the following:
A cleaning (or rinsing) composition for industrial or communal use; it can be universal or more specific, such as a composition for cleaning any of the following:
The composition according to the invention can be provided in any form and can be used in multiple ways.
Thus, it can be in the form of a gelled or ungelled liquid to be deposited as such, in particular by spraying,
It can be in the form of:
For satisfactory implementation of the invention, the phosphate ester is present in the composition forming the subject matter of the invention in an amount which is effective in contributing, to the surfaces, antideposition and/or antiadhesion properties with regard to soiling substances capable of being deposited on the surfaces.
The composition forming the subject matter of the invention can comprise, depending on its application, from 0.001 to 10% of its weight of at least one of the phosphate esters.
The pH of the composition or the pH of use of the composition according to the invention can vary, depending on the applications and the surfaces to be treated, from 1 to 14, indeed even from 0.5 to 14.
Extreme pH values are conventional in the applications of industrial or communal cleaning type. In the field of domestic applications, the pH values range instead from 1 to 13, depending on the applications.
The composition can be employed for the cleaning or rinsing of hard surfaces in an amount such that, after optional rinsing and after drying, the amount of phosphate esters deposited on the surface is typically from 0.0001 to 10 mg/m2, for example, 0.001 to 5 mg/m2, of surface treated.
Unless otherwise indicated, when molar mass is referred to, the reference will be to the weight-average molar mass, expressed in g/mol. The latter can be determined by aqueous gel permeation chromatography (GPC) or by light scattering (DLS or alternatively MALLS), with an aqueous eluent or an organic eluent (for example dimethylacetamide, dimethylformamide, and the like), depending on the composition of the polymer.
In a second aspect, the present invention is directed to a method for hydrophilizing a hard surface having a hydrophobic surface, comprising treating at least a portion of the hydrophobic surface with a treatment composition comprising a surface-active agent, an organophosphorus material, and an optional vinyl alcohol material, as described above to deposit a hydrophilizing layer on the portion of the hydrophobic surface.
In a third aspect the present invention is directed to a cleaning composition for pre-treating a hard surface of an article with the above-described organophosphorus material.
Consistent with this, the present invention is also directed to a pre-treated article, comprising:
If desired the layer may further comprise the above-described vinyl alcohol material and/or a surface-active agent.
Hydrophobic Hard Surface Substrate
The composition of the present invention is useful on hard surfaces. Hard surfaces are described above, for example, ceramic, porcelain, glass, metal, synthetic resins, and plastics. The “hard surfaces” according to the invention are surfaces which are not very porous and which are non-fibrillate; they are thus to be distinguished from textile surfaces (fabrics, fitted carpets, clothes, and the like, made of natural, artificial or synthetic materials).
In some instances the hard surface substrate having a hydrophobic surface. Suitable hydrophobic materials comprise, for example, hydrophobically modified inorganic materials, e.g., glass, porcelain, ceramic, tiles, silanized glass and silica, graphite, granite, stone, building facades, metal, and polymers.
Phosphate Esters (Organophosphorus Compounds)
As used herein, the term “alkyl” means a monovalent saturated straight chain or branched hydrocarbon radical, typically a monovalent saturated (C1-C30)hydrocarbon radical, such as for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, or n-hexyl, which may optionally be substituted on one or more of the carbon atoms of the radical. In one embodiment, an alkyl radical is substituted on one or more carbon atoms of the radical with alkoxy, amino, halo, carboxy, or phosphono, such as, for example, hydroxymethyl hydroxyethyl, methoxymethyl, ethoxymethyl, isopropoxyethyl, aminomethyl, chloromethyl or trichloromethyl, carboxyethyl, or phosphonomethyl.
As used herein, the term “hydroxyalkyl” means an alkyl radical that is substituted on one of its carbon atoms with a hydroxyl group.
As used herein, the term “alkoxyl” means an oxy radical that is substituted with an alkyl group, such as for example, methoxyl, ethoxyl, propoxyl, isopropoxyl, or butoxyl, which may optionally be further substituted on one or more of the carbon atoms of the radical.
As used herein, the term “cylcoalkyl” means a saturated cyclic hydrocarbon radical, typically a (C3-C8) saturated cyclic hydrocarbon radical, such as, for example, cyclohexyl or cyclooctyl, which may optionally be substituted on one or more of the carbon atoms of the radical.
As used herein, the term “alkenyl” means an unsaturated straight chain, branched chain, or cyclic hydrocarbon radical that contains one or more carbon-carbon double bonds, such as, for example, ethenyl, 1-propenyl, or 2-propenyl, which may optionally be substituted on one or more of the carbon atoms of the radical.
As used herein, the term “aryl” means a monovalent unsaturated hydrocarbon radical containing one or more six-membered carbon rings in which the unsaturation may be represented by three conjugated double bonds, such as for example, phenyl, naphthyl, anthryl, phenanthryl, or biphenyl, which may optionally be substituted one or more of carbons of the ring. In one embodiment, an aryl radical is substituted on one or more carbon atoms of the radical with hydroxyl, alkenyl, halo, haloalkyl, or amino, such as, for example, methylphenyl, dimethylphenyl, hydroxyphenyl, chlorophenyl, trichloromethylphenyl, or aminophenyl.
As used herein, the term “aryloxy” means an oxy radical that is substituted with an aryl group, such as for example, phenyloxy, methylphenyl oxy, isopropylmethylphenyloxy. In the present application, average molecular weights are weight average molecular weights unless otherwise specified.
As used herein, the indication that a radical may be “optionally substituted” or “optionally further substituted” means, in general, that is unless further limited, either explicitly or by the context of such reference, that such radical may be substituted with one or more inorganic or organic substituent groups, such as, for example, alkyl, alkenyl, aryl, aralkyl, alkaryl, a hetero atom, or heterocyclyl, or with one or more functional groups that are capable of coordinating to metal ions, such as hydroxyl, carbonyl, carboxyl, amino, imino, amido, phosphonic acid, sulphonic acid, or arsenate, or inorganic and organic esters thereof, such as, for example, sulphate or phosphate, or salts thereof.
As used herein, the terminology “(Cx-Cy)” in reference to an organic group, wherein x and y are each integers, indicates that the group may contain from x carbon atoms to y carbon atoms per group.
As described above, the water-soluble or dispersible organophosphorus material for use in the hard surface cleaning composition according to the present invention comprises a hydrophilizing agent comprising:
Organophosphorus material suitable for use in the present hard surface cleaner composition are also described in U.S. provisional patent application Nos. 60/842,265, filed Sep. 5, 2006 and 60/812,819, filed Jun. 12, 2006, both incorporated herein by reference.
In one embodiment, R6 and R8 are each and each R7 is independently H, (C1-C30) alkyl, (C1-C30) alkenyl, or (C7-C30) alkaryl.
In one embodiment, each R1 and each R2 is O, and the organophosphorus compound is selected from:
wherein R3, R4, R5, R6, R7, R8, and m are each as described above,
In one embodiment, each R1 is absent, each R2 is O, and the organophosphorus compound is selected from:
In one embodiment, each R1 is O, each R2 is absent, and the organophosphorus compound is selected from:
wherein R3, R4, R5, R6, R7, R8, and m are each as described above,
In one embodiment, each R3 is a divalent radical according to structure (V), (VI), (VII), or (VIII):
In one embodiment, each R4 and each R5 is independently absent or a divalent radical according to structure (V), (VI), or (VII), wherein R12, R13, R20, R21, R22, R23, p, p′, p″, q, r, r′, r″, s, t, t″, t, u, v, w, x, and y are as described above.
In one embodiment, each R3 is independently a divalent radical according to structure (V), (VI), or (VII) wherein R12, R13, R20, R21, R22, R23, p, p′, p″, q, r, r′, r″, s, t, t″, t, u, v, w, x, and y are as described above, and R4 and R5 are each independently absent or R3.
In one embodiment, each R3 is independently a divalent radical according to structure (V), wherein p is 2, 3, or 4, r is an integer from 1 to 25, s is 0, t is an integer of from 1 to 2, and R4 and R5 are each independently absent or R3.
In one embodiment, each R3 is independently a divalent radical according to structure (VI), wherein the R12 groups are fused to form, including the carbon atoms to which they are attached, a (C6-C8) hydrocarbon ring, each R13 is H, p′ is 2 or 3, u is 2, v is an integer of from 1 to 3, r′ is an integer from 1 to 25, t′ is an integer of from 1 to 25, the product of the quantity (v+r′) multiplied times t″ is less than or equal to about 100, more typically less than or equal to about 50, and R4 and R5 are each independently absent or R3.
In one embodiment, each R3 is independently a divalent radical according to structure (VII), wherein R20 is hydroxyl or hydroxyalkyl, R22 is H, alkyl, hydroxyl, or hydroxyalkyl, provided that R20 and R22 are not each hydroxyl, R21 and R23 are each independently methylene, di(methylene), or tri(methylene), w is 1 or 2, p″ is 2 or 3, r″ is an integer of from 1 to 25, t″ is an integer of from 1 to 25, the product of the quantity (w+r″) multiplied times t″ is less than or equal to about 100, more typically less than or equal to about 50, and R4 and R5 are each independently absent or R3.
