A method determines a capacity of a battery cell of a high-voltage battery of a motor vehicle. The method receives at least three open-circuit voltage values of the battery cell; determines state of charge values of the battery cell from the open-circuit voltage values on the basis of a predetermined open-circuit voltage curve; forms at least two pairs of values by combining in each case two of the at least three open-circuit voltage values; determines respective charge throughput values of the battery cell which are specific to the pairs of values by integrating a measured current of the battery cell over a period between two measuring times of the associated open-circuit voltage values; determines respective capacity raw values which are specific to the pairs of values on the basis of the associated charge throughput value which is specific to the pairs of values and the associated state of charge values which are specific to the pairs of values; and determines the capacity on the basis of the at least two capacity raw values which are specific to the pairs of values.

The invention relates to a method for determining a capacity of a battery cell of a high-voltage battery of a motor vehicle. The invention furthermore relates to an evaluation apparatus, to a monitoring device, to a high-voltage battery and to a motor vehicle.
What are of interest here are high-voltage batteries or high-voltage energy stores for electrically driveable motor vehicles, for example electric vehicles or hybrid vehicles. Such high-voltage batteries generally comprise a plurality of battery cells, for example Li-ion battery cells, that are arranged in an interior or reception space of a battery housing and connected there so as to form battery modules. In this case, the Li-ion battery cells are subject to ageing. This means that an available capacity of the battery cells drops with respect to an initial capacity or nominal capacity of the battery cells as the battery cells age. For many applications, for example for estimating the range of an electric vehicle, it is essential to know the actual currently available capacity of the battery cells. To this end, use is usually made of estimation methods that are based on determining the capacity from a charge throughput of the battery cells and two values of the state of charge. In order to determine the two state of charge values, the open circuit voltage or OCV of the battery cell is measured at two different measurement times. In order to determine the charge throughput, a measured current of the battery cell is integrated over a time interval between the two measurement points.
This method results in the disadvantage that measurement errors, which may be caused for example by sensor noise when recording the open circuit voltage and the current, have a large influence on the result of the capacity calculation. The capacity calculated in this way thus possibly does not correspond to the actual currently available capacity.
The object of the present invention is to provide a solution as to how a capacity of a battery cell of a high-voltage battery for a motor vehicle is able to be determined particularly easily, reliably and accurately.
This object is achieved according to the invention by a method, an evaluation apparatus, a monitoring device, a high-voltage battery and a motor vehicle having the features according to the respective independent patent claims. Advantageous embodiments of the invention are the subject matter of the dependent patent claims, the description and the figures.
The invention relates to a method for determining a capacity of a battery cell of a high-voltage battery of a motor vehicle. In this case, first of all at least three open circuit voltage values, measured at different measurement times, of the battery cell are received and at least three state of charge values of the battery cell are determined from the open circuit voltage values on the basis of a predetermined open circuit voltage curve that describes a relationship between the open circuit voltage and the state of charge of the battery cell. At least two pairs of values of the open circuit voltage or of the state of charge are furthermore determined by combining in each case two of the at least three open circuit voltage values or state of charge values. Furthermore, respective charge throughput values, specific to the pairs of values, of the battery cell are determined by integrating a measured current of the battery cell over a time interval between the two measurement times of the associated open circuit voltage values. Finally, respective capacity raw values specific to the pairs of values are determined based on the associated charge throughput value specific to the pairs of values and the associated state of charge values specific to the pairs of values, and the capacity is determined based on the at least two capacity raw values specific to the pairs of values.
The invention furthermore relates to an evaluation apparatus for a monitoring device for monitoring a high-voltage battery of a motor vehicle, which evaluation apparatus is designed to perform a method according to the invention. A monitoring device according to the invention for monitoring a high-voltage battery of a motor vehicle comprises at least one voltage sensor for recording at least three open circuit voltage values of a battery cell of the high-voltage battery at different measurement times, at least one current sensor for recording a current of the battery cell and an evaluation apparatus according to the invention.
The invention furthermore encompasses a high-voltage battery having a multiplicity of battery cells and a monitoring device according to the invention. A motor vehicle according to the invention comprises a high-voltage battery according to the invention. The motor vehicle is in particular a passenger vehicle in the form of an electric or hybrid vehicle.
The embodiments set forth below with reference to the method according to the invention and its advantages apply analogously to the evaluation apparatus according to the invention, to the monitoring device according to the invention, to the high-voltage battery according to the invention and to the motor vehicle according to the invention.
The battery cell whose capacity is monitored is in particular a Li-ion battery cell of the high-voltage battery. The high-voltage battery is in particular a traction battery for a motor vehicle designed as an electric or hybrid vehicle. In the battery cell, the open circuit voltage and the current consumed by the battery cell are first of all measured over a predetermined measurement time interval. All of the battery cells of the high-voltage battery may in particular be monitored. To this end, the monitoring device may record the current and the open circuit voltage for each battery cell. In the case of a series connection of the battery cells, the monitoring device, in order to record the current, may have a current sensor that measures the current flowing through the series connection as the current of the battery cell to be monitored. In order to record the open circuit voltage, the monitoring device may have a voltage sensor for each battery cell. The current sensor and the voltage sensors may communicate the respective measured values to the evaluation apparatus of the monitoring device. The evaluation apparatus may be for example a superordinate evaluation apparatus for all of the battery cells of the high-voltage battery and be integrated into a battery controller of the high-voltage battery.
The measurement time interval is in this case selected such that the capacity of the battery cell does not change, or changes only insignificantly, during this time. By way of example, the measurement time interval may be one week at most. During this measurement time interval, values of the open circuit voltage or of the quiescent voltage are recorded at least three measurement times. A first open circuit voltage value is thus recorded at a first measurement time, a second open circuit voltage value is recorded at a second measurement time and a third open circuit voltage value is recorded at least one third measurement time. The state of charge value of the battery cell is then determined for each open circuit voltage value. The state of charge values are in this case determined or read from the predetermined open circuit voltage curve. The open circuit voltage curve or open circuit voltage function is predetermined for the respective battery cell and describes the relationship between the open circuit voltage and the state of charge. In the open circuit voltage curve, a state of charge value is thus assigned uniquely to each open circuit voltage value. The open circuit voltage curve may be stored or saved for example in a storage apparatus of the high-voltage battery and be read by the evaluation apparatus.
The at least two pairs of values are formed from these at least three open circuit voltage values or state of charge values. It is pointed out that the order of the steps described above is not mandatory. The pairs of values may for example first of all be determined from the recorded open circuit voltage values and the state of charge values specific to the pairs of values may then be determined. It may however also be the case that the state of charge values are first of all determined from the open circuit voltage values and pairs of values are then formed from the state of charge values. By way of example, a first pair of values that comprises the first and the second open circuit voltage value or state of charge value is formed, and a second pair of values that comprises the second and the third open circuit voltage value or state of charge value is formed. As an alternative to the first or the second pair of values or in addition to the two pairs of values, a third pair of values that comprises the first and the third open circuit voltage value or state of charge value may be formed.
A charge throughput value is furthermore determined for each of the formed pairs of values. To this end, the current that was consumed by the battery cell between the measurement times of the open circuit voltage of this pair of values is recorded. A number of charge throughput values, corresponding to the number of pairs of values, is thus determined, wherein each charge throughput value is specific to a pair of values. A capacity raw value is then determined for each pair of values. The capacity raw value specific to the pairs of values is in this case determined on the basis of the charge throughput value determined for this pair of values and on the basis of the state of charge values determined for this pair of values. The respective capacity raw values specific to the pairs of values are in particular determined as the quotient between the associated charge throughput value specific to the pairs of values and the difference between the state of charge values specific to the pairs of values.
After the capacity raw values are determined, the currently available current capacity of the battery cell is determined. In this case, in order to determine the capacity, at least two capacity raw values that have been calculated from two different pairs of values of the open circuit voltage are available. On the basis of the capacity, it is then possible for example to determine a state of health of the battery cell as the ratio between the determined capacity and a nominal capacity of the battery cell.
Using the plurality of pairs of values or value combinations results in the advantage that measurement errors have less of an impact on the overall result of the capacity determination. The result of the capacity determination thereby becomes more accurate, such that for example ageing of the battery cell is able to be forecast reliably.
The capacity raw values are preferably determined in parallel. This means that the capacity raw values are determined in method steps that take place in parallel, for example at the same time. The capacity is thus not determined iteratively based on in each case two state of charge values, but rather the capacity is determined based on at least two currently present capacity raw values, wherein the capacity raw values are in each case determined from two different state of charge values.
Particularly preferably, the binomial coefficient is determined on the basis of a number of the recorded open circuit voltage values and a number, corresponding to the binomial coefficient, of pairs of values of the open circuit voltage or of the state of charge is determined. The binomial coefficient is determined as
      n    !        2                      (                  n          -          2                )            !      (where n is the number of recorded open circuit voltage values) and describes the number of combination possibilities for two open circuit voltage values without repetition. For example, for five open circuit voltage values, that is to say n=5, ten combinations are already possible. Ten pairs of values and therefore ten capacity raw values, on the basis of which the currently available capacity of the battery cell is then determined or estimated, may thus be determined. Forming a maximum possible number of pairs of values advantageously makes it possible to determine a particularly accurate value of the capacity with reduced errors.
In one embodiment of the invention, the capacity is determined as a mean value of the determined capacity raw values. In the simplest case, the arithmetic mean may thus for example be determined from the capacity raw values by summing the capacity raw values and dividing the sum by the number of capacity raw values. The capacity is thus able to be determined based on the capacity raw values particularly easily and quickly.
The capacity is preferably determined using an optimization method, in particular using the least squares method. Using the optimization method, the capacity is thus determined on the basis of the capacity raw values such that an overall estimation error is minimal. The capacity is thus able to be determined particularly accurately and reliably.
In one particularly advantageous embodiment of the invention, in addition to the at least two capacity raw values specific to the pairs of values, at least one capacity raw value based on a model is determined, wherein the capacity raw value based on a model is determined on the basis of at least one measured loading of the battery cell and on the basis of a predetermined battery cell model depending on the loading of the battery cell, and wherein the capacity is determined based on the at least two capacity raw values specific to the pairs of values and the at least one capacity raw value based on a model. The battery cell model may be for example a statistical ageing forecasting model and describes the dependency of the capacity of the battery cell on the loading of the battery cell during operation. The battery cell model may for example be predetermined and validated for the battery cell during development of the battery cell and be stored in the storage apparatus. In order then to determine the capacity raw value based on a model during operation of the high-voltage battery, the loading of the battery cell, for example a charge throughput and/or a temperature profile and/or state of charge residence times of the battery cell, may be measured and populated into the battery cell model as input variable. The battery cell model outputs a capacity raw value specific to a model as output variable. The at least one capacity raw value specific to a model and calculated on the basis of the battery cell model and the at least two capacity raw values specific to the pairs of values may then be fused or combined in order to determine the capacity of the battery cells.
By way of example, a plurality of capacity raw values specific to a model may be determined for different time intervals, such that the capacity raw values specific to a model each correspond to a pair of values and thus each correspond to a capacity raw value specific to the pairs of values. By way of example, to this end, a first temperature profile may be determined between the first and the second measurement time and at least one second temperature profile may be determined between the second and the third measurement time. On the basis of the temperature profiles and of the battery cell model, it is then possible to determine two capacity raw values specific to a model and that are then fused with the capacity raw values specific to the pairs of values.
Further features of the invention will become apparent from the claims, the figures and the description of the figures. The features and combinations of features mentioned above in the description and the features and combinations of features mentioned below in the description of the figures and/or shown on their own in the figures may be used not only in the respectively specified combination, but also in other combinations or on their own.
The invention will now be explained in more detail on the basis of one preferred exemplary embodiment and with reference to the drawings.
Identical and functionally identical elements are provided with the same reference signs in the figures.

