A lutein to zeaxanthin isomerization process which includes a saponification or alkali treatment of a plant extract containing lutein followed by a heating period under controlled conditions, is carried out in the presence of a surface active agent having an HLB of from 1 to 40 as a catalyst for the lutein to zeaxanthin isomerization reaction, at a temperature between 70 to 140xc2x0 C., in order to obtain a reaction product with high zeaxanthin concentrations of up to 80% of the total carotenoids.

The present invention is related to the obtainment of natural pigments from plant materials for use as food additives and, more particularly, it is related to a lutein to zeaxanthin isomerization process and to the product obtained with the same.
As consciousness towards the potential harm caused by some synthetic pigments previously used in foodstuffs for humans and animals is awakening throughout the world, the use of natural plant pigments has acquired more and more importance. It is because of this reason that extraction of colorants from natural sources such as flowers and fruits has been carried out for a long time all over the world.
In the Book xe2x80x9cColorantes Naturales de Mexicoxe2x80x9d, published by Industrias Resistol S. A. in 1988, several extraction methods of xe2x80x9cflower dyesxe2x80x9d are described, which comprise steps such as milling or boiling flower petals, and further addition of substances such as 96xc2x0 ethyl alcohol, alum and vinegar solutions. This book also describes a vast plurality of different applications of several colorants of natural origin.
Among such applications and particularly in the poultry industry, the yellow color of egg yolk and broiler skin is originated by the pigments contained in the feed these birds ingest. The importance of pigmentation is that a good pigmentation in the birds is associated with a good condition and high quality during the breeding of the broilers, which has become an essential factor for the chicken and egg commercialization.
The main compounds associated with skin pigmentation in broilers and egg yolk pigmentation in laying hens (as well as in other species like fishes and crustaceans) are the so-called carotenoids, which are related to carotene in its chemical structure. The main carotenoids associated with pigmentation in poultry industry are denominated, in general terms, as xanthophylls (from Greek roots: Xanthos=Yellow; and Phylos=friend, lover). Xanthophylls have the common characteristic of being water insoluble pigments that are slightly soluble in ethyl alcohol and ether.
These carotenoids are generally found in natural products such as alfalfa, corn gluten, marigold flower and chili, among others.
Traditional sources of xanthophylls involved in poultry pigmentation have been alfalfa and corn gluten, in which carotenoids are found in their free form.
Market demand has compelled aviculturists to intensify the pigmentation level in their products, thus compelling also the natural pigment industry to carry out research and development activities for finding alternative natural sources of carotenoids. Marigold flower (Tagetes erecta) has become a viable alternative for these purposes due to its high xanthophyll content, although these compounds are found in its esterified form therein.
Nowadays, marigold flower yellow pigments and pigments from other plant sources are commercialized in its saponified form and formulated in different solid or liquid vehicles. Such pigments have been used for more than four decades as food additives, mainly as colorants for skin pigmentation in broilers and egg yolk pigmentation in laying hens. Saponification of said yellow pigments is necessary to facilitate their absorption and assimilation by the birds, inasmuch as these pigments, which are in their esterified form, are hydrolyzed or converted into their free form after saponification, thus being absorbed by the birds more rapidly and efficiently.
In the Poultry Science journal, pages 1708 to 1714, volume 65 of 1986, an article by D. L. Fletcher et al was published, in which the effect of saponification of marigold flower extracts and their pigmenting capacity in egg yolk and broiler skin is analyzed.
In industry, pigment extraction from marigold flower, as well as from other plant varieties, is traditionally carried out by means of different kinds of solvents to form concentrated extracts containing carotenoids in the esterified form, usually called oleoresins, oily extracts or crude extracts. In order to achieve a higher pigmenting capacity, the xanthophyll containing extracts are further treated to hydrolyze the esterified xanthophylls, generally by means of saponification processes.
In order to obtain the free form of such pigments, there is a variety of processes to hydrolyze xanthophylls, such as the process described in U.S. Pat. No. 3,783,099, granted on Jan. 1, 1974, in which the plant material containing xanthophylls is mixed with an enzyme such as cellulase, protease, etc. and a chelating agent such as ethylenediamine tetra-acetic acid (EDTA), which achieves the hydrolysis of the esters at constant pH conditions and carries away the xanthophylls in their free form, thus avoiding a further saponification step.
At industrial scale, the most common hydrolysis process used, as mentioned above, is the saponification or alkali treatment of plant extracts. The state of the art acknowledges a variety of saponification processes of esterified xanthophylls from plant extracts.
U.S. Pat. No. 3,523,138, granted on Aug. 4, 1970, describes several processes for treating marigold flower extracts by means of aqueous solutions of alkali metal hydroxides in the presence of low molecular weight alkyl alcohols, in which temperatures ranging from 0 to 150xc2x0 C. can be used with reaction times of between 1 minute and 8 hours, depending on the temperature employed, since the reaction time is reduced when the temperature is increased. This patent states that, in order to obtain an optimum result at 90xc2x0 C., the process should take 3 hours.
Mexican Certificate of Invention No. 1697, granted on May 4, 1978, describes a process for obtaining a powdered pigmenting concentrate with enhanced activity, starting from oleoresins containing xanthophylls, in which the xanthophylls contained in marigold flowers are extracted using solvents such as chloroform, hexane or acetone, that are removed in a later stage, thus obtaining a pasty mass containing xanthophylls, fats, resins and waxes, which were carried away by the solvent. Once xanthophylls are extracted, an emulsion is formed by means of a surfactant, for instance a detergent, in order to assist in the incorporation of the pasty mass in aqueous alkali solutions, such as ammonium hydroxide, potassium hydroxide or sodium hydroxide, in order to carry out saponification at a temperature of from 50 to 90xc2x0 C. during a period of time of from 15 to 60 minutes, after which an antioxidant and a xanthophyll fixer such as lecithin, as well as a substance that adheres to xanthophylls such as carboxymethyl cellulose, gelatin or palmitates are added. The solution obtained is then neutralized using a precipitating agent such as phosphoric acid, silicic acid or magnesium chloride, in order to neutralize and carry away the xanthophylls. Finally, the precipitate formed is filtered, washed, dried and ground in order to obtain the final powdered pigment.
In the prior art discussed in the above referred to Certificate of Invention, it is established that until that moment, no process for the obtention of powdered pigmenting concentrates starting from xanthophyll oleoresins in order to enhance their activity, had ever been conceived.
Mexican Certificate of Invention No. 6010, granted on Sep. 24, 1984, describes a process for obtaining a stable xanthophyll pigmenting concentrate from marigold flower, comprising the steps of extracting oil from marigold flowers using a solvent; saponifying the oily extract-solvent mixture with an alkali at a temperature of from 55 to 65xc2x0 C. at atmospheric pressure; removing the solvent for obtaining a xanthophyll-rich concentrate, and stabilizing the concentrate by means of the addition of an antioxidant selected from ethoxyquin and ascorbic acid.
In the prior art discussed in Certificate of Invention No. 6010, several documents are cited, including the Mexican Certificate of Invention No. 1697. In these documents, it is possible to ascertain the research and development carried out from the year 1915 in the field of xanthophylls, as well as in their pigmenting effects and the different ways to achieve the xanthophylls saponification. It is important to mention that the novelty of the process claimed in Mexican Certificate of Invention No. 6010 was the fact that the saponification process was carried out in dry conditions and no further neutralization step was required.