In one embodiment of the organophosphorus compound according to structure (II),
R6 and R8 are each and each R7 is independently H or (C1-C30)hydrocarbon, which hydrocarbon may optionally be substituted on one or more carbon atoms by hydroxyl, fluorine, alkyl, alkenyl or aryl and/or interrupted at one or more sites by an O, N, or S heteroatom, or —POR9R10, more typically, R6, R8, and each R7 are each H.
R4 and R5 are each absent,
each R3 is independently a divalent radical according to structure (V), (VI), or (VII), and
m is an integer of from 1 to 5.
In one embodiment of the organophosphorus compound according to structure (II):
R6, R8, and each R7 are each H,
R4 and R5 are each absent,
each R3 is independently a divalent radical according to structure (V),
each p is independently 2, 3, or 4, more typically 2 or 3,
each r is independently a number of from 1 to about 100, more typically from 2 to about 50,
each s is 0,
each t is 1, and
m is an integer of from 1 to 5.
In one embodiment, the organophosphorus material is selected from:
In one embodiment of the organophosphorus compound according to structure (II):
R6, R8, and each R7 are each H
R4 and R5 are each absent,
each R3 is independently a divalent radical according to structure (VI),
the R12 groups are fused to form, including the carbon atoms to which they are attached, a (C6-C8)hydrocarbon ring,
each R13 is H
p′ is 2 or 3,
u is 2,
v is 1,
r′ is a number of from 1 to 25,
t′ is a number of from 1 to 25,
the product of the quantity (v+r′) multiplied times t′ is less than or equal to about 100, and
m is an integer of from 1 to 5.
In one embodiment of the organophosphorus compound according to structure (II):
R6, R8, and each R7 are each H
R4 and R5 are each absent,
each R3 is independently a divalent radical according to structure (VII),
R20 is hydroxyl or hydroxyalkyl,
R22 is H, alkyl, hydroxyl, or hydroxyalkyl,
R23 and R21 are each independently methylene, di(methylene), or tri(methylene),
w is 1 or 2,
p″ is 2 or 3,
r″ is a number of from 1 to 25,
t″ is a number of from 1 to 25
the product of the quantity (w+r″) multiplied times t″ is less than or equal to about 100, and
m is an integer of from 1 to 5.
In one embodiment, the organophosphorus compound is according to structure (III), each R3 is a divalent radical according to structure (V) with s=0 and t=1, R4 and R5 are each absent, and R6, R7, and R8 are each H.
In one embodiment, the organophosphorus compound is according to structure (IV), wherein R3 and R5 are each according to structure (V), with s=0 and t=1, and R6 and R8 are each H.
In one embodiment, the organophosphorus material (b)(I) comprises a condensation reaction product of two or more molecules according to structure (I).
In one embodiment, the organophosphorus material (b)(I) comprises a condensation reaction product of two or more molecules according to structure (I) in the form of a linear molecule, such as, for example, a linear condensation reaction product according to structure (X), formed by condensation of a molecule according to structure (II) with a molecule according to structure (IV):
wherein R4, R7, p, r are each as described above.
In one embodiment, the organophosphorus material (b)(I) comprises a condensation reaction product of two or more molecules according to structure (I) in the form of a crosslinked network. A portion of an exemplary crosslinked condensation reaction product network is illustrated by structure (XI):
wherein
R1, R2, R4, R5, R6, R7, R8, and m are each as described above, and
each R3′ is independently a residue of an R3 group of a compound according to structure (I), as described above, wherein the R3 group is a alkyleneoxy or poly(alkyleneoxy) moiety substituted with hydroxyl-, hydroxyalkyl-, hydroxyalkyleneoxy- or hydroxypoly(alkyleneoxy)- on one or more carbon atoms of the alkyleneoxy or poly(alkyleneoxy) moiety, and —R3′—R4— and —R3′—R5— each represent a respective linkage formed by condensation of such an R3 group and a —R3′—R5— or —R8—R5— group of molecules of another molecule of a compound according to structure (I).
In one embodiment, the organophosphorus material (b)(I) comprises a condensation reaction product of two or more molecules according to structure (I) and the condensation reaction product forms a covalently crosslinked organophosphorus network. Typically the solubility of the covalently crosslinked organophosphorus network in water is less than that of the organophosphorus compound according to structure (I), more typically, the covalently crosslinked organophosphorus network is substantially insoluble in water.
As used herein, the term “salts” refers to salts prepared from bases or acids including inorganic or organic bases and inorganic or organic acids.
In one embodiment, the organophosphorus material (b)(I) is in the form of a salt that comprises an anion derived (for example, by deprotonation of a hydroxyl or a hydroxyalkyl substituent) from of an organophosphorus compound according to structure (I) and one or more positively charged counterions derived from a base.
Suitable positively charged counterions include inorganic cations and organic cations, such as for example, sodium cations, potassium cations, calcium cations, magnesium cations, copper cations, zinc cations, ammonium cations, tetraalkylammonium cations, as well as cations derived from primary, secondary, and tertiary amines, and substituted amines.
In one embodiment, the cation is a monovalent cation, such as for example, Na+, or K+.
In one embodiment, the cation is a polyvalent cation, such as, for example, Ca+2, Mg+2, Zn+2, Mn+2, Cu+2, Al+3, Fe+2, Fe+3, Ti+4, Zr+4, in which case the organophosphorus compound may be in the form of a “salt complex” formed by the organophosphorus compound and the polyvalent cation. For organophosphorus compound having two or more anionic sites, e.g., deprotonated hydroxyl substituents, per molecule, the organophosphorus compound-polyvalent cation complex can develop an ionically crosslinked network structure. Typically the solubility of the ionically crosslinked organophosphorus network in water is less than that of the organophosphorus compound according to structure (I), more typically, the ionically crosslinked organophosphorus network is substantially insoluble in water.
Suitable organophosphorus compounds can be made by known synthetic methods, such as by reaction of one or more compounds, each having two or more hydroxyl groups per molecule, with phosphoric acid, polyphosphoric acid, and or phosphoric anhydride, such as disclosed, for example, in U.S. Pat. Nos. 5,550,274, 5,554,781, and 6,136,221.
In one embodiment, cations are immobilized on a water insoluble substrate to form a water insoluble cationic particle and the hydrophilizing layer further comprises cationic particles. Suitable substrates include inorganic oxide particles, including for example, oxides of single elements, such as cerium oxide, titanium oxide, zirconium oxide, halfnium oxide, tantalum oxide, tungsten oxide, silicon dioxide, and bismuth oxide, zinc oxide, indium oxide, and tin oxide, and mixtures of such oxides, as well as oxides of mixtures of such elements, such as cerium-zirconium oxides. Such particle may exhibit a mean particle diameter (“D50”) of from about 1 nanometer (“nm”) to about 50 micrometers (“μm”), more typically from about 5 to about 1000 nm, even more typically from about 10 to about 800 nm, and still more typically from about 20 to about 500 nm, as determined by dynamic light scattering or optical microscopy. In one embodiment, aluminum cations are immobilized on silica particles.
Vinyl Alcohol Material
In one embodiment, the hard surface cleaner, and the hydrophilizing layer, further comprises the above-disclosed vinyl alcohol material (b)(II). In one embodiment, which offers improved solubility in water and improved processability, the vinyl alcohol material (b)(II) comprises a polymer that comprises monomeric units according to structure (I-a) (a “vinyl alcohol polymer”).
In one embodiment, the vinyl alcohol polymer exhibits a weight average molecular weight of greater than or equal to about 10,000, more typically from about 10,000 to about 100,000, even more typically from about 10,000 to about 30,000. In an alternative embodiment, which offers improved durability, the vinyl alcohol polymer a weight average molecular weight of greater than or equal to about 100,000, more typically form about 100,000 to about 200,000.
In another embodiment, which offers a balance between processability and durability, the vinyl alcohol polymer exhibits a weight average molecular weight of greater than or equal to about 50,000, more typically from about 50,000 to about 150,000, even more typically from about 80,000 to about 120,000.
In one embodiment, the vinyl alcohol polymer is made by polymerizing a vinyl ester monomer, such as for example, vinyl acetate, to form a polymer, such as a poly(vinyl acetate) homopolymer or a copolymer comprising monomeric units derived from vinyl acetate, having a hydrocarbon backbone and ester substituent groups, and then hydrolyzing at least a portion of the ester substitutent groups of the polymer to form hydroxy-substituted monomeric units according to structure (I-a). In one embodiment, which offers improved solubility in water and improved processability, the vinyl alcohol polymer exhibits a degree of hydrolysis of greater than or equal to about 88%, more typically from about 88% to about 95%. As used herein in reference to a vinyl alcohol polymer that is made by hydrolyzing a polymer initially having a hydrocarbon backbone and ester substituent groups, the term “degree of hydrolysis” means the relative amount, expressed as a percentage, of vinyl ester-substituted monomeric units that were hydrolyzed to form hydroxy-substituted monomeric units. In another embodiment, which offers improved solubility in water and improved durability, the vinyl alcohol polymer exhibits a degree of hydrolysis of greater than or equal to about 99%. In yet another embodiment, which offers a compromise between solubility in water and durability, the polymer exhibits a degree of hydrolysis from about 92 to about 99%.