Method for determining a capacity of a battery cell, evaluation device, monitoring apparatus, high-voltage battery and motor vehicle

Bayerische Motoren Werke Aktiengesellschaft


A method for connecting pipe members for an endoscope includes the steps of arranging two pipe members each made of a corrosion-resistant alloy material by fitting one in another so that a passage is defined through the two pipe members, jetting inert gas toward an exterior of an area at which the two pipe members are to be connected, injecting inert gas through the passage defined through the two pipe members, and connecting the two pipes by laser welding such that a laser beam is irradiated toward the exterior of the area at which the two pipe members are to be connected with jetting the inert gas toward the exterior of the area at which the two pipe members are to be connected and injecting the inert gas through the passage defined by through the two pipe members.

1. Technical Field
The present invention relates to a method of connecting pipe members for an endoscope.
2. Related Art
Generally, pipe members used for endoscopes are made of corrosion-resistant alloy materials, and pipe members are connected by welding or silver-alloy brazing and the like to have a watertight structure. In recent years, laser beam irradiation so-called laser welding has been used in view of easiness of operation and steadiness of welding. An example of such a configuration is disclosed in Japanese Patent Provisional Publication No. HEI 4-25007.
When laser welding is performed, a connection area irradiated with a laser beam tends to be unnecessarily oxidized due to increase of temperature. In such a case, the connection strength may be largely lowered.

Method of connecting pipe members for endoscope


Various embodiments are directed to techniques managing telephone numbers and other telecommunication identifiers when placing and receiving calls or messages from a single device. In some embodiments, one of a plurality of outbound telephone numbers or other identifiers associated with the device or an application executing on the device may be selected when making an outbound telephone call or sending a message. In another embodiment, an outbound telephone number or other identifier is automatically selected when making an outbound telephone call or sending a message based on an association of that outbound telephone number with the intended recipient of the call or message.

People often have multiple phone numbers that may be associated with a single device. For example, some mobile phone applications can accommodate multiple user phone numbers on the same device. One example of such an application is RingTo™ developed by Bandwidth.com, Inc. RingTo™ may be executed on Apple™ IOS platforms and Android™ platforms and allows users to port one or more telephone numbers to a cloud based server. These telephone numbers may be used to make outgoing telephone calls and receive incoming telephone calls on Apple™ IOS or Android™ devices executing the RingTo™ application.
While users appreciate access to multiple telephone numbers on a single device, especially for incoming calls, it can be problematic to track which of the telephone numbers to use when making an outbound call. For example, a user may have both a personal telephone number and a business telephone number associated with the same device. When making a call for business purposes, the user prefers to use the business telephone number. Similarly, when making a personal call, the user prefers to use the personal telephone number.
What is needed is a mechanism that permits the user to select, on a per call basis, which telephone number of a plurality to associate with an outbound telephone call.

Techniques for telecommunications contact management on an end user device


A metallic container end closure is provided which includes a channel or groove in a predetermined location in at least one of an inner panel wall, outer panel wall, or chuckwall, and which is formed by a shaping tool. An apparatus and method for spin-forming the end closure with the improved geometry is also provided herein.

Containers, and more specifically metallic beverage containers, are typically manufactured by interconnecting a beverage can end closure on a beverage container body. In some applications, an end closure may be interconnected on both a top side and a bottom side of a can body. More frequently, however, a beverage can end closure is interconnected on a top end of a beverage can body which is drawn and ironed from a flat sheet of blank material such as aluminum. Due to the potentially high internal pressures generated by carbonated beverages, both the beverage can body and the beverage can end closure are typically required to sustain internal pressures exceeding 90 psi without catastrophic and permanent deformation. Further, depending on various environmental conditions such as heat, over fill, high CO2 content, and vibration, the internal pressure in a typical beverage can may at times exceed 100 psi. Thus, beverage can bodies and end closures must be durable to withstand high internal pressures, yet manufactured with extremely thin and durable materials such as aluminum to decrease the overall cost of the manufacturing process and the weight of the finished product.
Accordingly, there exists a significant need for a durable beverage container end closure which can withstand the high internal pressures created by carbonated beverages, and the external forces applied during shipping, yet which is made from a durable, lightweight and extremely thin metallic material with a geometric configuration which reduces material requirements. Previous attempts have been made to provide beverage container end closures with unique geometric configurations to provide material savings and improve strength. One example of such an end closure is described in U.S. Pat. No. 6,065,634 To Crown Cork and Seal Technology Corporation, entitled "Can End and Method for Fixing the Same to a Can Body". Other inventions known in the art have attempted to improve the strength of container end closures and save material costs by improving the geometry of the countersink region. Examples of these patents are U.S. Pat. Nos. 5,685,189 and 6,460,723 to Nguyen et al, which are incorporated herein in their entirety by reference. Another pending application which discloses other improved end closure geometry is disclosed in pending U.S. patent application Ser. No. 10/340,535, which was filed on Jan. 10, 2003 and is further incorporated herein in its entirety by reference. Finally, the assignee of the present application owns another pending application related to reforming and reprofiling a container bottom, which is disclosed in pending U.S. Pat. No 11/020,944 and which is further incorporated herein by reference in its entirety.
The following disclosure describes an improved container end closure which is adapted for interconnection to a container body and which has an improved countersink, chuck wall geometry, and unit depth which significantly saves material costs, yet can withstand significant internal pressures.
Previous methods and apparatus used to increase the strength of a container end closure have generally been attempted using traditional forming presses, which utilize a sequence of tooling operations in a reciprocating press to create a specific geometry. Unfortunately with the use of small gauge aluminum and other thin metallic materials, it has become increasingly difficult to form a preferred geometry without quality control issues as a result of the physical properties of the end closure and the difficulty of retaining a desired shape. Furthermore, when a thin metallic material is worked in a traditional forming press, certain portions of the end closure may be thinned, either from stretching, bending operations, commonly known as "coining". When excessive thinning occurs, the overall strength and integrity of the end closure may be compromised. Further, it is practically impossible to form certain geometries with a typical die press. Thus, there is a significant need in the industry for a new method and apparatus for forming a preferred shape in an end closure, and which uses rollers and other mechanical devices which can form a preferred shape in the end closure without requiring traditional forming presses and the inherent problems related thereto.
Furthermore, new end closure geometries are needed which have distinct shapes and provide superior strength and buckle resistance when interconnected to pressurized containers. As previously mentioned these geometries are typically not feasible using traditional end closure manufacturing techniques. Thus, there is a significant need for new end closure geometries which have improved strength characteristics and which are capable of being formed with thin walled metallic materials.

Method and apparatus for forming a reinforcing bead in a container end closure


A method for improving the integrity of a cosmetic film applied to nails or surrounding cuticle surfaces comprising applying to the surface an effective amount of a composition comprising less than 5% by weight of the total composition of a fluorinated oil. The invention also comprises a nail and cuticle conditioning composition and a semi-permanent film forming composition containing the fluorinated oil.