Mexican Certificate of Invention No. 6320, granted on Apr. 1, 1985, describes an improved process for obtaining stabilized liposoluble extracts starting from vegetable raw materials (such as marigold flower), in which the base plant extract is saponified with a concentrated sodium and/or potassium hydroxide solution at a temperature within the range of from 60 to 90xc2x0 C. in the presence of an emulsifier-thickener, such as carboxymethyl cellulose, gelatin or soluble starch. During the process for obtaining the extract, the humidity is controlled and the saponification reaction is carried out under vacuum or reduced pressure conditions within 0.1 and 0.05 atm, considering an average reaction time of 3 hours for obtaining a yield of from 95 to 100% saponification.
The discussion of the prior art cited in Mexican Certificate of Invention No. 6320, states that the main drawback of xanthophyll powdered extracts is their instability due to the powder surface contact with the oxygen of the atmosphere, including the containers where they are contained. This document claims as a novelty a process in which metallic precipitating agents and stabilizers are used to improve the properties of the powdered pigments, as well as the saponification reaction carried out under vacuum conditions.
An additional aspect related to the final shade of egg yolk or broiler skin is the fact that such tonality is important according to the requirements of the different markets where this kind of pigments are used as food additives. In some markets, such as the oriental market, orange to red shades are clearly preferred, and this is why the producers of this kind of additives have taken care of developing processes and products tending to satisfy these requirements.
Among the xanthophylls usually extracted from marigold flower in esterified form, lutein and zeaxanthin may be found, with lutein being found in a higher ratio (80%). For this reason, lutein is also known as xanthophyll since it exists in largest quantities in nature.
U.S. Pat. No. 3,569,386, granted on Nov. 10, 1970, describes several compositions containing carotenoids which, when added as food additives for laying hens, give several tonalities in the resulting egg yolks. Similarly, in the Poultry Science journal, page 925, volume 64 of 1985, a study was published which refers to the influence of the type of xanthophylls coming from different sources, which are used as food additives.
In order to get the orange-red tonalities, traditional efforts have been oriented to develop mixtures of yellow pigments from marigold flower with red pigments from chili (Capsicum annum). However, it is well known that some products rich in zeaxanthin, like corn gluten, either alone or combined with marigold flower extracts, lead to the same satisfactory results from the commercial point of view. Chemical Abstracts No. 108473z vol. 73, 1970 and No. 145772c vol. 89, 1978, describe the use of xanthophyll based pigments as additives for combined broiler feeds, and more specifically, the use of mixtures of lutein and zeaxanthin with other xanthophylls for coloring egg yolk and broiler skin. Lutein to zeaxanthin ratio determines the specific tonality of the final color imparted by these pigments when used as food additives.
In view of the facts mentioned above, research on different carotenoids has been done in order to produce those having the highest pigmenting activity. It has been found that a high zeaxanthin content in the pigments used as food additives is desirable, and this is one of the reasons why the lutein to zeaxanthin isomerization process has become an important matter for research and development in the poultry pigmenting industry.
Lutein to zeaxanthin isomerization reaction has been known for more than 40 years as it can be verified in some references as Karrer P. et al, published in Helv. Chim. Acta 30, p. 266, 1947, in which such isomerization and others are carried out in the presence of sodium ethoxide.
In the xe2x80x9cActa Chem. Scand.xe2x80x9d B28 Num. 1, p. 137, 1974 journal, A. G. Andrewes describes a lutein to zeaxanthin isomerization reaction in the presence of polar solvents such as methyl alcohol, potassium methoxide, methyl sulfate and mixtures thereof.
Evidences concerning heat promoted carotenoid isomerization reactions can be found in U.S. Pat. No. 3,989,757, granted on Nov. 2, 1976, in which a carotenoid isomerization process is described. The process comprises heating the carotenoids by means of a water bath at temperatures of from 50 to 120xc2x0 C.
Development of more accurate analytical techniques, such as the so-called high-performance liquid chromatography (HPLC) has made it possible to determine as a percentage ratio, the lutein and zeaxanthin contents in marigold flower extracts, as well as the percentage ratios obtained after isomerization reactions using state of the art saponification processes.
The papers related to carotenoid hydrolysis mentioned above, describe a wide variety of saponification processes or alkali treatments of marigold flower oleoresins or extracts, carried out under a large diversity of reaction conditions of temperature, pressure, atmosphere, time, quantity and nature of the alkaline substances, solvents, precipitating agents, etc. Also, some evidence can be found of several factors that are able induce carotenoid isomerization, such as high temperature and the presence of an alkali and/or an alcohol.
For these latter reasons, it is not surprising that in some saponification processes of the prior art it has been empirically observed that the zeaxanthin content rises after the saponification, when the temperature also rises beyond certain limits.
Based on the above information and analyzing the prior art, the following hypothesis could be advanced: The improvements in the pigmenting activity described in some of the papers related to the obtention of xanthophylls, were due, in a certain way, to the enhanced absorption of the extract in the broilers, induced by the intake of the free form of the carotenoids produced by the saponification process and, additionally, to an unnoticed partial lutein to zeaxanthin isomerization occurring during the same saponification reaction, which increased the zeaxanthin content, regardless of the fact that the aviculturists did not have any evidence of this circumstance.
Therefore, it can be concluded that traditional saponification processes are carried out together with lutein to zeaxanthin isomerization, inasmuch as it has been empirically observed that the final zeaxanthin content rises when the temperature in the saponification process also rises. It has been also observed that the contents of other carotenoids in the final pigment are modified when higher temperatures are used, thus evidencing that other isomerization reactions are taking place during the traditional saponification reaction, probably due to the high temperature imposed in those processes.
On the other hand, instability of the carotenoids contained in pigments has always been a problem for pigment manufacturers, inasmuch as oxygen, moisture, light and temperature affect these compounds (carotenoid susceptibility to chemical degradation). For this reason, several processes aimed to accomplish the stabilization of xanthophyll compositions can be found in the prior art.
Until now, it has not been possible to achieve a 100% effective method to keep all the xanthophylls contained in plant extracts or in any composition stable when exposed to the environmental noxious factors. Therefore, the above mentioned stabilization processes are only techniques for delaying the degradation of the total carotenoids contained in a composition. For instance, in the aforementioned U.S. Pat. No. 3,523,138, a stabilization method based on temperature control within the scale of from 0 to 150xc2x0 C. is described. The aforementioned Mexican Certificates of Invention describe stabilization methods based on antioxidant and precipitating agents addition, and U.S. Pat. No. 3,535,426, granted on Oct. 20, 1970, describes a stabilization method of dry marigold flower concentrates using antioxidants, fats and heat exposure.
The above mentioned stabilization processes have had as their main objective the preservation of the initial total carotenoid content in products containing said carotenoids almost unchanged for a long time (at least 6 months approximately), and are used in combination with the traditional saponification or hydrolysis processes.
It has been observed that the lutein to zeaxanthin isomerization yields obtained during the prior art saponification reactions and stabilization processes can be high under high temperature conditions. However, this affects adversely the xanthophyll stability and the zeaxanthin content, inasmuch as it is not high enough for commercial purposes, reason by which, producers in general keep their process conditions only to accomplish the saponification reaction in conventional terms, thus obtaining saponified products having an initial zeaxanthin content of approximately 6% with respect to the total carotenoids, with lutein remaining as the main xanthophyll contained in marigold extracts, inasmuch as lutein seems to be more stable. The isomerization of higher amounts of lutein is accomplished by setting the saponification reaction temperatures to between 50 to 90xc2x0 C. under various increased pressure conditions.