In one embodiment, the vinyl alcohol polymer has a linear polymeric structure. In an alternative embodiment, the vinyl alcohol polymer has a branched polymeric structure.
In one embodiment, the vinyl alcohol polymer is a vinyl alcohol homopolymer that consists solely of monomeric units according to structure (I-a).
In one embodiment, the vinyl alcohol polymer is a vinyl alcohol copolymer that comprises monomeric units having a structure according to structure (I-a) and further comprises comonomeric units having a structure other than structure (I-a). In one embodiment, the vinyl alcohol polymer is a copolymer that comprises hydroxy-substituted monomeric units according to (I-a) and ester substituted monomeric units and is made by incomplete hydrolysis of a vinyl ester homopolymer.
In one embodiment a vinyl alcohol copolymer comprises greater than or equal to about 50 mole % (“mol %”), more typically greater or equal to than about 80 mol %, monomeric units according to structure (I-a) and less than about 50 mol %, more typically less than about 20 mol %, comonomeric units having a structure other than structure (I-a).
As described above, vinyl alcohol polymers having monomeric units according to structure (I-a) are typically derived from polymerization of vinyl ester monomers and subsequent hydrolysis of vinyl ester-substituted monomeric units of the polymer. Suitable vinyl alcohol copolymers are typically derived by copolymerization of the vinyl ester monomer with any ethylenically unsaturated monomer that is copolymerizable with the vinyl ester monomer, including for example, other vinyl monomers, allyl monomers, acrylic acid, methacrylic acid, acrylic ester monomers, methacrylic ester monomers, acrylamide monomers, and subsequent hydrolysis of at least a portion of the ester-substituted monomeric units to form hydroxy-substituted monomeric units according to structure (I-a).
In one embodiment, the vinyl alcohol polymer comprises monomeric units according to structure (I-a) and further comprises hydrophilic monomeric units other than the monomeric according to structure (I-a). As used herein, the term “hydrophilic monomeric units” are those wherein homopolymers of such monomeric units are soluble in water at 25° C. at a concentration of 1 wt % homopolymer, and include, for example, monomeric units derived from, for example, hydroxy(C1-C4)alkyl (meth)acrylates, (meth)acrylamide, (C1-C4)alkyl (meth)acrylamides, N,N-dialkyl-acrylamides, alkoxylated (meth)acrylates, poly(ethylene glycol)-mono methacrylates and poly(ethyleneglycol)-monomethylether methacrylates, hydroxy(C1-C4)acrylamides and methacrylamides, hydroxyl(C1-C4)alkyl vinyl ethers, N-vinylpyrrole, N-vinyl-2-pyrrolidone, 2- and 4-vinylpyridine, ethylenically unsaturated carboxylic acids having a total of 3 to 5 carbon atoms, amino(C1-C4)alkyl, mono(C1-C4)alkylamino(C1-C4)alkyl, and di(C1-C4)alkylamino(C1-C4)alkyl (meth)acrylates, allyl alcohol, dimethylaminoethyl methacrylate, dimethylaminoethylmethacrylamide.
In one embodiment, the vinyl alcohol polymer comprises monomeric units according to structure (I-a) and further comprises hydrophobic monomeric units. As used herein, the term “hydrophobic monomeric units” are those wherein homopolymers of such monomeric units are insoluble in water at 25° C. at a concentration of 1 wt % homopolymer, and include, for example, monomeric units derived from (C1-C18)alkyl and (C5-C18)cycloalkyl (meth)acrylates, (C5-C18)alkyl(meth)acrylamides, (meth)acrylonitrile, vinyl (C1-C18)alkanoates, (C2-C18)alkenes, (C2-C18)haloalkenes, styrene, (C1-C6)alkylstyrenes, (C4-C12)alkyl vinyl ethers, fluorinated (C2-C10)alkyl (meth)acrylates, (C3-C12)perfluoroalkylethylthiocarbonylaminoethyl (meth)acrylates, (meth)acryloxyalkylsiloxanes, N-vinylcarbazole, (C1-C12) alkyl maleic, fumaric, itaconic, and mesaconic acid esters, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, chloroprene, vinyl chloride, vinylidene chloride, vinyltoluene, vinyl ethyl ether, perfluorohexyl ethylthiocarbonylaminoethyl methacrylate, isobornyl methacrylate, trifluoroethyl methacrylate, hexa-fluoroisopropyl methacrylate, hexafluorobutyl methacrylate, tristrimethylsilyloxysilylpropyl methacrylate, and 3-methacryloxypropylpentamethyldisiloxane.
As used herein, the term “(meth)acrylate” means acrylate, methacrylate, or acrylate and methacrylate and the term (meth)acrylamide” means acrylamide, methacrylamide or acrylamide and methacrylamide.
In one embodiment, the polymer comprising monomeric units according to structure (I-a) a random copolymer. In another embodiment, the copolymer comprising monomeric units according to structure (I-a) is a block copolymer.
Methods for making suitable vinyl alcohol polymers are known in the art. In one embodiment, a polymer comprising monomeric units according to structure (I-a) is made by polymerizing one or more ethylenically unsaturated monomers, comprising at least one vinyl ester monomer, such vinyl acetate, by known free radical polymerization processes and subsequently hydrolyzing at least a portion of the vinyl ester monomeric units of the polymer to make a polymer having the desired degree of hydrolysis. In another embodiment, the polymer comprising monomeric units according to structure (I-a) is a copolymer made by known controlled free radical polymerization techniques, such as reversible addition fragmentation transfer (RAFT), macromolecular design via interchange of xanthates (MADIX), or atom transfer reversible polymerization (ATRP).
In one embodiment, the vinyl alcohol polymer is made by known solution polymerization techniques, typically in an aliphatic alcohol reaction medium.
In another embodiment, the vinyl alcohol polymer is made by known emulsion polymerization techniques, in the presence of one or more surfactants, in an aqueous reaction medium.
In one embodiment, the vinyl alcohol material comprises a microgel made by crosslinking molecules of a vinyl alcohol polymer.
In one embodiment the vinyl alcohol material comprises a salt, such as a sodium or potassium salt, of a vinyl alcohol polymer.
In one embodiment, the hydrophilizing layer comprises one or more poly(vinyl alcohol) polymers. Poly(vinyl alcohol) polymers are manufactured commercially by the hydrolysis of poly(vinyl acetate). In one embodiment, the poly(vinyl alcohol) has a molecular weight of greater than or equal to about 10,000 (which corresponds approximately to a degree of polymerization of greater than or equal to about 200), more typically from about 20,000 to about 200,000 (which corresponds approximately to a degree of polymerization of from about 400 to about 4000, wherein the term “degree of polymerization” means the number of vinyl alcohol units in the poly(vinyl alcohol) polymer. In one embodiment, the poly(vinyl alcohol) has a degree of hydrolysis of greater than or equal about 50, more typically greater than or equal about 88%.
In one embodiment, the hydrophilizing layer comprises an organophosphorus material (b)(I) and optional vinyl alcohol material (b)(II). For example, some potential weight ratios of these ingredients are as follows based on 100 pbw of the hydrophilizing layer:
from greater than 0 pbw to less than 100 pbw, or from about 0.1 pbw to about 99.9 pbw, or from about 1 pbw to about 99 pbw, organophosphorus material (b)(I), and
optionally from greater than 0 pbw to less than 100 pbw, or from about 0.1 pbw to about 99.9 pbw, or from about 1 pbw to about 99 pbw, vinyl alcohol material (b)(II).
Liquid Carrier
In one embodiment, the treatment composition of the present invention comprises an organophosphorus material (b)(I) and optional vinyl alcohol material (b)(II) and a liquid carrier. For example, in one embodiment, the treatment composition of the present invention comprises the organophosphorus material (b)(I) and a liquid carrier.
In one embodiment, the liquid carrier is an aqueous carrier comprising water and the treatment solution is in the form of a solution, emulsion, or dispersion of the organophosphorus material and additives. In one embodiment, the liquid carrier comprises water and a water miscible organic liquid. Suitable water miscible organic liquids include saturated or unsaturated monohydric alcohols and polyhydric alcohols, such as, for example, methanol, ethanol, isopropanol, cetyl alcohol, benzyl alcohol, oleyl alcohol, 2-butoxyethanol, and ethylene glycol, as well as alkylether diols, such as, for example, ethylene glycol monoethyl ether, propylene glycol monoethyl ether and diethylene glycol monomethyl ether.
In one embodiment, the treatment composition comprises, based on 100 parts by weight (“pbw”) of the composition:
from about 0.1 to about 20 pbw, or from about 1 to about 5 pbw, organophosphorus material, and
from about 80 to 99 pbw, more typically, from about 90 to about 98 pbw, liquid carrier.