The invention is in the field of cosmetic compositions for application to nails and surrounding cuticle tissue.
The application of cosmetic and personal care products to the skin almost always involves the formation of a film on the skin. For example, application of a foundation to the face involves formation of a colored film on the skin. The same is true of products such as lipstick, eyeshadow, blush, nail enamel, and nail treatment products. The product is applied to the appropriate keratinous surface and allowed to dry. A film is formed which adheres to the skin for the appropriate period of time before being removed by chemical processes, or washed off with water.
The attributes of a cosmetic film depend on the type of product that is being formulated. Still, no matter what type of cosmetic is being prepared, the film integrity is of importance. Film integrity plays a direct role in the wear, appearance, and durability of the cosmetic.
Accordingly, there is a need for methods and ingredients that will enhance the integrity of a cosmetic film that is formed upon a keratinous surface. Film integrity is particularly important for products that are applied to the fingernails or toenails and surrounding cuticle tissue because these extremities are exposed to a wide variety of environmental assaults such as abrasion, detergents, bumping, and so on. Accordingly, cosmetic films applied to nails and surrounding tissue should advantageously have excellent moisture barrier properties, be capable of forming a cohesive film on the area that exhibits improved resistance to typical environmental assaults, and in addition be aesthetically pleasing.
Unexpectedly, it has been discovered that formulating compositions applied to nails and surrounding cuticle tissue with less than 5%, more preferably less than 1% by weight of a fluorinated oil will provide compositions that exhibit substantially improved films.
The invention comprises a method for improving the integrity of a cosmetic film formed on fingernails, toenails, and surrounding cuticular tissue comprising applying to said surfaces a composition containing less than 5% by weight of a fluorinated oil.
The invention also comprises a nail and cuticle conditioning composition comprising 0.00001 to 5% of a fluorinated oil, and 10-99% of a non-fluorinated oil.
The invention also comprises a semi-permanent film forming composition comprising 0.00001-5% of a fluorinated oil, 5-99% solvent and 1-85% of a film forming polymer.
The fluorinated oil will improve the film integrity in a variety of ways. First, due to its water repellant nature, the fluorinated oil in the composition will cause the composition to exhibit improved moisture barrier properties when applied to the desired surface due to phase separation. In particular, the fluorinated oil separates from the core composition and acts as improved barrier. This in turn may cause improvement in conditions such as dryness, cracking, and other undesirable characteristics of the nails and surrounding cuticle tissue. Often these types of conditions are exacerbated by exposure of the hands to detergents, water, and other environmental assaults. In addition, the presence of a fluorinated oil in semi-permanent film forming compositions such as nail enamel, will improve the integrity of the film by causing the film formed to exhibit improved gloss, leveling, and mar resistance in addition to water repellency. The improved gloss is due to the fluorinated oil migrating to the surface of the film formed on the nail after the nail enamel is applied to the nail and dried, e.g. phase separation. The solvents evaporate in the drying process, leaving the fluorinated oil on the surface of the dried film. The resulting finish exhibits improved gloss, improved water repellency, and the superficial fluorinated oil layer improves mar resistance. The term xe2x80x9cmar resistancexe2x80x9d means that the dried film is not as readily scratched or scuffed. In addition, the improved leveling provided by the fluorinated oil enables the nail enamel film to be evenly applied without bubbles or other surface aberrations, which irregularities also impair the integrity of the film. A film that maintains its integrity is better able to protect the surface to which it is applied. The amount of the fluorinated oil is critical in achieving the desired phase separation. In particular, if the amount of fluorinated oil is too great there will be little or no phase separation and the compositions will not exhibit the desired properties. If the amount of fluorinated oil is too small, not enough of the oil is present to exhibit the desired properties.
The amount of fluorinated oil contained within the composition is within a very narrow range. In particular, if the fluorinated oil is present at more than 5% by weight, the resulting compositions may be unstable and may separate with time, and will not provide the benefits described herein. The compositions used in the method of the invention may be oil based compositions for conditioning nails and surrounding tissue, or they may be semi-permanent film forming compositions in the form of pigmented nail enamel, basecoats, or topcoats. While both types of compositions are capable of forming a film on the nails and surrounding tissue to which they are applied, the nail enamel type compositions form what is referred to as a xe2x80x9csemi-permanentxe2x80x9d film in that the film cannot be removed by soap and water alone, but requires removal by organic solvent based removers. The term xe2x80x9cfilmxe2x80x9d when used in accordance with the invention means the film formed by conditioning compositions such as lotions, creams and the like which may be removed by soap and water, as well as the semi-permanent films formed by nail enamel compositions such as basecoats, topcoats, and color nail enamel products that require removal by organic solvent compositions.
The invention comprises a method for improving the integrity of a cosmetic film applied to nails or surrounding cuticle surfaces comprising applying to the surface an effective amount of a composition comprising less than about 5% by weight of the total composition of a fluorinated oil. (All percentages mentioned herein are percentages by weight unless otherwise indicated.)
The invention also comprises a nail and cuticle conditioning composition comprising 0.00001 to 5% of a fluorinated oil, and 10-99% of a non-fluorinated oil.
The invention also comprises a semi-permanent film forming composition comprising 0.00001-5% of a fluorinated oil, 5-99% solvent and 1-85% of a film forming polymer.
I. The Method of the Invention
Any type of composition normally applied to skin or surrounding cuticle tissue may be suitable for use in the claimed method so long as that composition is a suitable vehicle for the fluorinated oil and requisite amounts of the fluorinated oil is stable therein. Examples of such compositions include nail and cuticle treatment creams, lotions, and the like as well as nail enamel compositions including basecoats, topcoats, nail strengtheners, and regular pigmented nail enamel. The integrity of the film formed is improved in moisture barrier properties, and in the case of semi-permanent films, those films exhibit improved gloss, mar resistance, and water repellency as well.
The compositions containing the fluorinated oil may be applied to the nails or cuticle tissue one or more times per day. In the case where the composition is a cuticle or nail conditioning cream or lotion, the composition may be applied as often as desired. In the case where the composition is a nail enamel composition, the composition may be applied one or more times per day or as often as instructed by the product manufacturer.
The fluorinated oil used in the method of the invention may be an organic oil or a silicone oil.
The composition used in the method contains less than 5% by weight of the fluorinated oil. Including more than 5% by weight may cause the composition to be unstable and prone to separation, which comprises the commercial value of the compositions. Preferably the amount of fluorinated oil ranges from 0.0001 to 5, preferably 0.0005 to 3, more preferably 0.0005 to 1, more preferably 0.001 to 0.5%, most preferably from 0.001-0.05% by weight of the total composition. The fluorinated oil may be an organic oil or a silicone oil. The term xe2x80x9cfluorinated oilxe2x80x9d means an ingredient that is a liquid, semi-solid, or solid (e.g. having a wax-like consistency) at room temperature and has one or more fluorine substitutions in the molecular structure. Preferably, the fluorinated oil is a liquid or semi-solid at room temperature and has a viscosity of 5 to 500,000, more preferably 10 to 250,000 centipoise, most preferably 20 to 200,000 centipoise at 25xc2x0 C.
Suitable fluorinated oils include silicones, esters, or perfluoropolyethers.
A. Fluorinated Silicone Oils
Suitable fluorinated silicone oils include trimethylsilyl endcapped fluorosilicone oils, polytrifluoropropylmethylsiloxanes, and similar silicones. Such silicones may be linear or cyclic, and will contain one or more fluorine atoms substituted for the hydrogen atoms on the carbon atom. Preferably the fluorinated silicone is a water insoluble nonvolatile silicone. The term xe2x80x9cnonvolatilexe2x80x9d means that the silicone has a vapor pressure of less than 2 mm. of mercury at 20xc2x0 C.
One type of fluorinated silicone that may be used in the method of the invention is disclosed in U.S. Pat. No. 5,473,038 which is hereby incorporated by reference in its entirety. Such silicones have the general formula:
wherein:
Rxe2x80x2 is xe2x80x94(CH2)axe2x80x94CH3
R is C1-4 alkyl, xe2x80x94(CH2)axe2x80x94(CF2)bCF3
a is 0 to 100
b is 0 to 100
c is 0 to 100
d is 0 to 100
e is 0 to 100, with the proviso that the polymer must contain at least one fluorine substituted moiety.
Preferred are fluorinated silicones of the above formula wherein Rxe2x80x2 and R are C1-4 alkyl, c is 1-100, d is 1-100, e is 0, and R is xe2x80x94(CH2)axe2x80x94(CF2)bCF3 wherein a is 1-12 and b is 0 to 10.
Particularly preferred are the fluorinated silicones trifluoromethyl C1-4 alkyl dimethicone and fluoro C2-8 alkyl dimethicone.
Another fluorosilicone suitable for use in the method comprises fluorinated dimethicone copolyols as disclosed in U.S. Pat. No. 5,446,114, which is hereby incorporated by reference. Such compounds have the general formula:
wherein:
Rxe2x80x2 is C1-4 alkyl, or xe2x80x94(CH2)3xe2x80x94Oxe2x80x94(EO)axe2x80x94(PO)bxe2x80x94(EO)cxe2x80x94H
R is C1-4 alkyl, xe2x80x94(CH2)axe2x80x94(CF2)bCF3
EO is xe2x80x94(CH2CH2xe2x80x94O)xe2x80x94
PO is xe2x80x94(CH2CH(CH3)xe2x80x94O)xe2x80x94
a is 0 to 100
b is 0 to 100
c is 0 to 100
d is 0 to 100
e is 0 to 100, with the proviso that the polymer must contain at least one fluorine substituted radical and at least one alkylene oxide moiety.
Also suitable as the fluorinated silicone are fluorine containing silicone polyester compounds as disclosed in U.S. Pat. No. 5,235,017 which is hereby incorporated by reference in its entirety. Such compounds are formed by the esterification of
a dimethicone copolyol having the general formula:
wherein
o is 1 to 20
q is 1 to 20
EO is xe2x80x94(CH2xe2x80x94CH2xe2x80x94Oxe2x80x94)xe2x80x94
PO is xe2x80x94(xe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94Oxe2x80x94)xe2x80x94; and
x, y, and z are integers ranging from 0 to 20 with a diacid selected from the group:
HO(O)Cxe2x80x94(CH2)cxe2x80x94C(O)OH; HO(O)Cxe2x80x94(CH2)dxe2x80x94CHxe2x95x90CHxe2x80x94(CH2)exe2x80x94C(O)OH and dimer acids, wherein c, d, and e are independently integers from 1 to 10; and
a fluorine containing hydroxy compound having the following formula:
Fxe2x80x94Cxe2x80x94(F2)xe2x80x94[Cxe2x80x94(F2)]nxe2x80x94CH2xe2x80x94CH2xe2x80x94OH
wherein n ranges from 3 to 17.
One example of a such a compound is dimethiconol fluoroalcohol dilinoleic acid.
Other types of fluorinated silicone that may be used in the claimed method are silicone fluoroesters as disclosed in U.S. Pat. No. 6,008,397 which is hereby incorporated by reference in its entirety. These silicones are made by reacting a carboxy silicone and a fluoroalcohol.
B. Fluorinated Organic Oils
Also suitable for use in the claimed method are various types of fluorinated organic oils such as esters, perfluoropolyethers, and so on.
1. Esters
Fluorine containing citrate esters are particularly suitable for use in the claimed method. Such esters are disclosed in U.S. Pat. No. 5,312,968, which is hereby incorporated by reference. Further examples of such esters include those of the general formula:
wherein R1, R2, and R3 are each independently
an alkyl having 4 to 30 carbon atoms, or
xe2x80x94(CH2)x(CF2)yCF3
where x is 0-10, and y is 1-20; with the proviso that at least one of R1, R2 and R3 is xe2x80x94(CH2)x(CF2)yCF3
Preferred is the above compound wherein R1 and R2 are 4-20 alkyl and R3 is xe2x80x94(CH2)x(CF2)yCF3. Particularly preferred is wherein Rxe2x80x2 and R2 are octyldodecyl and R3 is xe2x80x94(CH2)x(CF2)yCF3 wherein x is 2 and y is 4. This compound has the CTFA name dioctyldodecyl fluoroheptyl citrate.