As the market is demanding nowadays products with high zeaxanthin content, several processes have been developed for producing zeaxanthin only, including from microbiological approaches, such as that referred to in the Chemical Abstract No. 16923v vol. 79, 1973, to chemical syntheses as that published in U.S. Pat. No. 3,558,712. However, until now not one single process capable of obtaining high zeaxanthin concentrations from plant extracts which also preserve the chemical stability of the total carotenoids for a long time, has ever been reported.
U.S. Pat. No. 5,523,494 describes a saponification process by which high zeaxanthin yields can be achieved. However, it has been noted that the product obtained using this process does not possess the necessary chemical stability of the total carotenoids for a long time, inasmuch as said product shows a very short shelf life.
In addition, U.S. Pat. No. 5,780,693, describes a process for the production of zeaxanthin from lutein or an ester thereof, which is based on the documents of Karrer and Andrewes discussed above. U.S. Pat. No. 5,780,693 describes a process carried out at high temperatures and that uses alkali hydroxides in aqueous solutions, instead of potassium methanolate in methanol, as a base, in the presence of dimethyl sulphoxyde (DMSO) as solvent. However, it also mentions that other organic solvents, mainly immiscible in water, can substitute DMSO, provided that an effective amount of a phase transfer catalyst is used. It is important to stress the fact that phase transfer catalysts only improve the mass transfer between the reactants by forming a ion pair that allows the base to migrate from the alkaline aqueous solution to the immiscible organic phase where the other reactant is dissolved, so as to permit the occurrence of the reaction, but without acting as catalysts of the isomerization itself.
In view of the above, for long it has been sought to overcome the drawbacks of the lutein to zeaxanthin isomerization processes of the prior art, by providing an improved process for the isomerization of lutein to zeaxanthin, which in addition to the elimination of the above established disadvantages, could lead to the obtention of a stable product having a zeaxanthin content considerably higher than that obtained by prior art processes.
Having in mind the defects of the prior art, it is an object of the present invention to provide a lutein to zeaxanthin isomerization process, which will allow the obtention of products with high zeaxanthin contents.
Another object of the present invention is to provide a lutein to zeaxanthin isomerization process of the above mentioned character, which will permit to shorten the time in which high yields of lutein to zeaxanthin isomerization are obtained during saponification and stabilization of plant extracts containing lutein.
It is an additional object of the present invention to provide a lutein to zeaxanthin isomerization process of the above nature, which will allow the obtention of a high zeaxanthin content reaction product which can be further treated keeping the stability of the total carotenoid content in a composition for a long time.
It has been surprisingly found that, when using surfactants having a Hydrophile-Lipophile Balance (HLB) of from 1 to 40, in a process for the saponification and stabilization of lutein containing plant extracts such as marigold flower, alfalfa, chilli or any extract of a plant variety containing carotenoids, that said surfactant agents act as selective catalytic agents for the lutein to zeaxanthin isomerization.
Among the surfactant agents used as catalytic agents for the lutein to zeaxanthin isomerization, the following can be mentioned in a descriptive, but not limitative manner: propylene glycol, keto-stearyl 20-POE alcohol, ethylene glycol distearate, ammonium lauryl sulfate, sodium lauryl sulfate, triethanol amide lauryl sulfate, alkyl benzene sodium sulfonate, polyglycolic esters of fatty acids, nonyl phenol 30-POE, polyethylene glycol distearate, sorbitan monostearate 20-POE, sorbitan mono-oleate 20-POE, or mixtures thereof.
As mentioned in the background chapter hereinabove, the lutein to zeaxanthin isomerization process of the prior art is accomplished by means of an overheated conventional saponification process, which only permits to obtain low isomerization yields and low chemical stability in respect to the total carotenoid content. It is worth pointing out that the conventional saponification process uses thickening agents such as carboxymethyl cellulose, gelatin or soluble starch, for emulsifying the plant extracts, in order to be able to carry out the saponification using an aqueous alkali solution; however, until now there is no evidence that may indicate that the use of such surfactant agents have as a consequence an increase in the yield of the lutein to zeaxanthin isomerization.
The lutein to zeaxanthin isomerization process of the present invention consists in the addition of the surfactant agent acting as catalyst, during the saponification or alkali treatment of a plant extract containing lutein, maintaining for an additional period of time the reaction temperature. It is important to mention that a saponification of the susceptible compounds of up to 95%, commonly occurs in the first hour of reaction.
The complete process is carried out for a period of time of approximately from 1 to 6 hours, depending on the saponification process, the catalyst and the kind of plant extract used, thus obtaining an approximate lutein conversion yield of from 25 to 96% of the lutein contained initially in the plant extract.
The saponification of the plant extract containing lutein is carried out preferably using concentrated aqueous or alcoholic alkali solutions, such as of sodium hydroxide, potassium hydroxide, calcium hydroxide or mixtures thereof. The alcohols used for preparing the alcoholic solutions are selected from methanol, ethanol, isopropyl alcohol and other low molecular weight alcohols. The saponification reaction is carried out at a temperature range from about 60 to 140xc2x0 C.; at a reduced or positive pressure, preferably atmospheric pressure; in an inert atmosphere, in an atmosphere with humidity control or at atmospheric conditions, preferably at atmospheric conditions.
The surfactant agents useful as isomerization catalysts, must be present in the saponification reaction in proportions approximately between 1 to 35% by weight of the quantity of the oily plant extract containing lutein, preferably between 5 to 15% by weight approximately.
In accordance with a specific embodiment of the present invention, marigold flower extracts are subjected to the process of the present invention. The saponification of the extracts is carried out in a potassium hydroxide aqueous solution having concentrations at room temperature of approximately from 20 to 70%, preferably 50%, at a reaction temperature approximately between 110 to 120xc2x0 C. and at atmospheric pressure, without atmosphere control, the preferred catalyst proportions being between 5 to 15% approximately. In this embodiment, the temperature is held between 70 to 140xc2x0 C. approximately during a period of time of from about 60 to 90 minutes, once the saponification has been completed. The complete process in this embodiment takes from 2 to 3 hours approximately.
Once the process is completed, a reaction product is obtained, which contains zeaxanthin in a range of concentrations of from 20% to 80% of the total carotenoids. The final zeaxanthin content mainly depends on the kind of plant extract to be saponified, on the saponification process used, on the selected catalytic agent and on the stabilization time.
The reaction product obtained can be further purified or directly formulated in different extracts, namely, liquid or solid formulations having high or low zeaxanthin concentrations. Additionally, several inert ingredients can be used according to the final use.
Once having a high zeaxanthin saponified extract, as those obtained by means of the present invention, it is possible to obtain products or compositions having standard carotenoid concentrations and diverse specific zeaxanthin proportions, the obtention of which will not require the relatively difficult and inaccurate control of the conditions of an isomerization process. Instead of depending on the process conditions, by means of the simple mixing of such high zeaxanthin plant extracts with other conventional extracts or pigmenting compositions of commercial type which have low zeaxanthin concentrations, such as Cromophyl-LR or Cromophyl-20R, it is possible to obtain a wide variety of solid or liquid products having different compositions, in different concentrations or with standardized zeaxanthin proportions.
The following examples are intended to illustrate the present invention in all aspects, but are not to be taken as limitations of the scope thereof.