In one embodiment, the treatment composition further comprises, based on 100 parts by weight (“pbw”) of the composition, from about 0.01 to about 10 pbw, or from about 0.1 to about 5 pbw, colloidal inorganic particles.
In one embodiment, the treatment composition further comprises, based on 100 parts by weight (“pbw”) of the composition, from about 0.01 to about 2 pbw or from about 0.1 to about 0.5 pbw poly(vinyl alcohol).
In one embodiment, the treatment composition further comprises based on 100 parts by weight (“pbw”) of the composition, from about 0.0001 to about 1 pbw or from about 0.001 to about 0.1 pbw multivalent cationic particles.
In one embodiment, the treatment composition of the present invention comprises an organophosphorus material (b)(I) and a vinyl alcohol material (b)(II) and a liquid carrier.
In one embodiment, the treatment composition comprises, based on 100 parts by weight (“pbw”) of the composition,
from about 0.1 to about 20 pbw, or from about 1 to about 5 pbw, organophosphorus material (b)(I),
from about 0.1 to about 20 pbw, or from about 1 to about 5 pbw, vinyl alcohol material (b)(II), and
from about 80 to 99 pbw, or from about 90 to about 98 pbw, liquid carrier.
The treatment composition may optionally further comprise, based on 100 pbw weight of the composition up to about 10 pbw of other components, such as, salts, sugars, surfactants, and rheology modifiers. Suitable salts include, for example, NaCl, KCl, NH3Cl, N(C2H5)3Cl. Suitable sugars include monosaccharides and polysaccharides, such as, for example, glucose or guar gum. Suitable rheology modifiers include, for example, alkali swellable polymers, such as acrylic acid polymers, hydrogen bridging rheology modifiers, such as carboxymethylcellulose or hydroxyethylcellulose, and hydrophobic associative thickeners, such as hydrophobically modified cellulose derivatives and hydrophobically modified alkoxylated urethane polymers.
In one embodiment, the hydrophilizing layer is deposited on at least a portion of the hydrophobic surface of a substrate by contacting the surface with a treatment solution comprising the organophosphorus material and a liquid carrier and then removing the liquid carrier. In one embodiment, the liquid carrier is a volatile liquid carrier and the carrier is removed by allowing the carrier to evaporate.
The hydrophobic surface of substrate may be contacted with the treatment composition by any convenient method such as, for example, by immersing the substrate in the treatment composition or by applying the treatment composition to the surface of the substrate by brushing or spraying.
In one embodiment, a hydrophilizing layer is deposited on the hydrophobic surface of the hard surface by treating the hard surface with the treatment composition.
In one embodiment, the hydrophilizing layer is deposited on at least a portion of the substrate by immersing the substrate in an aqueous treatment composition comprising the organophosphorus material and an aqueous carrier and then removing the aqueous carrier by evaporation to leave an amount of hydrophilizing layer disposed on at least a portion of the hard surface of the substrate.
In one embodiment, the hydrophilizing layer disposed on at least a portion of the hydrophobic surface of the substrate in an amount, typically from about 0.0001 gram to about 10 grams hydrophilizing layer per square meter of surface area, effective to decrease the hydrophobicity of the portion of the surface.
In one embodiment, the hydrophilized surface of the present invention comprises from about 0.017 to about 17, or from about 0.17, to about 3 grams of the hydrophilizing layer per square meter of surface area.
In one embodiment, the hydrophilized substrate of the present invention is a material having hydrophobic surfaces, such as, for example, hydrophobic synthetic polymeric surfaces, such as poly(olefin), and a hydrophilizing layer disposed on at least a portion of the surfaces in an amount effective to render the substrate sufficiently hydrophilic to facilitate cleaning with aqueous media. As used herein, terms “aqueous medium” and “aqueous media” are used herein to refer to any liquid medium of which water is a major component. Thus, the term includes water per se as well as aqueous solutions and dispersions.
In one embodiment, the hydrophilized substrate is durable, in the sense that at least a portion of the organophosphorus compound remains on the surfaces of the substrate when the hydrophilized substrate is contacted with an aqueous medium. One aspect of the durability of the hydrophilic properties of hydrophilized substrate of the present invention can be evaluated by rinsing a hydrophilized substrate in water and measuring the surface tension of rinse water. Although not a hard surface, this effect is demonstrated by testing a hydrophilized fiber substrate in which the rinse water exhibits a surface tension of from about 20 to about 70 milliNewtons per meter (mN/m), more preferably from about 25 to about 70 mN/m, as determined according to American Society for Testing and Materials test no. ASTM 1331 using a Wilhemy plate (Kruss Instruments). For example, the fabric is rinsed according to the following procedure:
One aspect of the increased hydrophilicity of the hydrophilized substrate of the present invention can be evaluated by a “strikethrough” test on fibers. Although not a hard surface, the hydrophilized fabric, exhibits a strikethrough time, as determined according to European Disposable and Nonwovens Association test no. EDANA 150.3-96 of from less than about 10 seconds, more preferably from about 2 to about 5 seconds, and still more preferably from about 2 to about 4 seconds. The strikethrough time may be measured according to the following procedure:
The cleaning or rinsing composition according to the invention additionally comprises at least one surface-active agent. The latter can be nonionic, anionic, amphoteric, zwitterionic or cationic.
Anionic Surface-Active Agents
Typical anionic surface-active agents for use in the present invention, by way of example, are:
A description of nonionic surface-active agents is given in U.S. Pat. No. 4,287,080 and U.S. Pat. No. 4,470,923. Mention may in particular be made of condensates of alkylene oxide, in particular of ethylene oxide and optionally of propylene oxide, with alcohols, polyols, alkylphenols, fatty acid esters, fatty acid amides and fatty amines; amine oxides; sugar derivatives, such as alkylpolyglycosides or esters of fatty acids and of sugars, in particular sucrose monopalmitate; long-chain (of 8 to 28 carbon atoms) tertiary phosphine oxides; dialkyl sulfoxides; block copolymers of polyoxyethylene and of polyoxypropylene; polyalkoxylated esters of sorbitan; fatty esters of sorbitan; poly(ethylene oxide)s and fatty acid amides modified so as to confer thereon a hydrophobic nature (for example, fatty acid mono- and diethanolamides comprising from 10 to 18 carbon atoms).
Typical nonionic surface-active agents for use in the present invention, by way of example, are:
Typical amphoteric surface-active agents for use in the present invention, by way of example, are:
Typical zwitterionic surface-active agents for use in the present invention, by way of example, are disclosed in U.S. Pat. No. 5,108,660.
A number of suitable zwitterionic surfactants are alkyl dimethyl betaines, alkyl amidopropyldimethyl betaines, alkyl dimethyl sulfobetaines or alkyl amidopropyldimethyl sulfobetaines, such as MIRATAINE JCHA, MIRATAINE H2CHA or MIRATAINE CBS, sold by Rhodia, or those of the same type sold by Sherex Company under the name of “Varion CADG Betaine” and “Varion CAS Sulfobetaine”, or the condensation products of fatty acids and of protein hydrolysates.
Other zwitterionic surfactants are also disclosed in U.S. Pat. No. 4,287,080 and in U.S. Pat. No. 4,557,853.
Another zwitterionic is a betaine, for example, those disclosed by US Patent Application Publication No. 2006/0217286 incorporated herein by reference in its entirety.
Cationic Surface-Active Agents
Typical cationic surface-active agents for use in the present invention include those of the quaternary ammonium salts of formula:
R1R2R3R4N+X−
where
Mention may also be made of other cationic surface-active agents, such as:
quaternary ammonium salts of formula
R1′R2′R3′R4′N+X−
where
Mention may in particular be made of:
Additional examples of appropriate surfactants are compounds generally used as surface-active agents denoted in the well-known handbook “Surface Active Agents”, volume I, by Schwartz and Perry, and “Surface Active Agents and Detergents”, volume II, by Schwartz, Perry and Berch.
The surface-active agents represent from 0.005 to 60%, in particular from 0.5 to 40%, of the weight of the composition of the invention, this being according to the nature of the surface-active agent(s) and the destination of the cleaning composition.
Advantageously, an organophosphate ester (II)(1)/surface-active agent(s) ratio by weight is between 1/1 and 1/1000, advantageously 1/2 and 1/200.
Additional Additives
The cleaning or rinsing composition according to the invention can additionally comprise at least one other additive chosen in particular from conventional additives present in compositions for cleaning or rinsing hard surfaces.
Mention may be made of a number of potential additional additives.
Chelating agents, in particular of the water-soluble aminophosphonates and organic phosphonates type, such as:
Sequestering or scale-inhibiting agents, such as the following:
Inorganic builders (detergency adjuvants which improve the surface properties of surfactants) of the type:
Bleaching agents of the perborates or percarbonates type, which may or may not be combined with acetylated bleaching activators, such as N,N,N′,N′-tetraacetylethylenediamine (TAED), or chlorinated products of the chloroisocyanurates type, or chlorinated products of the alkali metal hypochlorites type, or aqueous hydrogen peroxide solution (in a proportion of 0 to 30% of the total weight of said cleaning composition).