Also suitable are fluorinated meadowfoam esters which are prepared by the esterification of meadowfoam oil with one or more fluorinated alcohols using the same synthetic methods taught in U.S. Pat. No. 5,786,388, which is hereby incorporated by reference. In particular, this patent teaches the synthesis of meadowfoam esters by esterification of the fatty acids found in meadowfoam oil with one or more alcohols. Such alcohols may be regular fatty alcohols or fluorinated alcohols. Particularly preferred is a fluorinated meadowfoam ester having the CTFA name fluoro octyldodecyl meadowfoamate.
2. Perfluoropolyethers
Also suitable are perfluoropolyethers like those disclosed in U.S. Pat. Nos. 5,183,589, 4,803,067, and 5,183,588, all of which are incorporated by reference, are also suitable. These perfluoropolyethers are commercially available from Montefluos under the tradename Fomblin.
The fluorinated oils may be used in one or more compositions designed to be applied to nails or surrounding cuticle tissue, as more fully described below.
II. The Compositions Used in the Method
The compositions used in the method of the invention may be conditioning compositions which provide a film on the keratinous surface that is removed by soap and water washing, or the film may be semi-permanent which means that it is not removed without use of chemicals such as organic solvents. Examples of both types of compositions include cuticle moisturizers and conditioners, nail strengthening conditioners, nail enamel basecoat or topcoat composition, or regular pigmented nail enamel. The compositions may contain water or may be anhydrous. Preferably the compositions are substantially anhydrous which means that they contain less than 5% by weight of water, more preferably less than 3%, most preferably less than 1% by weight of water. Although the preferred compositions are substantially anhydrous, a wide variety of compositions suitable for use in the invention may contain appreciable amounts of water such as waterborne nail enamel, cuticle creams and lotions, etc.
A. Conditioning and Moisturizing Compositions
A variety of conditioning and moisturizing compositions containing the fluorinated oil may be used in the method of the invention. Such compositions may contain oils, structuring agents such as waxes, extracts, nutrients, preservatives, and so on.
1. Oils
A wide variety of non-fluorinated oils may be used in the compositions. Generally such compositions contain about 10-99%, preferably 15-90%, more preferably 20-85% by weight of the total composition of one or more oils. Suitable oils include silicone oils and organic oils which may be volatile or nonvolatile.
(a) Volatile Oils
The oils used may be volatile or nonvolatile. The term xe2x80x9cvolatilexe2x80x9d means that the oil has a measureable vapor pressure, or a vapor pressure of at least 2 mm. of mercury at 20xc2x0 C. The term xe2x80x9cnonvolatilexe2x80x9d means that the oil has a vapor pressure of less than 2 mm. of mercury at 20xc2x0 C. Suitable volatile solvents generally have a viscosity of 0.5 to 10 centistokes at 25xc2x0 C. Suitable volatile oils include linear silicones, cyclic silicones, paraffinic hydrocarbons, or mixtures thereof.
Cyclic silicones (or cyclomethicones) are of the general formula:
where n=3-6.
Linear volatile silicones in accordance with the invention have the general formula:
(CH3)3Sixe2x80x94Oxe2x80x94[Si(CH3)2xe2x80x94O]nxe2x80x94Si(CH3)3
where n=0-7, preferably 0-5.
Linear and cyclic volatile silicones are available from various commercial sources including Dow Corning Corporation and General Electric. The Dow Corning volatile silicones are sold under the tradenames Dow Corning 244, 245, 344, and 200 fluids. These fluids comprise octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, and mixtures thereof.
Also suitable as the volatile oils are various straight or branched chain paraffinic hydrocarbons having 5 to 40 carbon atoms, more preferably 8-20 carbon atoms. Suitable hydrocarbons include pentane, hexane, heptane, decane, dodecane, tetradecane, tridecane, and C8-20 isoparaffins as disclosed in U.S. Pat. Nos. 3,439,088 and 3,818,105, both of which are hereby incorporated by reference. Preferred volatile paraffinic hydrocarbons have a molecular weight of 70-225, preferably 160 to 190 and a boiling point range of 30 to 320, preferably 60-260 degrees C., and a viscosity of less than 10 cs. at 25 degrees C. Such paraffinic hydrocarbons are available from EXXON under the ISOPARS trademark, and from the Permethyl Corporation. Suitable C12 isoparaffins are manufactured by Permethyl Corporation under the tradename Permethyl 99A. Another C12 isoparaffin (isododecane) is distributed by Presperse under the tradename Permethyl 99A. Various C16 isoparaffins commercially available, such as isohexadecane (having the tradename Permethyl R), are also suitable. Transfer resistant cosmetic sticks of the invention will generally comprise a mixture of volatile silicones and volatile paraffinic hydrocarbons.
(b) Nonvolatile Oils
A variety of nonvolatile oils are also suitable for use in the cosmetic compositions of the invention. The nonvolatile oils generally have a viscosity of greater than 10 centipoise at 25xc2x0 C., and may range in viscosity up to 1,000,000 centipoise at 25xc2x0 C. Examples of nonvolatile oils suitable for use in the cosmetic sticks of the invention include esters of the formula RCOxe2x80x94ORxe2x80x2 wherein R and Rxe2x80x2 are each independently a C1-25, preferably a C4-20 straight or branched chain alkyl, alkenyl or alkoxycarbonylalkyl or alkylcarbonyloxyalkyl. Examples of such esters include isotridecyl isononanoate, PEG-4 diheptanoate, isostearyl neopentanoate, tridecyl neopentanoate, cetyl octanoate, cetyl palmitate, cetyl ricinoleate, cetyl stearate, cetyl myristate, coco-dicaprylate/caprate, decyl isostearate, isodecyl oleate, isodecyl neopentanoate, isohexyl neopentanoate, octyl palmitate, dioctyl malate, tridecyl octanoate, myristyl myristate, octododecanol, and fatty alcohols such as oleyl alcohol, isocetyl alcohol, and the like, as well as the esters disclosed on pages 24-26 of the C.T.F.A. Cosmetic Ingredient Handbook, First Edition, 1988, which is hereby incorporated by reference.
The oil may also comprise naturally occuring glyceryl esters of fatty acids, or triglycerides. Both vegetable and animal sources may be used. Examples of such oils include castor oil, lanolin oil, triisocetyl citrate, C10-18 triglycerides, caprylic/capric/triglycerides, coconut oil, corn oil, cottonseed oil, linseed oil, mink oil, olive oil, palm oil, illipe butter, rapeseed oil, soybean oil, sunflower seed oil, walnut oil, and the like.
Also suitable as the oil are synthetic or semi-synthetic glyceryl esters, e.g. fatty acid mono-, di-, and triglycerides which are natural fats or oils that have been modified, for example, acetylated castor oil, glyceryl stearate, glyceryl dioleate, glyceryl distearate, glyceryl trioctanoate, glyceryl distearate, glyceryl linoleate, glyceryl myristate, glyceryl isostearate, PEG castor oils, PEG glyceryl oleates, PEG glyceryl stearates, PEG glyceryl tallowates, and so on.
Also suitable as the oil are nonvolatile hydrocarbons such as isoparaffins, hydrogenated polyisobutene, mineral oil, squalene, petrolatum, and so on.
Straight or branched chain fatty alcohols having the formula Rxe2x80x94OH, wherein R is a straight or branched chain saturated or unsaturated alkyl having 6-30 carbon atoms, are also suitable oils. Such fatty alcohols include cetyl alcohol, stearyl alcohol, cetearyl alcohol, and the like.
Also suitable as the oil are various lanolin derivatives such as acetylated lanolin, acetylated lanolin alcohol, and so on.
Nonvolatile silicones, both water soluble and water insoluble, are also suitable as the oil component. Such silicones preferably have a viscosity of 10 to 600,000 centistokes, preferably 20 to 100,000 centistokes at 25xc2x0 C. Suitable water insoluble silicones include amodimethicone, bisphenylhexamethicone, dimethicone, hexadecyl methicone, methicone, phenyl trimethicone, simethicone, dimethylhydrogensiloxane, stearoxytrimethylsilane, vinyldimethicone, and mixtures thereof. Also suitable are water soluble silicones such as dimethicone copolyol, dimethiconol, and the like. Such silicones are available from Dow Corning as the 3225C formulation aid, Dow 190 and 193 fluids, or similar products marketed by Goldschmidt under the ABIL tradename.
Guerbet esters are also suitable oils. The term xe2x80x9cguerbet esterxe2x80x9d means an ester which is formed by the reaction of a guerbet alcohol having the general formula:
with a carboxylic acid having the general formula:
R3COOH,
or
HOOCxe2x80x94R3xe2x80x94COOH
wherein R1 and R2 are each independently a C4-20 alkyl and R3 is a substituted or unsubstituted fatty radical such as a C1-50 straight or branched chain saturated or unsaturated alkyl or alkylene, or phenyl, wherein the substituents are halogen, hydroxyl, carboxyl, and alkylcarbonylhydroxy. Particularly preferred is a carboxylic acid wherein the R group is such to provide an ingredient known as meadowfoam seed oil.
2. Vitamins and Antioxidants
The compositions used in the method of the invention may contain vitamins and/or coenzymes, as well as antioxidants. If so, 0.0001-10%, preferably 0.0005-8%, more preferably 0.001-5% by weight of the total composition are suggested. Suitable vitamins include the B vitamins such as thiamine, riboflavin, pyridoxin, and so on, as well as coenzymes such as thiamine pyrophoshate, flavin adenin dinucleotide, folic acid, pyridoxal phosphate, tetrahydrofolic acid, and so on. Also Vitamin A and derivatives thereof are suitable. Examples are Vitamin A palmitate, acetate, or other esters thereof, as well as Vitamin A in the form of beta carotene. Also suitable is Vitamin E and derivatives thereof such as Vitamin E acetate, nicotinate, or other esters thereof In addition, Vitamins D, K, and C are also suitable.
Suitable antioxidants are ingredients which assist in preventing or retarding spoilage. Examples of antioxidants suitable for use in the compositions of the invention are potassium sulfite, sodium bisulfite, sodium erythrobate, sodium metabisulfite, sodium sulfite, propyl gallate, cysteine hydrochloride, butylated hydroxytoluene, butylated hydroxyanisole, and so on.
3. Preservatives
The composition may contain 0.0001-8%, preferably 0.001-6%, more preferably 0.005-5% by weight of the total composition of preservatives. A variety of preservatives are suitable, including such as benzoic acid, benzyl alcohol, benzylhemiformal, benzylparaben, 5-bromo-5-nitro-1,3-dioxane, 2-bromo-2-nitropropane-1,3-diol, butyl paraben, calcium benzoate, calcium propionate, captan, chlorhexidine diacetate, chlorhexidine digluconate, chlorhexidine dihydrochloride, chloroacetamide, chlorobutanol, p-chloro-m-cresol, chlorophene, chlorothymol, chloroxylenol, m-cresol, o-cresol, DEDM Hydantoin, DEDM Hydantoin dilaurate, dehydroacetic acid, diazolidinyl urea, dibromopropamidine diisethionate, DMDM Hydantoin, and all of those disclosed on pages 570 to 571 of the CTFA Cosmetic Ingredient Handbook, Second Edition, 1992, which is hereby incorporated by reference.
4. Waxes
The compositions used in the method of the invention may, if desired, contain one or more waxes. If present, suggested ranges are from about 1-70%, preferably 1-30%, more preferably 1-25% by weight of a cosmetically acceptable natural or synthetic wax. The waxes that can be used are solid or semi-solid waxes having a melting point of 30 to 120xc2x0 C. and generally includes animal waxes, plant waxes, mineral waxes, silicone waxes, synthetic waxes, and petroleum waxes.
Examples of waxes in accordance with the invention include bayberry, beeswax, candelilla, carnauba, ceresin, cetyl esters, hydrogenated jojoba oil, hydrogenated jojoba wax, hydrogenated microcrystalline wax, hydrogenated rice bran wax, japan wax, jojoba butter, jojoba esters, jojoba wax, lanolin wax, microcrystalline wax, mink wax, montan acid wax, montan wax, ouricury wax, ozokerite, paraffin, PEG-6 beeswax, PEG-8 beeswax, rice bran wax, shellac wax, spent grain wax, sulfurized jojoba oil, synthetic beeswax, synthetic candelilla wax, synthetic carnauba wax, synthetic japan wax, synthetic jojoba oil, synthetic wax, stearoxy dimethicone, dimethicone behenate, stearyl dimethicone, and the like, as well synthetic homo- and copolymer waxes from the ethylene series. In the preferred embodiment of the invention the waxes are polymers of ethylene and/or propylene.
5. Plant Extracts
It may also be desireable to add various types of plant extracts. If so, 0.0001-5%, preferably 0.001-4%, more preferably 0.01-2% is suggested. Suitable plant extracts include intact and hydrolyzed extensins such as those set forth in U.S. Pat. No. 5,443,855, which is hereby incorporated by reference. Also suitable are extracts of acacia extract, algae, alfalfa, aloe, aloe barbadensis, gingko, bayberry, avocado, calendula, broom, apple, anise, birch, bitter orange, as well as those set forth on pages 493-494 of the CTFA Cosmetic Ingredient Handbook, Second Edition, 1992, which is hereby incorporated by reference. Particularly preferred is aloe barbadensis extract.
The conditioning compositions are applied to nails or cuticles and provide moisturization and conditioning to nail and cuticle tissue.
B. Semi-Permanent Film Forming Compositions
Suitable for use in practice of the claimed method are film forming compositions that provide a semi-permanent film removable with organic solvents, such as nail enamel.