Lutein to zeaxanthin isomerization process and product

Col. Lomas del Marquxc3xa9s C.P. 76146 Querxc3xa9taro, Qro.

Col. La Sierrita C.P. 76135, Querxc3xa9taro, Qro.


An electrical power system for an aircraft includes an ac generator bus, an air conditioning system ("ACS") generator and a main engine generator. The ACS generator supplies primary ac power to the bus while the frequency of the ac power is within a frequency range. If the frequency of the ac power goes outside the frequency range, the main engine generator supplies backup ac power to the bus. The frequency of the ac power generated the ACS generator is maintained between upper and lower limits. Such ac power can be used directly by certain ac loads onboard the aircraft. Other ac loads onboard the aircraft are supplied with fixed frequency ac power by reduced-size inverters.

The invention relates to electrical power systems for aircraft. More specifically, the invention relates to an aircraft electrical power system including an air conditioning system generator.
In an electrical power system of an aircraft, electrical equipment onboard the aircraft is typically connected to one or more electrical buses, and electricity is supplied to the buses by electrical generators that are driven by the aircraft's main engines. When a piece of equipment such as a galley oven is turned on, it uses electrical power. As the generator delivers the power to the piece of equipment, it places a load on the main engine. Consequently, the main engine is forced to work harder and burn additional fuel. This increase in fuel consumption results in higher operating costs for the aircraft.
The electrical power system also includes power conditioning electronics, which adds weight to the aircraft. The main engine generators are operated at variable speeds (due to varying shaft speed of the main engine) and therefore supply ac power at variable or "wild" frequencies. However, the electrical equipment typically runs on dc power or ac power at a fixed frequency such as 115 vac at 400 Hz. Typically, a rectifier unit is used for converting the ac generator power to dc power, and an inverter is used for converting the dc power to ac power having a fixed frequency. An inverter might add ninety pounds of weight to the aircraft. The added weight also increases the fuel consumption.
Additionally, the inverter is expensive. An inverter might cost more than ten thousand dollars.
There is a need to reduce fuel consumption and costs associated with the electrical power system of an aircraft.