Fillers of the sodium sulfate, sodium chloride, sodium carbonate, calcium carbonate, kaolin or silica type, in a proportion of 0 to 50% of the total weight of said composition.
Bleaching catalysts comprising a transition metal, in particular iron, manganese and cobalt complexes, such as those of the type [MnIV2(μ-O)3(Me3TACN)2](PF6)2, [FeII(MeN4py)(MeCN)](ClO4)2, [(CoIII)(NH3)5(OAc)](OAc)2, disclosed in U.S. Pat. Nos. 4,728,455, 5,114,606, 5,280,117, EP-A-909 809, U.S. Pat. No. 5,559,261, WO 96/23859, 96/23860 and 96/23861 (in a proportion of 0 to 5% of the total weight of said cleaning composition)
Agents which influence the pH of the composition, which are soluble in the cleaning or rinsing medium, in particular
Polymers used to control the viscosity of the mixture and/or the stability of the foams formed during use, such as cellulose derivatives or guar derivatives (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylguar, carboxymethylguar, carboxymethylhydroxypropylguar, and the like), xanthan gum, succinoglycan (Rheozan® sold by Rhodia), locust bean gum or carrageenans (in a proportion of 0 to 2% of the total weight of said cleaning composition).
Hydrotropic agents, such as short-chain C2-C8 alcohols, in particular ethanol, diols and glycols, such as diethylene glycol or dipropylene glycol, sodium xylenesulfonate or sodium naphthalenesulfonate (in a proportion of 0 to 10 g per 100 g of said cleaning composition).
Hydrating or moisturizing agents for the skin, such as glycerol or urea, or agents for protecting the skin, such as proteins or protein hydrolysates, vegetable oils, such as soybean oil, or cationic polymers, such as cationic guar derivatives (Jaguar C13S®, Jaguar C162® or Hicare 1000®, sold by Rhodia) (in a proportion of 0 to 40% of the total weight of said cleaning composition).
Biocides or disinfectants, such as
Solvents having a good cleaning or decreasing activity, such as:
Industrial cleaners, such as solutions of alkali metal salts of the phosphate, carbonate, silicate, and the like, type of sodium or potassium (in a proportion of 0 to 50% of the total weight of said cleaning composition).
Water-soluble organic solvents with little cleaning effect, such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol and their mixtures (in a proportion of 0 to 40% of the total weight of said cleaning composition).
Cosolvents, such as monoethanolamide and/or β-aminoalkanols, which are particularly advantageous in compositions with a pH of greater than 11, very particularly of greater than 11.7, as they help in reducing the formation of films and marks on hard surfaces (they can be employed in a proportion of 0.05 to 5% of the weight of the cleaning composition); solvent systems comprising monoethanolamide and/or β-aminoalkanols are disclosed in U.S. Pat. No. 5,108,660.
Antifoaming agents, such as soaps in particular. Soaps are alkali metal salts of fatty acids, in particular sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids comprising approximately from 8 to 24 carbon atoms and preferably from approximately 10 to approximately 20 carbon atoms; mention may in particular be made of mono-, di- and triethanolamine, sodium and potassium salts of mixtures of fatty acids derived from coconut oil and from ground walnut oil. The amount of soap can be at least 0.005% by weight, preferably from 0.5 to 2% by weight, with respect to the total weight of the composition. Additional examples of foam modifiers are organic solvents, hydrophobic silica, silicone oil and hydrocarbons.
Abrasives, such as silica or calcium carbonate.
Various additives, such as enzymes, silicates, fragrances, colorants, agents which inhibit corrosion of metals, preservatives, optical brighteners, opacifying or pearlescent agents, and the like.
The pH of the composition forming the subject matter of the invention or the pH of use of said composition can range from 0.5 to 14, preferably from 1 to 14.
Compositions of Alkaline Type
Compositions of alkaline type, with a pH of greater than or equal to 7.5, preferably of greater than 8.5, for domestic applications (very particularly with a pH from 8.5 to 12, in particular from 8.5 to 11.5) are of particular use for the removal of greasy soiling substances and are particularly well suited to the cleaning of kitchens.
They can typically comprise from 0.001 to 5%, or 0.005 to 2%, of their weight of organophosphorus material (b)(I).
The alkaline compositions generally comprise, in addition to the organophosphorus (b)(I), at least one additive chosen from the following:
a sequestering or scale-inhibiting agent (in an amount ranging from 0 to 40%, preferably from 1 to 40%, or from 2 to 30% or from 5 to 20%, of the weight of the composition),
a cationic biocide or disinfectant, in particular of quaternary ammonium type, such as (N-alkyl)benzyldimethylammonium chlorides, (N-alkyl)dimethyl(ethylbenzyl)ammonium chloride, N-didecyldimethylammonium halide and di(N-alkyl)dimethylammonium chloride (in an amount which can range from 0 to 60%, preferably from 0 to 40%, more preferably from 0 to 15% and very particularly from 0 to 5%, of the weight of the composition),
at least one nonionic, amphoteric, zwitterionic or anionic surface-active agent or their mixture; when a cationic surface-active agent is present, said composition in addition preferably comprises an amphoteric and/or nonionic surface-active agent (the total amount of surface-active agents can range from 0 to 80%, preferably from 0 to 50%, very particularly from 0 to 35%, of the weight of the composition),
if necessary, a pH modifier, in an amount which makes it possible to achieve, optionally after diluting or dissolving the composition, a pH of use ranging from 7.5 to 13; the pH modifier can in particular be a buffer system comprising monoethanolamine and/or a β-aminoalkanol and potentially but preferably “cobuffer” alkaline materials from the group consisting of aqueous ammonia, C2-C4 alkanolamines, silicates, borates, carbonates, bicarbonates, alkali metal hydroxides and their mixtures. The preferred cobuffers are alkali metal hydroxides.
from 0.5 to 98%, preferably from 25 to 95%, very particularly from 45 to 90%, by weight of water,
a cleaning or degreasing organic solvent, in an amount which can represent from 0 to 60%, preferably from 1 to 45%, very particularly from 2 to 15%, of the weight of said composition,
a cosolvent, such as monoethanolamine and/or β-aminoalkanols, in an amount which may represent from 0 to 10%, preferably from 0.05 to 10%, very particularly from 0.05 to 5%, by weight of said composition,
a water-soluble organic solvent with little cleaning effect, in an amount which can represent from 0 to 25%, preferably from 1 to 20%, very particularly from 2 to 15%, of the weight of said composition,
optionally a bleaching agent, a fragrance or other conventional additives.
The alkaline compositions can be provided in the form of a ready-for-use formulation or else of a dry or concentrated formulation to be diluted in water in particular before use; they can be diluted from 1- to 10 000-fold, preferably from 1- to 1000-fold, before use.
Advantageously, a formulation for cleaning kitchens comprises:
from 0.001 to 1% by weight of organophosphorus compound (B)(1),
from 1 to 10% by weight of water-soluble solvent, in particular isopropanol,
from 1 to 5% by weight of cleaning or degreasing solvent, in particular butoxypropanol,
from 0.1 to 2% by weight of monoethanolamine,
from 0 to 5% by weight of at least one noncationic surface-active agent, preferably an amphoteric or nonionic surface-active agent,
from 0 to 1% by weight of at least one cationic surface-active agent with a disinfecting property (in particular mixture of (n-alkyl)dimethyl(ethylbenzyl)-ammonium chloride and (n-alkyl)dimethylbenzylammonium chloride),
the total amount of surface-active agent(s) representing from 1 to 50% by weight,
from 0 to 2% by weight of a dicarboxylic acid as scale-inhibiting agent,
from 0 to 5% of a bleaching agent, and
from 70 to 98% by weight of water.
The pH of such a formulation is typically from 7.5 to 13, or from 8 to 12.
Compositions of Acidic Type
Compositions of acidic type, with a pH of less than 5, are of particular use for the removal of soiling substances of inorganic type; they are particularly well suited to the cleaning of toilet bowls.
They typically comprise from 0.001 to 5%, or from 0.01 to 2%, of their weight of organophosphorus material (b)(I).
The acidic compositions generally comprise, in addition to the organophosphorus material (b)(I), the following:
The acidic compositions are preferably provided in the form of a ready-for-use formulation.
Advantageously, a formulation for cleaning toilet bowls comprises:
A few other specific embodiments and forms of application of the composition of the invention are clarified below.
Thus, the composition according to the invention can be employed for making easier the cleaning treatment of glass surfaces, in particular of windows. This treatment can be carried out by the various known techniques. Mention may be made in particular of the techniques for cleaning windows by spraying with a jet of water using devices of the Kärcher® type.
The amount of organophosphorus (b)(I) introduced will generally be such that, during the use of the cleaning composition, after optional dilution, the concentration of organophosphorus (b)(I) is between 0.001 g/l and 2 g/l, preferably between 0.005 g/l and 0.5 g/l.
The composition for cleaning windows according to the invention typically comprises:
The cleaning formulations for windows comprising said polymer can also comprise:
The pH of the composition is advantageously between 1 and 6.