1. Solvents
Suitable solvents that may be used in nail coating compositions are organic solvents or water. Preferably, the composition contains 5-99%, preferably 10-95%, more preferably 15-85% by weight of the total composition of solvent. The solvent may be aqueous or non-aqueous or a mixture of both types of solvents. Suitable non-aqueous solvents include aliphatic or aromatic ketones such as acetone, diacetone alcohol, dihydroxyacetone, ethyl butyl valerolactone, methyl ethyl ketone, and the like; aliphatic or aromatic alcohols such as methanol, propanol, benzyl alcohol, butoxyethanol, butoxypropanol, butyl alcohol, 3-methyl-3-methoxy-butanol, t-butyl alcohol, butylene glycol, diethylene glycol, abietyl alcohol, propylene carbonate,hexyl alcohol, isopropanol, and the like; glycol ethers; esters such as butyl acetate, ethyl acetate, etc.
2. Film Forming Polymer
Semi-permanent compositions generally comprise one or more film forming polymers that form a semi-permanent film on the keratinous surface.
A wide variety of film forming polymers may be used in the cosmetic or personal care products of the invention. The film forming polymer must be capable of forming a film on the skin, nails, or hair. The film forming polymers may be natural or synthetic, or a combination of both, and may be in the form of solids, semi-solids, or liquids. The film forming polymer may be neutral or ionic in character, e.g. anionic, cationic, nonionic, or amphoteric. Suggested ranges of film forming polymer are 1-85%, preferably 2-80%, more preferably 5-70% by weight of the total composition.
(a). Synthetic Polymers
Suitable synthetic polymers include homopolymers, copolymers, and block and graft copolymers comprised of repeating monomers such as acrylic or methacrylic acid or esters thereof, urethanes, esters, amides, styrene, vinyl, silicon, and so on. The synthetic polymers may be present in the composition in ranges from 0.1-95%, preferably 1-85%, more preferably 3-45% by weight of the total composition.
Examples of synthetic film forming polymers include those set forth in the CTFA Cosmetic Ingredient Dictionary and Handbook, Eighth Edition, 2000, pages 1744 through 1747, which are hereby incorporated by reference, including those which are summarized herein.
(i) Silicone Resins
Cross-linked silicones, also known as silicone resins, can be plasticized with C1-20 esters of malic acid, and are suitable for use in the compositions and method of the invention. Preferred silicone resins have the general formula:
[(RRxe2x80x2Rxe2x80x3)3SiO1/2]x[SiO2]y
wherein R, Rxe2x80x2 and Rxe2x80x3 are each independently a C1-10 straight or branched chain alkyl or phenyl, and x and y are such that the ratio of (RRxe2x80x2Rxe2x80x3)3SiO1/2 units to SiO2 units is 0.5 to 1 to 1.5 to 1.
Preferably R, Rxe2x80x2 and Rxe2x80x3 are a C1-6 alkyl, and more preferably are methyl and x and y are such that the ratio of (CH3)3SiO1/2 units to SiO2 units is 0.75 to 1. Most preferred is this trimethylsiloxy silicate containing 2.4 to 2.9 weight percent hydroxyl groups which is formed by the reaction of the sodium salt of silicic acid, chlorotrimethylsilane, and isopropyl alcohol. The manufacture of trimethylsiloxy silicate is set forth in U.S. Pat. Nos. 2,676,182; 3,541,205; and 3,836,437, all of which are hereby incorporated by reference. Trimethylsiloxy silicate as described is available from Dow Corning Corporation under the tradename 2-0749 and 2-0747, which is a blend of about 40-60% volatile silicone and 40-60% trimethylsiloxy silicate. Dow Corning 2-0749 in particular, is a fluid containing about 50% trimethylsiloxy silicate and about 50% cyclomethicone. The fluid has a viscosity of 200-700 centipoise at 25xc2x0 C., a specific gravity of 1.00 to 1.10 at 25xc2x0 C., and a refractive index of 1.40-1.41.
(ii). Copolymers of Silicone and Organic Monomers
Also suitable for use as the film forming polymer in the compositions and method of the invention are copolymers of silicone and various organic, ethylenically unsaturated monomers, and optionally other monomers. Examples of such polymers are disclosed in U.S. Pat. No. 6,033,650, which is hereby incorporated by reference. Preferred examples of these polymers include graft or block copolymers comprised of silicon moieties and C1-12 alkyl acrylate or methacrylate monomers which may be substituted with one or more groups such as halogen or hydroxy, also referred to as silicone/acrylate copolymers. Suitable silicone acrylate copolymers may be purchased from 3M Company under the tradenames VS-70 and SA-70, or from Shin Etsu Silicones.
(iii). Urethane Homo- and Copolymers
Also suitable for use in the compositions and method of the invention are homo and copolymers of urethane. Homopolymers of urethane are often sold in an aqueous dispersion from vendors such as Alloid Colloids, B. F. Goodrich, and the like. Suitable urethane copolymers may be comprised of urethane monomers copolymerized with organic compounds, or other synthetic monomers.
(iv). Amides and Amines
Also suitable are various synthetic polymers containing amide or amine substituent groups. Examples of such polymers include nylon, ammonium polyacrylate, acrylamides copolymer, acrylates/acrylamide copolymers, acrylates ammonium acrylate copolymer, acrylates C10-20 alkyl acrylate cross polymer, acrylates/carbamate crosspolymer, acrylates ceteth-20 itaconate copolymer, acrylates/dimethylaminoethyl methacrylate copolymer, ammonium acrylates copolymer, ammonium polyacrylate, ammonium styrene/acrylates copolymer, ammonium vinyl acetate/acrylates copolymer, aminomethylpropanol/acrylates/dimethylaminoethylmethacrylate copolymer, and so on.
(v). Other Synthetic Polymers
Preferred are synthetic polymers are comprised of one or more monomers selected from the following general formula:
wherein R1 is H, a C1-30 straight or branched chain alkyl, aryl, aralkyl; R2 is a pyrrolidone, or a substituted or unsubstituted aromatic, alicyclic, or bicyclic ring where the substitutents are C1-30 straight or branched chain alkyl, or COOM wherein M is H, a C1-30 straight or branched chain alkyl, pyrrolidone, or a substituted or unsubstituted aromatic, alicylic, or bicyclic ring where the substitutents are C1-30 straight or branched chain alkyl which may be substituted with one or more halogens.
Even more preferred as synthetic polymers which comprise polar monomers such as acrylic acid or methacrylic acid, in combination with C1-6 esters thereof. Most preferred is a synthetic polymer which comprises monomers of butyl methacrylate and acrylic acid.
(b). Natural Polymers
A variety of natural polymers, or derivatives thereof are suitable, including cellulosics, chitins, chitosans, shellac, rosins, resins, animal or vegetable proteins and polypeptides, and so on. The natural polymers may be present in ranges from 0.1-95%, preferably 1-85%, more preferably 3-45% by weight of the total composition.
(i). Cellulosics
Examples of suitable cellulosic polymers include nitrocellulose, mono- or diesters of cellulose formed by the reaction of cellulose with various organic acids, for example straight or branched chain carboxylic acids having from one to twenty, preferably one to ten carbon atoms, which may be substitued with one or more hydroxyl groups, Examples of such cellulosics include cellulose acetate, cellulose acetate isobutyrate, cellulose acetate propionate, cellulose acetate propionate carboxylate. Also suitable are cellulose polymers prepared by reacting with groups such as hydroxyl, alkoxyalkyl, hydroxylalkyl where the alkoxyalkyl and alkyl groups have from about one to ten carbon atoms. Examples of such polymers are carboxylmethyl hydroxyethylcellulose, carboxymethylcellulose, ethyl cellulose, hydroxyethylcellulose, methyl ethylcellulose, hydroxypropylcellulose, hydroxylbutyl cellulose, hydroxybutyl methylcellulose, and so on.
(ii). Chitin or Chitosan
Chitins, or chitosan and derivatives thereof are also suitable natural film forming polymers for use in the compositions and method of the invention. Chitin is defined as a polysaccharide derived from the exoskeleton of marine invertebrates which contains chiefly N-acetyl-glucosamine residues. Chitosan is chitin that has been deacetylated. Both polymers may be used as is, or esterified to form mono-, di-, or triesters by reacting with various straight or branched chain organic acids having from one to thirty carbon atoms, alpha or beta hydroxy acids, or di- or tricarboxylic acids. Examples of chitin or chitosan esters include chitosan adipate, chitosan ascorbate, chitosan formate, chitosan glycolate, chitosan lactate, chitsan PCA, chitosan salicylate, chitosan succinamate, and so forth. Also suitable are simple derivatives of chitin or chitosan, which are formed by substituting moieties such as hydroxyl, C1-6 alkoxy, and the like on the polymer. Examples of such derivatives include carboxylbutyl chitosan, carboxylmethyl chitosan, carboxyethyl chitosan, carboxylbutyl chitosan, and so on.
(iii). Proteins
Also suitable as film forming polymers are various animal and vegetable proteins including hydrolyzed animal protein, albumin, serum albumin, hydrolyzed wheat protein, hydrolyzed soy protein, hydrolyzed animal collagen, and mixtures thereof.
(iv). Dextrans
Also suitable are dextrans and alkoxy, or alkoxylalkyl derivatives thereof such as carboxymethyl dextran, carboxylethyl dextran, and so on.
(v). Rosins, Resins and Gums
Also suitable are various natural resins and rosins and derivatives thereof such as Balsam Canada resin, hydrogenated rosin, glycol rosinate, shellac, and the like. Various gums are also suitable including acacia gum, and similar materials.
It may be desirable to have more than one film forming polymer in the composition. They polymers may be a combination of one or more synthetic polymers, or one or more natural polymers, or mixtures of both.
The preferred semi-permanent film forming compositions of the invention comprise nitrocellulose.
3. Plasticizers
Preferably, the nail enamel compositions contain one more plasticizers that plasticize the film formed on the nail after the composition is applied to the nail and allowed to try. Suggested ranges of plasticizer are 0.1-35%, preferably 0.5-30%, more preferably 1-25% by weight of the total composition. Suitable plasticizers include glyceryl, glycol, and citrate esters as disclosed in U.S. Pat. No. 5,066,484, which is hereby incorporated by reference. Examples of such esters include glyceryl tribenzoate, glyceryl triacetate, acetyl tributyl citrate, dipropylene glycol dibenzoate, and the like. Also suitable, are plasticizers of the following general formula:
wherein R1, R2, and R3 are each independently a C1-20 straight or branched chain alkyl or alkylene which may be substituted with one or more hydroxyl groups. Preferably, R1 is a C3-10 straight or branched chain alkyl; R2 is a C2-8 alkyl which may be substituted with one or more hydroxyl groups; and R3 is a C3-10 straight or branched chain alkyl. Examples of such compounds include dioctyl malate, diisopropyl adipate, dibutyl sebacate, dioactyl azelate, dioctyl succinate, dioctyl fumarate, and the like
4. Pigments
The semi-permanent film forming compositions of the invention may be pigmented or clear. If pigmented, generally 0.1-30% by weight of the total composition, preferably 0.5-20%, more preferably 1-15% of pigment is suggested. Pigments suitable for use in nail enamel compositions are well known and include iron oxides, DandC and FDandC colors, titanium dioxide, and the like. The pigments may be treated or coated with agents which modify the surface properties such as silicones. Examples of silicone treated pigments which can be used in the compositions of the invention are set forth in U.S. Pat. No. 4,832,944, which is hereby incorporated by reference.
5. Suspending Agents
If the semi-permanent film forming compositions of the invention contain pigments, it is desirable to also incorporate 0.01-15%, preferably 0.05-10%, more preferably 0.1-8% by weight of the total composition of a suspending agent which acts to suspend the pigments in the formulation. Suitable suspending agents are montmorillonite minerals and derivatives thereof, such as stearalkonium bentonite, hectorites, attapulgite, bentones, and the like, as well as polymeric compounds known as associative thickeners. Suitable associative thickeners generally contain a hydrophilic backbone and hydrophobic side groups. Examples of such thickeners include polyacrylates with hydrophobic side groups, cellulose ethers with hydrophobic side groups, polyurethane thickeners. Examples of hydrophobic side groups are long chain alkyl groups such as dodecyl, hexadecyl, or octadecyl; alkylaryl groups such as octylphenyl or nonyphenyl.
7. Other Ingredients
The semi-permanent film forming compositions may contain a variety of other ingredients including vitamins, antioxidants, preservatives and plant extracts in the same ranges as set forth herein with respect to the conditioning compositions.
The semi-permanent film forming compositions used in the method exhibit improved moisture barrier properties due to the presence of the fluorinated oil. In addition, such compostions provide films that are substantially glossier and more resistant to chipping or marring.