Aircraft electrical power system including air conditioning system generator


A wire strapping or tying device (46) is provided having a rotatable pinion-type knotter assembly (56) for twist-knotting of a pair of adjacent wire sections (50a, 50b), together with a shiftable knotter cover (266) movable between a home position for maintaining the sections (50a, 50b) within the assembly (56) and a remote knotter access position allowing ready access to the knotter assembly (56). The cover (266) is supported by arms (268, 270) which are pivotal about an axis spaced from and generally parallel with the cover (266). The cover (266) may be manually shifted to the remote knotter access position through an arc of at least 45°. Also, the knotter assembly (56) includes a primary body (128) supporting a rotatable, slotted knotter pinion (178). The body (128) is pivotally secured to frame plates (68, 70), allowing the body (128) to be pivoted to a convenient position for servicing of pinion (178). Preferably, a mechanical operator assembly (198) is employed to sequentially operate all of the device components in a precise, timed sequence. A single drive assembly (196) preferably in the form of a piston and cylinder assembly (200) is used to actuate the assembly (198).

1. Field of the Invention
The present invention is broadly concerned with wire strapping apparatus of the type used to apply knotted and tensioned wire ties to preformed bales such as compressed refuse bales. More particularly, the invention is concerned with such apparatus having features permitting quick and easy access to critical wire knotting components, so that the user may readily clear, repair and/or replace such components as necessary.
2. Description of the Prior Art
Various wire tying and strapping machines have been proposed in the past for applying knotted and tensioned wire ties to bales, packages or other articles. One class of these prior machines makes us of a continuous, two-piece wire track with an associated strapping device. In such units, a package or bale to be tied is positioned within the confines of the wire track, and a continuous strand of wire is advanced completely around the track and overlapped with itself. The wire is then tensioned and the overlapped sections are knotted together by twisting. This further tensions the wire to the point that the track sections are separated allowing the knotted and tensioned tie to snap into place about the bale or article. In some cases more complex devices are provided for ejecting the knotted wire from the track.
Commonly, a twister pinion is employed for twist-knotting of adjacent wire sections. Such a knotter pinion includes a slot to accommodate the wire sections and upon rotation of the pinion a defined number of turns or twists are created. In order to maintain the wires in the twister pinion and associated structure, a shiftable knotter cover located adjacent the twister pinion is used.
A significant problem with prior machines is the difficulty of readily clearing or servicing the twister pinion and related structure. Hence, in one prior machine design, it is necessary to physically detach the cover and disassemble the pinion apparatus for servicing purposes. In other instances, the cover is movable to only a very limited extent, making it very difficult to access the pinion.
Prior art patents relating to strapping devices include U.S. Pat. Nos. 4,777,554, 3,295,436, 2,922,359, and 4,817,519.


The present invention provides a canvass accessory device or xe2x80x9cPC Saddlebagxe2x80x9d that fits over the top of the computer tower and drapes down both sides of the tower. Both sides of the saddlebag have an inner and an outer side panels with pocket assemblies forming storage compartments for retaining a number of CDs in each assembly. The inner panels are integral with a top panel placed over the computer tower. The outer panels are integral with the bottom edge of the inner panels and fold upward to fasten at the top panel with fasteners in a closed configuration or vertical storage position. In the vertical storage position the outer panels can have exterior satchels and pouches accessible for document and disk storage. In an open configuration, the outer panels are released and rotated to expose the pocket assemblies on the inside surfaces of the outer panels and the outside surfaces of the inner panels where compact disks and computer software documents are organized and stored for easy retrieval and use. A carrying handle is attached to the top panel for removing the saddlebag from the computer tower and transporting it to another location in support of another computer.