Detergent Compositions for Washing Dishes in Automatic Dishwashers
The composition of the invention is also advantageous for making easier the cleaning of dishes in an automatic device. The composition can be either a detergent (cleaning) formulation used in the washing cycle or a rinsing formulation.
The detergent compositions for washing dishes in automatic dishwashers according to the invention advantageously comprise from 0.01 to 5%, or 0.1 to 3%, by weight of organophosphorus material (b)(I).
The detergent compositions for dishwashers also comprise at least one surface-active agent, preferably a nonionic surface-active agent, in an amount which can range from 0.2 to 10%, preferably from 0.5 to 5%, of the weight of said detergent composition, the remainder being composed of various additives and of fillers, as already mentioned above.
Thus, they can additionally comprise
The pH is advantageously between 8 and 14.
Compositions for Improving Rinsing of Dishes in Automatic Dishwashers
The compositions for making easier the rinsing of dishes in automatic dishwashers according to the invention can advantageously comprise from 0.02 to 10%, or from 0.1 to 5%, by weight of organophosphorus material (b)(I), with respect to the total weight of the composition.
The compositions can also comprise from 0.1 to 20%, preferably 0.2 to 15%, by weight, with respect to the total weight of said composition, of a surface-active agent, preferably a nonionic surface-active agent.
Mention may be made, among preferred nonionic surface-active agents, of surface-active agents of the following types: polyoxyethylenated C6-C12 alkylphenols, polyoxyethylenated and/or polyoxypropylenated C8-C22 aliphatic alcohols, ethylene oxide/propylene oxide block copolymers, optionally polyoxyethylenated carboxamides, and the like.
The compositions can additionally comprise from 0 to 10%, preferably from 0.5 to 5%, by weight, with respect to the total weight of the composition, of a calcium-sequestering organic acid, preferably citric acid.
They can also comprise an auxiliary agent of acrylate homopolymers, acrylate copolymers and any mixtures thereof, in a proportion of 0 to 15%, preferably 0.5 to 10%, by weight, with respect to the total weight of said composition.
The pH is advantageously between 4 and 12.
Compositions for Hand Washing Dishes
Another subject matter of the invention is a cleaning composition for making easier the washing of dishes by hand.
Preferred detergent formulations of this type comprise from 0.1 to 10 parts by weight of organophosphorus material (b)(I) per 100 parts by weight of said composition and comprise from 3 to 50, preferably from 10 to 40, parts by weight of at least one surface-active agent, preferably an anionic surface-active agent, chosen in particular from sulfates of saturated C5-C24, preferably C8-C16, aliphatic alcohols, optionally condensed with approximately from 0.5 to 30, preferably 0.5 to 8, very particularly 0.5 to 5, mol of ethylene oxide, in the acid form or in the form of a salt, in particular an alkali metal (sodium) salt, alkaline earth metal (calcium, magnesium) salt, and the like.
Preferably, they are lathering liquid aqueous detergent formulations for making easier the washing of dishes by hand.
The formulations can additionally comprise other additive, in particular other surface-active agents, such as:
The pH of the composition is advantageously between 4 and 10.
Exterior Cleaning
Another specific embodiment of the invention is a composition for making easier the exterior cleaning, in particular of the bodywork, of motorized vehicles (automobiles, trucks, buses, trains, planes, and the like) or buildings, e.g., facades, or outdoor stone work and sculptures.
In this case also, the hard surface cleaning composition can be a cleaning composition proper or a rinsing composition.
The cleaning composition for exterior cleaning advantageously comprises from 0.005 to 10% by weight of organophosphorus material (b)(I), with respect to the total weight of said composition, and:
The minimum amount of surface-active agent present in this type of composition is preferably at least 0.5% of the formulation.
The pH of the composition is advantageously between 8 and 13.
Ceramic Cleaner
The composition of the invention is also particularly suitable for making easier the cleaning of hard surfaces of ceramic type (tiling, bath tubs, bathroom sinks, and the like), in particular for bathrooms.
The cleaning formulation advantageously comprises from 0.02 to 5% by weight of organophosphorus material (b)(I), with respect to the total weight of said composition, and at least one surface-active agent.
Preference is given, as surface-active agents, to nonionic surface-active agents, in particular the compounds produced by condensation of alkylene oxide groups of hydrophilic nature with a hydrophobic organic compound which can be of aliphatic or alkylaromatic nature.
The length of the hydrophilic chain or of the polyoxyalkylene radical condensed with any hydrophobic group can be readily adjusted in order to obtain a water-soluble compound having the desired degree of hydrophilic/hydrophobic balance (HLB).
The amount of nonionic surface-active agent in the composition of the invention can be from 0 to 30% by weight, preferably from 0 to 20% by weight.
An anionic surfactant can optionally be present in an amount of 0 to 30%, advantageously 0 to 20%, by weight.
It is also possible, but not essential, to add amphoteric, cationic or zwitterionic detergents.
The total amount of surface-active compounds employed in this type of composition is generally between 0.5 and 50%, preferably between 1 and 30%, by weight and more particularly between 2 and 20% by weight, with respect to the total weight of the composition.
The cleaning composition can also comprise other minor Ingredients, such as:
The pH of the composition is advantageously between 2 and 12.
Showering Wall Rinsing Composition
The composition according to the invention is also suitable for making easier the rinsing of shower walls.
The aqueous compositions for rinsing shower walls comprise from 0.02% to 5% by weight, advantageously from 0.05 to 1%, of organophosphorus material (b)(I).
The other main active components of the aqueous compositions for rinsing showers of the present invention are at least one surface-active agent, present in an amount ranging from 0.5 to 5% by weight, and optionally a metal-chelating agent as mentioned above, present in an amount ranging from 0.01 to 5% by weight.
The aqueous compositions for rinsing showers advantageously comprise water with, optionally, a major proportion of at least one lower alcohol and a minor proportion of additives (between approximately 0.1 and approximately 5% by weight, more advantageously between approximately 0.5% and approximately 3% by weight and more preferably still between approximately 1% and approximately 2% by weight).
Some surface-active agents which can be used in this type of application are disclosed in U.S. Pat. Nos. 5,536,452 and 5,587,022, the content of which is incorporated by reference in the present description.
Preferred surfactants are polyethoxylated fatty esters, for example polyethoxylated sorbitan monooleates and polyethoxylated castor oil. Specific examples of such surface-active agents are the condensation products of 20 mol of ethylene oxide and of sorbitan monooleate (sold by Rhodia Inc. under the name Alkamuls PSMO-20® with an HLB of 15.0) and of 30 or 40 mol of ethylene oxide and of castor oil (sold by Rhodia Inc. under the names Alkamuls EL-620® (HLB of 12.0) and EL-719® (HLB of 13.6) respectively). The degree of ethoxylation is preferably sufficient to obtain a surfactant with an HLB of greater than 13.
The pH of the composition is advantageously between 7 and 14.
Glass-Ceramic Sheets Cleaning Composition
The composition according to the invention can also be employed for making easier the cleaning of glass-ceramic sheets.
Advantageously, the formulations for cleaning glass-ceramic sheets of the invention comprise:
The pH of the composition is advantageously between 7 and 14.
Reactor Cleaning Composition
As mentioned above, the composition according to the invention can also be employed in the field of industrial cleaning, in particular for making easier the cleaning of reactors.
Advantageously, the compositions comprise:
The pH of such a composition is generally from 1 to 14.
A second subject matter of the invention is the use, in a composition comprising at least one surface-active agent for cleaning or rinsing hard surfaces in an aqueous or aqueous/alcoholic medium, of at least one organophosphorus material (b)(I) as agent which makes it possible to contribute to the surface antideposition and/or antiadhesion properties with regard to soiling substances capable of being deposited on said surface.
A third subject matter of the invention is a method for improving the properties of compositions comprising at least one surface-active agent for cleaning or rinsing hard surfaces in a solvent medium (water, alcoholic, etc. . . . ) by addition to said compositions of at least organophosphorus material (b)(I).
A fourth subject matter of the invention is a method for facilitating the cleaning or rinsing of hard surfaces by bringing said surfaces into contact with a composition in a solvent medium (water, alcoholic, etc.) comprising at least one surface-active agent and at least one organophosphorus material (b)(I) employed or is present in the composition in an amount effective in contributing to said surfaces antideposition and/or antiadhesion properties with regard to soiling substances capable of being deposited on said surface.
The nature and the amounts of the organophosphorus compound (b)(I) present or employed in the composition, as well as the other additives and various forms of application of the composition, have already been mentioned above.
In this example egg-shell was stained with green/black tea stain.
In another experiment PEG400 phosphate ester (a polyethylene glycol phosphate ester) was mixed directly into the toothpaste without neutralization. An egg-shell was brushed with commercial toothpaste plus 20% PEG400 phosphate ester, then stained with green and black tea, and then brushed again with commercial tooth-paste plus 20% PEG400 phosphate ester.
In another experiment 20% sodium dodecyl sulphate (SDS) was mixed into the commercial toothpaste. The 20% SDS was used as a 100% powder.