Method for improving integrity of cosmetic films


Images are analyzed using sub-sectional component evaluation in order to augment classifier usage. An image of an individual is obtained. The face of the individual is identified, and regions within the face are determined. The individual is evaluated to be within a sub-sectional component of a population based on a demographic or based on an activity. An evaluation of content of the face is performed based on the individual being within a sub-sectional component of a population. The sub-sectional component of a population is used for disambiguating among content types for the content of the face. A Bayesian framework that includes a conditional probability is used to perform the evaluation of the content of the face, and the evaluation is further based on a prior event that occurred.

Human beings are emotional creatures and exhibit reactions to a variety of external events and internal feelings. Humans can express emotion in a variety of ways, such as by using voice tone and volume, or by gestures of hands and arms, and posture or body stance. However, one of the primary conveyors of emotion is that of facial expressions.
The human face is capable of expressing vast amounts of information and is key for many levels of human communication. Based on both conscious and unconscious positioning and movement of various facial muscles, the human face can form a plethora of facial expressions. The facial expressions can convey moods, emotions and the like. These expressions can include an open, welcoming countenance, a hostile, threatening countenance, and so on. The movements and positions of the facial muscles form expressions that convey emotions, where the emotions range from happy to sad and include angry, fearful, disgusted, and surprised, among many others. The facial expressions of a given person can be captured and analyzed. The facial expression analysis can be undertaken for purposes including facial recognition and facial identification, among other applications, and can determine a range of emotions and mental states. The mental states can include frustration, ennui, confusion, cognitive overload, skepticism, delight, satisfaction, calmness, stress, and many others.
Various human expressions can be recognized. For example, a smile is one of the most recognized emotions throughout the world. When smiling or laughing, the cheeks are pulled up and out, and the mouth sides are pulled backwards as well as slightly upwards. This slight upper movement pushes the upper eyelids and produces wrinkles around the eyes. Additionally, the mouth appears to get closer to the nose. A smile may indicate happiness. However, a smile can indicate other emotions as well. For example, an asymmetrical smile, formed by raising one side of the lips, can be indicative of contempt. There are many other mental states and facial expressions that are within the range of human emotion.
Gaining insight into the mental states of individuals represents an important tool for understanding events. For example, in advertising, understanding the resultant mental states of viewers of the advertisements is valuable for gauging the efficacy of those advertisements. However, it is very difficult to properly interpret mental states when the individuals under consideration may themselves be unable to accurately communicate their mental states. Furthermore, different people may respond differently to a given stimulus. For example, some people may smile when afraid or nervous. Thus, there is a difference between a facial expression and a mental state. The smile a person produces when nervous may be different than the smile produced when the person is happy.
Mental or emotional state can play a role in how people interpret external stimuli. Emotions such as happiness, sadness, fear, laughter, relief, angst, worry, anguish, anger, regret, and frustration are often reflected in facial expressions. Thus, the study of facial expressions and their meanings can provide important insight into human behavior.

Image analysis using sub-sectional component evaluation to augment classifier usage


Laser-addressable thermal transfer donor elements for producing color proofs, printing plates, films, printed circuit boards, and other media are disclosed. The thermal transfer donor elements include a substrate having a microstructured surface. The microstructured surface contain a plurality of randomly positioned discrete protuberances of varying heights and shapes. The donor elements further include a black metal layer on the microstructured surface and a gas-producing polymer layer over the black metal layer. The gas-producing polymer in the gas-producing polymer layer has a thermally available nitrogen content of greater than about 10 weight percent. A thermal mass transfer material (e.g., a colorant such as a dye or pigment) is included in or over the gas-producing polymer layer.