This invention is directed to a case or storage device for organizing and accessing vital computer disks and software documents and, in particular, a foldable case or saddlebag storage device with pocket assemblies that is placed over a computer tower for retention of compact disks and documents which are organized and easily accessed when needed.
Many times when using a personal computer (PC), software installation and operational disks and diskettes are needed to resolve computer problems, store data or to initiate and reload a program in the computer. Most software program disks and data storage disks are kept in a storage chest or cabinet at a location somewhat remote from the computer itself. These operational devices are usually not organized and a user generally can not find what is needed. A need remains to have an accessory devise or case at the location of the computer without using valuable desktop, drawer or computer cabinet space. The accessory device must provide for easy access to a relatively large number of disks or diskettes in support of a number of programs installed or available to install in the computer and/or needed to repair computer problems, or restore backup data.
A laptop or portable PC represents an even larger challenge for having software devices near the computer for support of the programs being used in the PC. Typically the carrying case for a laptop computer has a limited number of storage compartments or enclosures for peripheral devices, writing implements, tools and the like. Carrying cases for laptop computers are disclosed in U.S. Pat. Nos.: 5,217,119; 5,971148; and 6,105.763. These references give some insight into what type of pockets are used to provide storage for computer supporting equipment. However, the special requirements required for nomadic computing makes these cases unsuitable for the single location PC with the broad range of software used with the PC.
Compact disk storage and display devices are disclosed in U.S. Pat. Nos: 4,651,872; 5,762,246; and 5,996,786. The recording disk storage apparatus of ""786 includes a saddle shaped to fit over a computer component, such as a conventional computer tower. The storage apparatus has a plurality of box shaped cases which individually attach to the saddle placed over the computer tower. Access to stored recording disks is through a front door having a clear panel to visually observe the disks in each box shaped case. This means for storage and retrieval requires a strap to hold the saddle in place making the storage apparatus not portable. The use of compact disk storage pockets is illustrated in both the ""246 and the ""872 patents for storage at a remote location from the computer, or possibly a desk display location.
The need remains to provide storage for a large number of software installation disks, data storage disks and associated equipment and documents needed to support PC computer operations at a work station. Many times software installation disks needed to resolve computer problems can not be located. The storage device or case would provide immediate easy access to compact disks and documents critical to day-by-day operation of personal computers in a fast paced business environment. Access is at the location of the PC. In addition, a need exists to allow easy transporting of the compact disks (CDs) and equipment to another PC for parallel supporting requirements. Also, a need exists to remove data backup disks from the premises in case of fire or other catastrophic event. The storage and easy access accessory device or case is also referred to herein as a xe2x80x9cPC Saddlebagxe2x80x9d.
Accordingly, an object of the present invention is to provide immediate and easy access to compact disks with read only memory data for computer operation and maintenance which is critical for day to day operation of personal computers.
Another object of the present invention is to provide computer users with a convenient accessory device for locating vital compact disks and diskettes in support of their PCs and its operating programs without using costly storage space.
Still another object of the present invention is to eliminate the loss of valuable software program disks and documentation in case of a fire and to reduce the time involved in finding the correct software support materials when needed.
A further object of the present invention is to provide a tote device or foldable case for transporting compact disks and documentation from place to place in support of more than one personal computer.
The above objectives are accomplished according to the present invention by providing a canvass accessory device or xe2x80x9cPC Saddlebagxe2x80x9d that fits over the top of the computer tower and drapes down both lateral sides of the tower. Both sides of the saddlebag have inner and outer side panels essentially equal in size. Each panel includes a pocket assembly for retaining a number of CDs in storage pockets of the assembly. The inner panels have top first edges integral with lateral edges of a top panel placed over the computer tower. The outer panels are integral at a hinged edge with a bottom second edge of the inner panels and rotate upward about the hinged edge to fasten at a top free edge to the top panel with fasteners in a storage configuration or vertical storage position. In the vertical storage position the outer panels can have accessible exterior satchels or pouches for additional storage of disks and documents. In an open configuration, a respective outer panel is released from the top panel and rotated about its hinged edge to expose a first pocket assembly on the inside surface of the outer panel and a second pocket assembly on the outside surface of a respective inner panel. Compact disks are organized and stored using the pocket assemblies for ease of retrieval and use. A carrying handle is attached to the top panel for removing the saddlebag from the computer tower and transporting it to another location in support of another personal computer, or removal of disks containing backup data from the premises to another remote location in case of fire or other catastrophic event.
In one embodiment of the invention an accessory device is provided for placement on a computer tower with a tower top and lateral sides so that compact disks and documents can be conveniently stored and accessed by a user. The accessory device comprises a top panel having lateral edges spaced apart to be positioned above the lateral sides of the computer tower when placed on the tower. A pair of inner side panels each having a top first edge, a bottom second edge and an outside surface is included. The top first edge coexists with a respective lateral edge of the top panel for vertically supporting the inner side panel at a respective lateral side of the computer tower. The device includes a first pocket assembly carried by the outside surface of the inner side panel for holding the disks and documents. A pair of outer side panels is included with each outer panel having a free third edge, a hinged edge coexisting with the bottom second edge of the inner side panel, an inside surface and an outside surface. The outer side panel is generally equal in size to a respective inner side panel and is capable of being rotated about the hinged edge to place the outer side panel in a vertical storage position and in a rotated access position. A second pocket assembly is carried by the inside surface of the outer side panel for holding the disks and documents. The disks and documents stored in either first or second pocket assemblies are accessed by a respective outer side panel being in the rotated access position.
In another embodiment of the invention, a foldable case is used in combination with a computer for conveniently locating computer software documentation and compact disks. The computer comprises a computer tower having a front, a top and lateral sides with lateral edges located at the intersection of the top with the lateral sides. The case comprises a top panel with lateral edges and a handle for placement of the top panel on the top of the computer tower so that the lateral edges are adjacent the lateral edges of the computer tower. A plurality of panels of the case are generally equal in size, for placement adjacent the lateral sides of the computer tower. Inner side panels of the plurality of panels have a top first edge and a bottom second edge with the top first edge being continuous with the lateral edges of the top panel for supporting the inner side panels adjacent to the lateral sides of the computer tower. Outer side panels of the plurality of panels each having a free third edge and a hinged edge where the hinged edge is formed to be continuous with the bottom second edge of the inner side panels. The outer side panels are rotated upward about the hinged edge and placed adjacent to the inner side panels to provide a vertical storage position. The free third edge of the side panels are fastened to the top panel to secure the vertical storage position or storage configuration of the outer side panels while maintaining access to the front of the computer tower. A plurality of pocket assemblies of the case include a pair of first pocket assemblies each carried by an outside surface of the inner side panel and a pair of second pocket assemblies each carried by an inside surface of the outer side panel. Each one of the plurality of pocket assemblies comprises a plurality of pocket flaps for organizing and storing the compact disks, wherein the disks are accessed by releasing a respective outer side panel from the top panel and rotating the outer side panel about the hinged edge of the outer side panel to a rotated access position to expose at least one of the plurality of pocket assemblies.


This invention relates generally to the field of commercial and residential electrical wiring installation and, more specifically, to the protection of electrical wires when they are pulled into and out of electrical junction or other electrical wiring boxes. The preferred embodiment takes the form of a rectangular frame which snaps onto and covers the sharp upper edges of a box through which wire is to be pulled. It is preferable that the upper surface of the instant invention be manufactured so as to be smooth and rounded so that wire may pass over it with out risk of damage. Additionally, the preferred method of attaching the instant device to the junction box is by way of a slot or groove which has been cut so as to match the box dimensions as nearly as is possible.