In another experiment PEG1000 phosphate ester (a polyethylene glycol phosphate ester) was mixed directly into the toothpaste without neutralization.
In a separate test it was noted that treatment of egg-shell with SDS or PEG phosphate ester, then staining and then simple rinsing does not improve removal of stain compared to untreated egg-shell. This implies improved cleaning is not due to creation of anti-soiling layer, but due to better cleaning capability.
Comparison of
Thus, a low contact angle is observed for the crystal in pure water (i.e. good adsorption of the oil onto the crystal, which is undesirable) and a high contact angle is observed for the crystal in a solution of water and PEG 1000 phosphate ester (i.e. poor adsorption of the oil onto the crystal, which is desirable).
It is apparent that embodiments other than those expressly Described above come within the spirit and scope of the present claims. Thus, the present invention is not defined by the above description, but rather is defined by the claims appended hereto.
This application is a Continuation of U.S. application Ser. No. 12/137,738 filed Jun. 12, 2008 which claims the benefit of U.S. Provisional Application No. 60/943,517 filed Jun. 12, 2007.
| Number | Name | Date | Kind |
|---|---|---|---|
| 2438091 | Lynch | Mar 1948 | A |
| 2524218 | Bersworth | Oct 1950 | A |
| 2528378 | Mannheimer | Oct 1950 | A |
| 2530147 | Bersworth | Nov 1950 | A |
| 2658072 | Kosmin | Nov 1953 | A |
| 2826551 | Geen | Mar 1958 | A |
| 2874074 | Johnson | Feb 1959 | A |
| 2946725 | Norris et al. | Jul 1960 | A |
| 3033704 | Sherrill et al. | May 1962 | A |
| 3070510 | Cooley et al. | Dec 1962 | A |
| 3244724 | Guttmann | Apr 1966 | A |
| 3308067 | Diehl | Mar 1967 | A |
| 3332880 | Kessler et al. | Jul 1967 | A |
| 3538230 | Pader et al. | Nov 1970 | A |
| 3553139 | McCarty | Jan 1971 | A |
| 3598865 | Lew | Aug 1971 | A |
| 3599716 | Thompson | Aug 1971 | A |
| 3678154 | Widder et al. | Jul 1972 | A |
| 3681241 | Rudy | Aug 1972 | A |
| 3717630 | Booth | Feb 1973 | A |
| 3723322 | Diehl | Mar 1973 | A |
| 3793209 | Thompson | Feb 1974 | A |
| 3850831 | Hellsten et al. | Nov 1974 | A |
| 3862307 | Di Giulio | Jan 1975 | A |
| 3869412 | Waag | Mar 1975 | A |
| 3893929 | Basadur | Jul 1975 | A |
| 3912681 | Dickson | Oct 1975 | A |
| 3939911 | Maddox, Jr. et al. | Feb 1976 | A |
| 3948838 | Hinton, Jr. et al. | Apr 1976 | A |
| 3956198 | Bauer | May 1976 | A |
| 3959230 | Hays | May 1976 | A |
| 3959458 | Agricola et al. | May 1976 | A |
| 3964500 | Drakoff | Jun 1976 | A |
| 3976586 | Chakrabarti | Aug 1976 | A |
| 4001133 | Sorgenfrei et al. | Jan 1977 | A |
| 4008165 | Maddox, Jr. et al. | Feb 1977 | A |
| 4017410 | Sorgenfrei et al. | Apr 1977 | A |
| 4038027 | Kearney | Jul 1977 | A |
| 4049558 | Rasmussen | Sep 1977 | A |
| 4051234 | Gieske et al. | Sep 1977 | A |
| 4101457 | Place et al. | Jul 1978 | A |
| 4116984 | Prinzbach et al. | Sep 1978 | A |
| 4127489 | Pracht et al. | Nov 1978 | A |
| 4144226 | Crutchfield et al. | Mar 1979 | A |
| 4146495 | Crutchfield et al. | Mar 1979 | A |
| 4152416 | Spitzer et al. | May 1979 | A |
| 4152421 | Tsutsumi et al. | May 1979 | A |
| 4206215 | Bailey | Jun 1980 | A |
| 4235735 | Marco et al. | Nov 1980 | A |
| 4240919 | Chapman | Dec 1980 | A |
| 4261868 | Hora et al. | Apr 1981 | A |
| 4264580 | Barberio | Apr 1981 | A |
| 4278129 | Walton | Jul 1981 | A |
| 4287080 | Siklosi | Sep 1981 | A |
| 4288333 | van Zon et al. | Sep 1981 | A |
| 4298494 | Parslow et al. | Nov 1981 | A |
| 4321256 | Hasegawa et al. | Mar 1982 | A |
| 4342744 | Arai et al. | Aug 1982 | A |
| 4350680 | Harvey et al. | Sep 1982 | A |
| 4361465 | Graham | Nov 1982 | A |
| 4361611 | Schafer et al. | Nov 1982 | A |
| 4364837 | Pader | Dec 1982 | A |
| 4391722 | Schwartz et al. | Jul 1983 | A |
| 4393935 | Walton | Jul 1983 | A |
| 4470923 | Koster | Sep 1984 | A |
| 4483779 | Llenado et al. | Nov 1984 | A |
| 4507219 | Hughes | Mar 1985 | A |
| 4525291 | Smith et al. | Jun 1985 | A |
| 4536317 | Llenado et al. | Aug 1985 | A |
| 4536318 | Cook et al. | Aug 1985 | A |
| 4536319 | Payne | Aug 1985 | A |
| 4541483 | Walton | Sep 1985 | A |
| 4548744 | Connor | Oct 1985 | A |
| 4557853 | Collins | Dec 1985 | A |
| 4559056 | Leigh et al. | Dec 1985 | A |
| 4565647 | Llenado | Jan 1986 | A |
| 4579681 | Ruppert et al. | Apr 1986 | A |
| 4597898 | Vander Meer | Jul 1986 | A |
| 4599188 | Llenado | Jul 1986 | A |
| 4614519 | Ruppert et al. | Sep 1986 | A |
| 4627977 | Gaffar et al. | Dec 1986 | A |
| 4664839 | Rieck | May 1987 | A |
| 4702857 | Gosselink | Oct 1987 | A |
| 4711730 | Gosselink et al. | Dec 1987 | A |
| 4721580 | Gosselink | Jan 1988 | A |
| 4728455 | Rerek | Mar 1988 | A |
| 4734099 | Cyprien | Mar 1988 | A |
| 4746456 | Kud et al. | May 1988 | A |
| 4752409 | Drapier et al. | Jun 1988 | A |
| 4770666 | Clauss | Sep 1988 | A |
| 4801395 | Chazard et al. | Jan 1989 | A |
| 4813482 | Walton | Mar 1989 | A |
| 4831176 | Holmberg et al. | May 1989 | A |
| 4836949 | Klajnscek | Jun 1989 | A |
| 4859358 | Gabriel et al. | Aug 1989 | A |
| 4877896 | Maldonado et al. | Oct 1989 | A |
| 4886609 | Walton | Dec 1989 | A |
| 4891160 | Vander Meer | Jan 1990 | A |
| 4894220 | Nabi et al. | Jan 1990 | A |
| 4902499 | Bolish, Jr. et al. | Feb 1990 | A |
| 4933101 | Cilley et al. | Jun 1990 | A |
| 4968451 | Scheibel et al. | Nov 1990 | A |
| 4976879 | Maldonado et al. | Dec 1990 | A |
| 5015466 | Parran, Jr. et al. | May 1991 | A |
| 5019373 | Carter et al. | May 1991 | A |
| 5038864 | Dunleavy | Aug 1991 | A |
| 5064553 | Dixit et al. | Nov 1991 | A |
| 5098590 | Dixit et al. | Mar 1992 | A |
| 5104643 | Grollier et al. | Apr 1992 | A |
| 5114606 | van Vliet et al. | May 1992 | A |
| 5130043 | Prince et al. | Jul 1992 | A |
| 5160450 | Okahara et al. | Nov 1992 | A |
| 5236615 | Trinh et al. | Aug 1993 | A |
| 5280117 | Kerschner et al. | Jan 1994 | A |
| 5332528 | Pan et al. | Jul 1994 | A |
| 5334325 | Chaussee | Aug 1994 | A |
| 5352376 | Gutzmann | Oct 1994 | A |
| 5370865 | Yamagishi et al. | Dec 1994 | A |
| 5405542 | Trinh et al. | Apr 1995 | A |
| 5413727 | Drapier et al. | May 1995 | A |
| 5415807 | Gosselink et al. | May 1995 | A |