The phenomenon of laser-induced ablation transfer imaging is generically known and is believed to entail both complex non-equilibrium physical and chemical mechanisms. Such laser-induced ablation transfer is thought to be effected by the rapid and transient accumulation of pressure beneath and/or within a mass transfer layer initiated by imagewise irradiation. Transient pressure accumulation can be attributed to one or more of the following factors: rapid gas formation via chemical decomposition and/or rapid heating of trapped gases, evaporation, photo expansion, thermal expansion, ionization and/or by propagation of a pressure-wave. The force produced by the release of such pressure is sufficient to cause transfer of the imaging layer to an adjacent receptor element. The force is preferably sufficient to effect the complete transfer of the exposed area of an entire layer rather than the partial or selective transfer of components thereof.
Laser-induced thermal mass transfer of materials from a donor sheet to a receptor layer has been described in the patent and technical literature for nearly thirty years. However, few commercial systems have utilized this technology. Exposure fluences required to transfer materials to a receptor have been, at best, on the order of 0.1 Joule/cm.sup.2 (i.e., J/cm.sup.2). Consequently, lasers capable of emitting more than 5 Watts of power, typically water-cooled Nd:YAG lasers, have been required to produce large format images (A3 or larger) in reasonable times. These lasers are expensive and impractical for many applications. More recently, single-mode laser diodes and diode-pumped lasers producing 0.1-4 Watts in the near infrared region of the electromagnetic spectrum have become commercially available. Diode-pumped Nd:YAG lasers are good examples of this type of source. They are compact, efficient, and relatively inexpensive. In order to use these new sources in a single-beam, large format imaging system, the exposure fluence of thermal transfer materials should be reduced to less than 0.04 J/cm.sup.2 and the exposure pixel dwell time should be less than 300 nanoseconds. There have been many unsuccessful efforts in the art to achieve this goal.
Recently, however, U.S. Pat. No. 5,278,023, entitled "PROPELLANT-CONTAINING THERMAL TRANSFER DONOR ELEMENTS," disclosed a thermal transfer donor element containing a gas-producing polymer having a thermally available nitrogen content of greater than about 10 weight percent, a radiation absorber, and a thermal mass transfer material. Such gas-producing polymers generate a high propulsive force, thereby decreasing the exposure fluence required to induce transfer of imaging material to a receptor layer material. For this reason, the gas-producing polymers enable the use of simple, single-beam scanners based on diode-pumped lasers such as diode-pumped Nd:YAG lasers.
Generally, three types of radiation absorbers are used in thermal mass transfer imaging systems: dyes, particles, and thin layers of metal. The use of dyes as a radiation absorber is disclosed in U.S. Pat. No. 5,156,938. In this role, however, dyes are undesirable because of their high cost, reactivity/incompatibility with other components of the thermal transfer system (which, in turn, leads to instability and a low shelf life), and susceptibility to decomposition under the high temperature conditions which exist during thermal imaging.
Particle-type radiation absorbers are disclosed in, e.g., U.S. Pat. No. 4,588,674, UK Patent Application GB 2 083 726, and Japanese Kokai Patent Application No. SHO 63[1988]-161445. Such particles are generally dispersed in a binder. The most common particle-type radiation absorber is carbon black. Because the particles are discrete and randomly distributed in the binder, they must be present in relatively thick (i.e., greater than 0.5 micrometers) layers in order to generate sufficient heat for mass transfer. Since the amount of radiant energy required to heat a layer is directly proportional to the thickness of that layer, however, such thick layers are undesirable from both a speed and energy usage standpoint. In addition, when carbon black is used as a particle absorber (which is typically the case), the persistent color of the particles generally restricts their use to thermal mass transfer systems which are black and white.
Thin-layered metal absorbers avoid the disadvantages of dye and particle absorbers by combining low cost, high compatibility and high stability with the ability to provide sufficient heat for mass transfer when coated in thin (i.e., around 0.1 to 0.01 micrometers) layers. In this manner, thin-layered metal radiation absorbers increase the efficiency of the imaging process by allowing greater speed and lower energy usage. For example, copending U.S. patent application Ser. No. 08/033,112, filed Mar. 18, 1993 and entitled "LASER PROPULSION TRANSFER USING BLACK METAL COATED SUBSTRATES," discloses a thermal transfer donor element containing, in order, a substrate, a black metal radiation absorbing layer on one surface of the substrate, a gas generating polymer layer over the black metal layer, and a colorant over the black metal layer. The donor element is particularly useful for ablative thermal mass transfer imaging.

Thermal transfer donor element comprising a substrate having a microstructured surface

Minnesota Mining and Manufacturing Company


In a device for regulating the power output of an electrical generator in motor vehicles having an internal combustion engine, in which the generator has a regulator unit, which prevents exceeding at least one limiting temperature by regulation, the regulator unit is connected via a bidirectional interface to an electronic control unit assigned to the internal combustion engine. The control unit and the regulator unit are designed in such a way that the regulator unit, after transmitting at least one value relevant to the limiting temperature from the control unit to the regulator unit, stores the particular applicable limiting temperature determined by this value.

The present invention relates to a device for regulating the power output of an electrical generator in motor vehicles.
A device of this type is known, for example, from German patent document DE 101 06 944 A1. In the known generator regulator units having temperature limiting for thermal protection, the limiting temperatures are permanently and unchangeably programmed in the regulator units. Therefore, a special limiting temperature tailored to the individual application must be provided in the regulator units for every application in the vehicle. A high variant manifold thus arises when constructing generators having integrated regulator units.
It is an object of the present invention to improve a device of the type cited above in regard to standardization and thus cost optimization.
This and other objects and advantages are achieved according to the present invention by a device for regulating the power output of an electrical generator in motor vehicles having an internal combustion engine, in which the generator has a regulator unit, which prevents exceeding at least one limiting temperature by regulation. The regulator unit is connected via a bidirectional interface to an electronic control unit assigned to the internal combustion engine. The control unit and the regulator unit are designed in such a way that the regulator unit, after transmitting at least one value relevant to the limiting temperature from the control unit to the regulator unit, stores the particular applicable limiting temperature determined by this value.
A value relevant to the limiting temperature may, for example, be the particular applicable limiting temperature itself, an offset value which is added by the regulator unit to a base value to reach the particular applicable limiting temperature, or a parameter by which the regulator unit selects the particular applicable limiting temperature from a parameter-related list of limiting temperatures. The parameter may be an application-specific data relating to the cooling conditions of the generator and/or an operation-specific data relating to the heat generation in the generator environment, or may be calculated therefrom.
The control unit may determine the value relevant to the limiting temperature as a function of at least one application-specific data relating to the cooling conditions of the generator, such as the engine installation space, as a fixed value.
Alternatively or additionally, the control unit may determine the value relevant to the limiting temperature variably as a function of at least one operationally-specific data relating to the heat generation in the generator surroundings, such as the instantaneous engine speed or the instantaneous engine output.
The present invention is based on the following findings:
The regulator unit may be programmed with the same base value as the limiting temperature for every application in the vehicle. According to the present invention, this base value may be overwritten using a particular new applicable limiting temperature or have a new offset value applied to it, resulting in a new applicable limiting temperature, when the unit is first put into operation in the vehicle, at least for the application-specific adaptation. The base value may also be used as an emergency operation limiting temperature in case of interface error. According to the present invention, different limiting temperatures may be determined for various components. The temperature limiting may occur according to the prior art.
Through the present invention, it is possible to provide standards which may be designed as correspondingly flexible by the interface communication. Through these standards, it is possible to achieve significantly simpler component handling in the replacement part market. Unnecessary trimming of the generator output power or no limiting at temperatures which are too high is often to be observed due to the limiting at a single fixed limiting temperature according to the prior art.
Other objects, advantages and novel features of the present invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings.

Device for regulating the power output of an electrical generator in motor vehicles


The present invention discloses novel steroid mimics wherein a tri- or tetravalent phosphorous atom is isosterically substituted at any one of the seventeen positions occupied by the carbon atom in the steroidal skeleton, and wherein each adjacent position to the phosphorous is either unsubstituted or optionally substituted by nitrogen or an oxygen atom to satisfy the valency of said phosphorous atom. The invention is illustrated schematically below using both aromatic and non-aromatic steroids. Although the isosteric substitution