This invention relates generally to the field of commercial and residential electrical wiring installation and, more specifically, to the protection of electrical wires when they are pulled into and out of electrical junction or other electrical wiring boxes.
As part of the process of installing or removing electrical wiring and/or fiber optics in commercial and residential buildings, it is common practice to run wire through tubular metal pipes or conduits which might be located in the walls, ceiling, floors, etc. The conduit runs terminate in open faced metallic junction boxes which provide access to the wiring which is otherwise encased within conduit. It is customary to securely mount these boxes within a wall, the ceiling , or the floor. During installation, wiring is pulled through a box and into the conduit until such time as the necessary length of wire within (and outside of) the conduit is obtained. In a related operation, it may be necessary to remove existing wiring from a single conduit or a an entire building, in which case the wiring is pulled out of the conduit. However, since these two operations implicate similar concerns, they will not be discussed separately hereinafter. Additionally, note that the term xe2x80x9cwiresxe2x80x9d and xe2x80x9cwiringxe2x80x9d as they are used hereinafter will be used in the broadest possible sense to refer to conventional electrical power lines, as well as to computer network cables (including thick and thin Ethernet, twisted pair, etc.), fiber optic lines, etc.
Pulling wires into junction boxes and through the conduit fixtures can be a very difficult process because of friction between the wiring and the conduit. As a consequence, it may require a great deal of force to move the wire through the junction box and into the conduit. However, it is well known to those skilled in the art that the process of pulling wire into or out of a junction box risks damage to the wire from the sharp edges of that box. Pulling the wire across the edges of the junction boxxe2x80x94and especially where that is done with great forcexe2x80x94can potentially abrade the insulation covering of the wires, which can in some cases completely expose the interior of the wire. Obviously, wiring that has been damaged in this way poses a long-term threat to the integrity of the building wiring system.
In an ideal scenario, the conscientious electrician will strive to orient the wire so that it exits the box as nearly as possible at a 180 degree angle with respect to the conduit, so that when it is pulled the amount of friction generated thereby is reduced. This orientation also tends to minimize the risk of physical damage from the sharp edges of the junction box as the wire is moved past. Further, and in a perfect world, there will be another person on the other end of the wire to guide it into the box, thereby minimizing the same risks on the opposite end.
However, it is not always possible to pull the wire at the optimum angle because, for example, the box may be mounted near the floor or high above the electrician""s head on the ceiling. (When working on a ladder it is much safer to pull xe2x80x9cdownxe2x80x9d than xe2x80x9claterallyxe2x80x9d.) Further, the increased cost and inconvenience occasioned by the involvement of another person at the other end of the wire to guide it into the box may result in the electrician just performing the task by him or herself, at a risk of skinning the installed wire. As a consequence, it is not unusual to see an electrician pulling wire through the wall unassisted. Finally, even when it might be possible to do otherwise, some employees might choose not to pull at the xe2x80x9coptimumxe2x80x9d angle because they believe there is no real risk of damage to the wire or perhaps because it is just easier to do this operation incorrectly.
Others have considered this problem but the solutions suggested heretofore have not been entirely satisfactory. Wire guides in the shape of curved horns have been suggested for attachment to one end of a conduit where it is mounted to ajunction box so that the wires may be fed into the conduit at a proper angle. One example of such a device is described in U.S. Pat. No. 2,515,724. In U.S. Pat. No. 4,132,665, a rigid funnel for use in feeding wires through ajunction box and associated conduit is disclosed. These prior art devices have not found broad acceptance in the related trades because they tend to be relatively large and bulky and not very easy to use.
Other approaches use various combinations of rollers and pulleys. However, these approaches suffer from the disadvantage that they must be securely attached to the box, usually with thumb screws or the like (which results in additional time being spent to install and remove the device). Additionally, roller-based solutions are subject to their own friction/crimping problems. For example, if the wire is pulled at an angle that causes it to rub against a roller guide or roller support, binding of the wire and scraping of the insulation may result. Thus, these sorts of solutions can only accommodate wires that enter the device within a fairly narrow range of angles. Finally, solutions involving rollers or pulleys also tend to be relatively bulky and expensive to build. Since these sorts of devices are installed remotely from where the user is actually working, it is inevitable that the device will at least occasionally be forgotten and left at the job site where it could be lost or stolen. Obviously, the more expensive the device the less likely that an electrician would be willing to replace it and the electrician might choose instead to risk the possibility that hidden damage might be introduced into wires, which damage might not be discovered until months or years later. Examples of such prior art devices are disclosed in U.S. Letters Pat. Nos. 4,358,089; 4,033,551; 3,944,184; 3,113,759; 2,746,715; and 2,727,721. These references teach rigidly mounted, or rigidly held guides or pulleys which they can be used either for pulling wires into, or out of, electrical conduit.
Heretofore, as is well known in the electrical arts, there has been a need for an invention to address and solve the above-described problems. Accordingly, it should now be recognized, as was recognized by the present inventor, that there exists, and has existed for some time, a very real need for a device that would address and solve the above-described problems.
Before proceeding to a description of the present invention, however, it should be noted and remembered that the description of the invention which follows, together with the accompanying drawings, should not be construed as limiting the invention to the examples (or preferred embodiments) shown and described. This is so because those skilled in the art to which the invention pertains will be able to devise other forms of this invention within the ambit of the appended claims.
In accordance with a preferred aspect of the instant invention, there is provided an electrical wire guide which serves to protect one or more insulated electrical wires as they are drawn into or pulled out of an electrical wiring junction box or similar rigidly mounted device.
Broadly speaking, the instant device is an edge protector which fits snugly over all four edges of a conventional junction box. The preferred embodiment takes the form of a rectangular frame which snaps onto and covers the sharp upper/outer edges of a box through which wire is to be pulled. It is preferable that the upper surface of the instant invention, i.e., the portion of the instant device that contacts the wire, be manufactured so as to be smooth and rounded so that wire may pass over it with out risk of damage. The rounded portion of the device is stationary, i.e, non-rotating, so that it is critical that at least this portion present a smooth contact surface to the wire. Additionally, the preferred method of attaching the instant device to the junction box is by way of a slot or groove which has been cut so as to match the box dimensions as nearly as is possible. Thus, the instant device is preferably held in place by friction. Of course, it is well within the ability of one having ordinary skill in the art to adapt this device to work with junction boxes that are shaped other than as a rectangle (e.g., a round junction box). It is critical, though, that all of the edges of the junction box be covered by the device of the instant application.
Among the many advantages to the sort of tool taught herein are the simplicity of its design which means that it can be built and marketed relatively inexpensively; its ease of installation and removal; its ability to accommodate electrical lines coming into (and exiting from) the box at any angle; its low profile and light weight which makes it possible for the electrician to carry a number of these devices on his or her person; and, its ability to be installed on boxes which have been enclosed within walls that are covered by plaster or wall board. The design of the instant device will allow it to work, for example, in multi-gang boxes, through wall boxes, and all tile and plaster rings regardless of their thickness.
The foregoing has outlined in broad terms the more important features of the invention disclosed herein so that the detailed description that follows may be more clearly understood, and so that the contribution of the instant inventor to the art may be better appreciated. The instant invention is not to be limited in its application to the details of the construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. Rather, the invention is capable of other embodiments and of being practiced and carried out in various other ways not specifically enumerated herein. Further, the disclosure that follows is intended to cover all alternatives, modifications and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims. Finally, it should be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting, unless the specification specifically so limits the invention.
While the instant invention will be described in connection with a preferred embodiment, it will be understood that it is not intended to limit the invention to that embodiment. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.