| 5415860 | Beucherie et al. | May 1995 | A |
| 5510042 | Hartman et al. | Apr 1996 | A |
| 5510306 | Murray | Apr 1996 | A |
| 5534197 | Scheibel et al. | Jul 1996 | A |
| 5550274 | Reierson | Aug 1996 | A |
| 5554781 | Reierson | Sep 1996 | A |
| 5559261 | Sivik | Sep 1996 | A |
| 5565145 | Watson et al. | Oct 1996 | A |
| 5573709 | Wells | Nov 1996 | A |
| 5607680 | Brissonnet et al. | Mar 1997 | A |
| 5611991 | Naraghi | Mar 1997 | A |
| 5648584 | Murray | Jul 1997 | A |
| 5648585 | Murray et al. | Jul 1997 | A |
| 5686024 | Dahanayake et al. | Nov 1997 | A |
| 5710121 | Tracy et al. | Jan 1998 | A |
| 5798326 | Goldstein et al. | Aug 1998 | A |
| 5804542 | Scheper et al. | Sep 1998 | A |
| 5824289 | Stoltz | Oct 1998 | A |
| 5849960 | Singleton et al. | Dec 1998 | A |
| 5853710 | Dehan et al. | Dec 1998 | A |
| 5858343 | Szymczak | Jan 1999 | A |
| 5879469 | Avram | Mar 1999 | A |
| 5902574 | Stoner et al. | May 1999 | A |
| 5902778 | Hartmann et al. | May 1999 | A |
| 5939052 | White, Jr. et al. | Aug 1999 | A |
| 5968893 | Manohar et al. | Oct 1999 | A |
| 6017936 | Polson et al. | Jan 2000 | A |
| 6136221 | Reierson | Oct 2000 | A |
| 6149693 | Geib | Nov 2000 | A |
| 6150222 | Gardner et al. | Nov 2000 | A |
| 6187391 | Kataoka et al. | Feb 2001 | B1 |
| 6220352 | Walton | Apr 2001 | B1 |
| 6222077 | Singleton | Apr 2001 | B1 |
| 6242404 | Dahanayake et al. | Jun 2001 | B1 |
| 6271409 | Geib | Aug 2001 | B1 |
| 6297201 | Geib | Oct 2001 | B1 |
| 6342468 | Geib | Jan 2002 | B1 |
| 6387137 | Geib | May 2002 | B1 |
| 6420323 | Geke et al. | Jul 2002 | B2 |
| 6448324 | Nodera et al. | Sep 2002 | B1 |
| 6525005 | Kravitz et al. | Feb 2003 | B1 |
| 6566313 | Hohenstein et al. | May 2003 | B1 |
| 6569261 | Aubay et al. | May 2003 | B1 |
| 6579466 | David et al. | Jun 2003 | B1 |
| 6593288 | Aubay et al. | Jul 2003 | B2 |
| 6726757 | Sarkisian | Apr 2004 | B2 |
| 6767410 | Aubey et al. | Jul 2004 | B2 |
| 6767560 | Paek | Jul 2004 | B2 |
| 6864314 | Yeung et al. | Mar 2005 | B1 |
| 6924260 | Aubay | Aug 2005 | B2 |
| 7241724 | Carnali et al. | Jul 2007 | B2 |
| 7262153 | Shpakoff et al. | Aug 2007 | B2 |
| 7332023 | Rehman et al. | Feb 2008 | B2 |
| 7381251 | Baker et al. | Jun 2008 | B2 |
| 7381695 | Minevski | Jun 2008 | B2 |
| 7416735 | El-Nokaly et al. | Aug 2008 | B2 |
| 7521404 | Luu et al. | Apr 2009 | B2 |
| 7524800 | Futterer et al. | Apr 2009 | B2 |
| 7550419 | Futterer et al. | Jun 2009 | B2 |
| 7557072 | Futterer et al. | Jul 2009 | B2 |
| 7608571 | Futterer et al. | Oct 2009 | B2 |
| 7919073 | Futterer et al. | Apr 2011 | B2 |
| 7919449 | Futterer et al. | Apr 2011 | B2 |
| 7923428 | Geffroy et al. | Apr 2011 | B2 |
| 20020174605 | Hokkirigawa | Nov 2002 | A1 |
| 20030044469 | Viladot Petit et al. | Mar 2003 | A1 |
| 20030228339 | El Nokaly et al. | Dec 2003 | A1 |
| 20040185027 | Reierson et al. | Sep 2004 | A1 |
| 20040191471 | Yahata et al. | Sep 2004 | A1 |
| 20040247534 | Stoltz | Dec 2004 | A1 |
| 20050020466 | Man | Jan 2005 | A1 |
| 20050031705 | Tyndall et al. | Feb 2005 | A1 |
| 20050037939 | Lawrence | Feb 2005 | A1 |
| 20050082090 | Grainger | Apr 2005 | A1 |
| 20050184273 | Morelli et al. | Aug 2005 | A1 |
| 20050199428 | Dixon | Sep 2005 | A1 |
| 20060088482 | Wulknitz et al. | Apr 2006 | A1 |
| 20060093559 | Fabry | May 2006 | A1 |
| 20060135384 | Luu et al. | Jun 2006 | A1 |
| 20060159631 | Buch et al. | Jul 2006 | A1 |
| 20060217286 | Geoffroy et al. | Sep 2006 | A1 |
| 20060241008 | Baker et al. | Oct 2006 | A1 |
| 20070000067 | Shi | Jan 2007 | A1 |
| 20070079964 | Shpakoff et al. | Apr 2007 | A1 |
| 20070145617 | Finney et al. | Jun 2007 | A1 |
| 20070166243 | Yoshida et al. | Jul 2007 | A1 |
| 20070286893 | Marsh et al. | Dec 2007 | A1 |
| 20070286894 | Marsh et al. | Dec 2007 | A1 |
| 20080028986 | Futterer et al. | Feb 2008 | A1 |
| 20080095719 | Herrmann et al. | Apr 2008 | A1 |
| 20080220031 | Wunsch et al. | Sep 2008 | A1 |
| 20080312118 | Futterer et al. | Dec 2008 | A1 |
| 20090123396 | Reierson et al. | May 2009 | A1 |
| 20090123407 | Futterer et al. | May 2009 | A1 |
| 20090169493 | Reierson et al. | Jul 2009 | A1 |
| 20090233837 | Futterer et al. | Sep 2009 | A1 |
| 20090238775 | Futterer et al. | Sep 2009 | A1 |
| Number | Date | Country |
|---|---|---|
| 1182101 | Feb 1985 | CA |
| 1271030 | Jan 2000 | CN |
| 218380 | Feb 1983 | CS |
| 2829022 | Jan 1980 | DE |
| 35 31 128 | May 1986 | DE |
| 199 54 830 | May 2001 | DE |
| 0011984 | Jun 1980 | EP |
| 0066915 | Dec 1982 | EP |
| 0132043 | Jan 1985 | EP |
| 0132046 | Jan 1985 | EP |
| 0219048 | Apr 1987 | EP |
| 0488868 | Jun 1992 | EP |
| 0561656 | Sep 1993 | EP |
| 0909809 | Apr 1999 | EP |
| 1752524 | Feb 2002 | EP |
| 1196523 | Apr 2002 | EP |
| 1196527 | Apr 2002 | EP |
| 1196528 | Apr 2002 | EP |
| 2236926 | Feb 1975 | FR |
| 2334698 | Jul 1977 | FR |
| 849433 | Sep 1960 | GB |
| 1314897 | Apr 1973 | GB |
| 1475798 | Jun 1977 | GB |
| 1498520 | Jan 1978 | GB |
| 1 515 792 | Jun 1978 | GB |
| 1537288 | Dec 1978 | GB |
| 1578930 | Nov 1980 | GB |
| 2054598 | Feb 1981 | GB |
| 2 192 194 | Jan 1988 | GB |
| 2192194 | Jan 1988 | GB |
| 2200356 | Aug 1988 | GB |
| 2283036 | Apr 1995 | GB |
| 2 283 755 | May 1995 | GB |
| 2283755 | May 1995 | GB |
| 47050654 | Dec 1972 | JP |
| 56062833 | May 1981 | JP |
| 62033785 | Feb 1987 | JP |
| 1-020378 | Jan 1989 | JP |
| 3-157323 | Jul 1991 | JP |
| 047547 | Jan 1992 | JP |
| 05-263362 | Oct 1993 | JP |
| 6313271 | Nov 1994 | JP |
| 11-256479 | Sep 1999 | JP |
| 2001176864 | Jun 2001 | JP |
| 2003-342140 | Dec 2003 | JP |
| 2004-076165 | Mar 2004 | JP |
| 2005-013929 | Jan 2005 | JP |
| 9532272 | Nov 1995 | WO |
| 9532997 | Dec 1995 | WO |
| 9623859 | Aug 1996 | WO |
| 9623860 | Aug 1996 | WO |
| 9623861 | Aug 1996 | WO |
| 9742287 | Nov 1997 | WO |
| 9742288 | Nov 1997 | WO |
| 9838973 | Sep 1998 | WO |
| 9838973 | Sep 1998 | WO |
| 9841505 | Sep 1998 | WO |
| 0037736 | Jun 2000 | WO |
| 2004082500 | Sep 2004 | WO |
| 2006005721 | Jan 2006 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20090124525 A1 | May 2009 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60943517 | Jun 2007 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12137738 | Jun 2008 | US |
| Child | 12349490 | US |