It is to be noted that throughout this application various publications are referenced by Arabic numerals within brackets. Full citations for these publications are listed at the end of the specification. The disclosures of these publications are hereby incorporated by reference in their entireties into this application in order to more fully describe the state of the art to which this invention pertains.
Targeted delivery of medically useful elements to a particular site continues to be of considerable importance in diagnosis, prognosis, and therapy of various lesions [1]. For example, gadolinium is used extensively for magnetic resonance imaging (MRI); barium and iodine are used for X-ray computed tomography (CT); technetium, indium, lutetium, samarium, and iodine are used for planar imaging and single photon emission tomography (SPECT); gallium and fluorine are used for positron emission tomography (PET); rhenium, samarium, yttrium, lutetium, and phosphorous are used for radiotherapy; and europium, ruthenium, and rhenium have potential utility for optical imaging and optical tomography. In particular, 32P, a β-emitting radioisotope of phosphorous, has considerable radiotherapeutic potential for various lesions depending on its incorporation into a selected molecular carrier. For example, incorporation of 32P into a steroid receptor binding molecules such as androgens, estrogens, antiestrogens, progestins, and the like may be useful for the treatment of steroid receptor positive tumors; incorporation into somatostatin receptor binding molecules such as octreotide may be useful for the treatment of neuroendocrine tumors; or incorporation into carbohydrate receptor binding molecules such as selectins or integrins may be useful for inflammatory process.
Conventional bioconjugate method of delivering diagnostic and therapeutic agents, both small molecules and macromolecules, such as drugs, enzymes, metal complexes, fluorescent and radioactive probes, and the like to a particular tissue involves the external attachment of these agents to a targeting carrier whose size is typically considerably larger than the effector molecules. This methodology has been referred to as "external bifunctional" approach, and has been quite successful in the development of in vitro diagnostic products. However, one of most vexing problems in bioconjugate chemistry with respect to the development of in vivo diagnostic and therapeutic agents is that the external attachment of a radionuclide complex to small molecule carriers almost always impedes receptor binding [2]. This problem can be readily resolved by the use of macromolecular carriers such as antibodies or reasonably large peptides where the epitope topology is not much altered. An epitope is a specific region of the molecule that is actually involved in the adhesion of the effector and carrier through the intermolecular forces. Unfortunately, macromolecular bioconjugates present many problems with respect to bioavailability, pharmacokinetics, and biodistribution. Moreover, for nuclear medicine applications, the external bifunctional agents presents additional radiotoxicity of critical non-target tissues such as the liver and the kidney due to unacceptably large percent injected dose to and poor clearance from these organs. In order to address both of the aforementioned problems, viz., receptor binding and bioavailability, we have previously introduced a general concept referred to as 'internal bifunctional' approach or 'small molecule drug mimics' wherein the medically useful atom is integrated into a known effector molecule thereby preserving the overall size and shape of the original molecule. This approach was based on the well established principle that antibodies, enzymes, and receptors are multispecific, i.e., they will bind to molecules that are topologically similar to the natural antigens, substrates, or ligands. The concept of radionuclide metal ion based drug mimics was independently proposed by Rajagopalan [3, 4] and Katzenellenbogen [5]. Katzenellenbogen's work on steroid mimics confirmed experimentally that the idea of integrating a metal ion into natural receptor ligands is a viable strategy for targeted delivery of diagnostically and therapeutically useful radionuclides to target tissues [2, 5–7].
Our previous work on steroid mimics focused on isosteric substitution of metal ions such as technetium and rhenium into various positions in aromatic and non-aromatic steroidal framework as illustrated schematically by generic structures 1 and 2 [4]. A considerable difficulty with respect to incorporating a metal ion into a carbon framework is the deviation
from tetrahedral geometry. For example, Tc(V) and Re(V) oxidation state forms a square pyramidal geometry, which may contribute to reduced receptor binding capability. Furthermore, 186Re obtained from the generator is not carrier free, i.e., only 5% is in the radioactive form; the rest of the material is the non-radioactive ('cold') isotope of rhenium. Therefore, this presents a formidable challenge to prepare steroid mimics with very high specific activity needed for radiotherapeutic purposes. In contrast, 32P can be obtained in a carrier-free from. Thus, there is a need in the art to prepare novel radiodiagnostic and radiotherapeutic steroidal compositions with high specific activity and having high affinity for steroid receptors. Accordingly, the present invention focuses phosphorous-based steroid mimics. Although phosphasteroids have been known for sometime [8, 9], surprisingly there has not been much activity in developing them into medically useful products. Introducing a phosphorous atom into the steroidal skeleton solves two key problems: (a) the preservation of tetrahedral geometry, and (b) the preparation of steroid mimics having very high specific activity. In addition, steroids are transported across cell membrane from the blood to the cytoplasm via steroid binding proteins (SBP) [10]. Since the phosphorous containing steroid mimics of the present invention have same topology at the original steroids, it is anticipated that the mimics will bind to SBP and transported into the cell in the same manner as the native steroid molecules.

Abstract: phosphorous atom in the above structures 3–7 is indicated at 13, 14, and 17 positions, it is to be noted that the phosphorous can be substituted at any one of the seventeen positions in non-aromatic or eleven positions in aromatic steroids. The phosphorous atom may be trivalent or tetravalent, and may be radioactive or non-radioactive. The adjacent atoms, X, Y, or Z may be carbon, oxygen, or nitrogen. Other positions in the steroid mimics 3–8 may be optionally substituted alkyl, aryl, or other polar or non-polar functional groups to optimize biodistribution, receptor binding, and pharmacokinetic properties.


A corrosion resistant coating to protect metallic and polymeric composite surfaces from corrosion and water promoted deterioration that is environmentally safe and non-toxic and is applied in one coat without the use of a primer is provided. The coating comprises a tough, flexible polyurethane binder and a corrosion inhibiting pigment selected from the group consisting of zinc hydroxy phosphite, zinc phosphate, calcium ion-exchanged silica, calcium strontium zinc phosphosilicate. The coating is effective in protecting both aluminum and steel surfaces against corrosion in salt spray environments and in protecting polymeric composite materials such as ablative coatings used in aerospace against deterioration after exposure to water.

This invention deals with environmentally safe, non-toxic, protective coatings to provide corrosion resistance to metallic surfaces that are subjected to corrosive environmental conditions and/or thermal stress.
Painting of aluminum and steel structures in the aerospace/seacoast environment requires the use of separate primers and topcoat primers containing toxic and environmentally hazardous lead and chromium compounds. Such coatings often contain high levels of volatile organic compounds which may also be detrimental to the environment and human health. Application of two different coatings, primer and topcoat is labor intensive and also requires inventorying two types of materials thereby increasing the cost of using such coatings. Inspection and measurement of each coating further increases labor costs and is prone to error. Although existing single coat primer-topcoat paints provide some degree of remedy for some of these problems they also have extremely short pot life making them difficult to work with and do not have the level of corrosion inhibitive properties to satisfy launch vehicle requirements.
There is, therefore, a need for an environmentally safe, non-toxic, coating composition to protect aluminum and steel structures and machinery, such as those used in aerospace as well as other industries, from corrosion produced by exposure to environments such as the seacoast. Such a composition should be safe and efficient to use and require only one coat to provide effective corrosion protection. In addition, the coating composition should be substantially free of environmentally hazardous and toxic substances such as lead and chromium compounds and volatile organic compounds. A further requirement for such a coating is that it should have a long pot life to enable efficient use without an undue waste of material. Furthermore, should the coating become damaged, it should be easy to repair in an inexpensive, safe and convenient manner.
The present invention is directed to meeting the foregoing needs by providing a two part resin composition comprising a combination of resins containing non-toxic corrosion inhibiting pigments and low levels of volatile organic compounds. The coating composition has a pot life of about three to about four hours and excellent solvent resistance. The coating composition is applied as a single coat without the need of a primer coat and provides excellent corrosion protection to aluminum and steel substrates when exposed to salt spray. The first part or part A of the coating composition comprises saturated polyester polyols having an equivalent weight of about 100 to an equivalent weight of about 2500. The second part or part B of the coating composition comprises a polyisocyanate composition with the polyisocyanate composition selected from polyisocyanate compositions consisting of hexamethylene diisocyanate, the biuret of hexamethylene diisocyanate (HDI), the trimer of HDI and mixtures and reaction products thereof. Other compounds and polymers having reactive groups that can react with isocyanate functions such as epoxy resins can also comprise part A. The corrosion resistant composition comprising a polymeric matrix resulting, from the reaction of polyisocyanate composition and the polyol contains corrosion inhibiting pigments selected from the group consisting of zinc hydroxy phosphite, zinc phosphate, calcium ion-exchanged silica, calcium strontium zinc phosphosilicate and mixtures thereof and is applied to a substrate metal in one coat without the need of a primer.
The corrosion resisting coating of the present invention is formed from a two part resin composition comprising a combination of resins containing non-toxic corrosion inhibiting pigments and low levels of volatile organic compounds. The two parts of the coating composition, part A and part B, are mixed prior to application and react to form a strongly adherent solvent resistant polymeric matrix comprising a polyurethane that contains corrosion inhibiting pigments selected from the group consisting of zinc hydroxy phosphite, zinc phosphate, calcium ion-exchanged silica, calcium strontium zinc phosphosilicate and mixtures thereof and is applied to a substrate metal in one coat without the need of a primer. The pot life of the formulation after mixing is about three to about four hours. The first part or part A of the coating composition comprises a saturated polyester polyol comprising a reaction product of phthalic anhydride and trimethylol propane (also known in the art as TMP) having an equivalent weight of about 100 to an equivalent weight of about 2500. Preferably, the saturated polyester polyols comprising part A are characterized by an equivalent weight of about 225 to about 600, an acid number not greater than about 4 and a hydroxyl number of about 104 to about 220. Preferred saturated polyester polyols are selected from compositions that are characterized by an acid number (on solution) of about 0 to about 3, a hydroxyl number (on solution) of about 104 to about 120, with an equivalent weight (on solution) of about 468 to about 539 and an equivalent weight (on solids) of about 374 to about 431 with representative commercially available formulations marketed under the name Chempol(copyright) 18-2217 (Freeman Chemical Corporation, Port Washington, Wis.) and Mobay 670A-80 (Bayer, Mobay Corporation, Pittsburgh, Pa.) and compositions that are characterized by an acid number (on solution) of about 1 to about 4, a hydroxyl number (on solution) of about 155 to about, 190, with an equivalent weight (on solution) of about 312 to about 328 and an equivalent weight (on solids) of about 480 with representative commercially available formulations marketed under the name Chempol(copyright) 18-2230 (Freeman Chemical Corporation, Port Washington, Wis.) and Desmophen 650A-65 (Bayer, Mobay Corporation, Pittsburgh, Pa.) and compositions that are characterized by a maximum acid number of about 3, a hydroxyl number of about 200 to about 220, with an average equivalent weight of about 267 with a representative commercially available formulation marketed under the name Desmophen 631A-75 (Bayer Corporation, Industrial Chemicals Division, Pittsburgh, Pa.) and other equivalent compositions and formulations and mixtures thereof.
The second part or part B of the coating composition preferably comprises an aliphatic or cycloaliphatic polyisocyanate resin based on hexamethylene diisocyanate (also known in the art as HDI) having an average equivalent weight of about 255. A commercially available formulation comprising such a polyisocyanate based on HDI is Desmodur N-75 (Bayer, Mobay Corporation, Pittsburgh, Pa.), however other equivalent compositions and formulations may also be used. In practice the polyisocyanate comprises a biuret of HDI, but an HDI trimer can also be used. Other polyisocyanates such as those enumerated in U.S. Pat. No. 5,043,373, which is herein incorporated by reference, may also be used to formulate part B of the present composition.
Typical formulations for Part A and Part B of resin matrices for corrosion resistant coating compositions are given in Example 1, Table 1. Standard methods known in the art are used in preparing these resin matrices, for example those described in Hegedus et al, U.S. Pat. No. 4,885,324 which is herein incorporated by reference and the previously incorporated U.S. Pat. No. 5,043,373. Generally, the quantities of polyol and polyisocyanate are preferably adjusted to provide an approximately 1:1 ratio of hydroxyl to isocyanate groups when part A and part B are mixed. However, effective resin matrices can be obtained when the concentration of either of these functional groups in the mixture exceeds the other by about 20%. The following examples demonstrate the overall superior performance of the preferred polymeric matrix compositions which are derived from coating formulation 1 and coating formulation 3 in Example 1.

Self priming high performance environmentally compatible protective coating