Edge protector for electrical junction boxes


An optically clear, transparent or translucent hair conditioner in the form of a water-in-silicone oil emulsion is described. Said hair conditioner contains a silicone surfactant, a hydrophobic, nonsurfactant silicone compound present in the hair conditioner in liquid form, a basic or cationic nitrogen atom-containing hair-conditioning compound, a nonionic, silicone-free surfactant, a polyhydric alcohol and an electrolyte. The hair conditioner can be used as a leave-in hair treatment or as a hair rinse.

This application is a 371 of PCT/8900/10134 filed Oct. 14, 2000.
The object of the invention is a hair conditioner which, in particular, can be used as a leave-in hair treatment or as a hair rinse, is in the form of an optically clear, transparent or at least translucent product and contains a silicone surfactant, a hydrophobic, nonsurfactant silicone compound present in the hair conditioner in liquid form, a basic or cationic nitrogen atom-containing hair conditioning compound and a nonionic, silicone-free surfactant.
As a rule, conventional hair-conditioning preparations such as rinse-off treatments or leave-on treatments are formulated on the basis of aqueous emulsions. Essential ingredients are cationic substances, for example cationic surfactants, hydrophobic substances, such as fatty alcohols and other oil components, emulsifiers and other specific agents and odorants. The most important ingredients are the cationic surfactants, fatty alcohols and emulsifiers. Schrader provides a review of the basic formulations of rinses and hair treatments in xe2x80x9cGrundlagen und Rezepturen der Kosmetikaxe2x80x9d [Fundamentals and Formulations of Cosmetics], 2nd edition, 1989, pp. 728-737. The main function of hair conditioners is to improve the stylability, compatibility, luster and feel of the treated hair. The treated hair often feels somewhat heavier or more highly loaded, which is not always desirable. Moreover, the conventional oil-in-water [O/W] hair-care emulsions are normally milky white and opaque. Desirable are products which are in an optically more attractive form and clear, transparent or at least translucent. Various forms of clear hair-care compositions are known and described, for example, in E. Flick, xe2x80x9cCosmetic and Toiletry Formulationsxe2x80x9d, second edition, volume 2, pp. 373 ff. These clear hair-care compositions are based on polymers with a thickening action such as, for example, cellulose derivatives (tradenames Natrosol(copyright), Methocel(copyright)), high-molecular-weight chitosan derivatives (tradename Kytamer(copyright) PC), complex polysaccharides (tradenames karaya gum, tragacanth, Jaguar(copyright) brands, Keltrol(copyright) brands) and acrylic acid polymers. All these prior art clear hair-care compositions have the serious drawback that their efficacy is so low that it does not even come close to that of a conventional hair-care compositions based on a mixture of a fatty alcohol and a quaternary surfactant. Moreover, the distributability of these clear products is not as good as that of conventional O/W hair-care emulsions. For this reason, these clear hair-care compositions known from the prior art do not sell as well as do the standard products.
The goal was therefore to provide a composition which meets the typical requirements placed on hair conditioners in terms of hair conditioning and distributability and at the same time is in an optically attractive, particularly optically clear or at least translucent form. We have now found that this goal can be reached by means of a hair conditioner having the composition described hereinbelow. The object of the invention is an optically clear, transparent or translucent hair conditioner in the form of a water-in-silicone oil emulsion containing
(A) at least one silicone surfactant selected from among the siloxane/polyoxyalkylene copolymers,
(B) at least one hydrophobic nonsurfactant silicone compound present in the hair conditioner in liquid form,
(C) at least one basic or cationic nitrogen atom-containing hair-conditioning compound,
(D) at least one nonionic silicone-free surfactant,
(E) 15 to 50 wt. % of water,
(F) 15 to 50 wt. % of at least one polyhydric alcohol and
(G) at least one electrolyte.
The entire silicone oil phase preferably represents less than 40 wt. % and particularly less than 20 wt. %, and the aqueous phase preferably more than 60 wt. % and particularly more than 80 wt. % of the overall composition. The hair conditioner meets very satisfactorily the requirements placed on hair conditioners in terms of conditioning action. The hair conditioner distributes itself readily on the hair. After the treatment, the hair is appreciably smoother and softer both in the wet and in the dry condition. The compatibility and stylability of the hair is better, and the hair is disentangled and lustrous. Moreover, the composition according to the invention makes it possible to produce the hair conditioner in an optically attractive, clear formulation which in turn permits advantageous packing in a transparent container made, for example, of glass or transparent plastic, for example polyethylene, polypropylene or polyethylene terephthalate.
The silicone surfactant (A) is present in the hair conditioner of the invention preferably in an amount from 0.01 to 10 wt. %, particularly from 0.1 to 5 wt. % and more preferably from 0.4 to 2 wt. %. Suitable silicones are the siloxane/polyoxyalkylene copolymers. These are siloxanes with polyalkylene oxide groups, particularly silicones modified with polypropylene oxide, polyethylene oxide or a mixture thereof. The alkylene oxide groups can be in a lateral or terminal position or the compounds can be linear polydimethylsiloxane/polyalkylene oxide block copolymers. The alkylene oxide-modified siloxanes have the INCI [International Nomenclature of Cosmetic Ingredients] designation xe2x80x9cdimethicone copolyolxe2x80x9d. Preferred silicone surfactants are those of general formula (I)
Axe2x80x94Bxxe2x80x94Dyxe2x80x94Axe2x80x83xe2x80x83(I)
wherein
A stands for the monovalent group R2R1SiOxc2xd
B denotes the divalent group R2SiO,
D denotes the divalent group RR1SiO,
R independent of each other denote H, C1-C6-alkyl or aryl, preferably H or C1-C4-alkyl and most preferably methyl,
R1 stands for an oxyalkylene-containing group, hydrogen or methyl,
x denotes a numeral from 10 to 1000, preferably from 10 to 500 and particularly from 20 to 200, and
y denotes a numeral from 0 to 100 and preferably from 1 to 50, providing that the compound contains at least one oxyalkylene-containing R1 group.
The R1 group preferably denotes a group of general formula (II)
xe2x80x94R2(OCnH2n)mR3xe2x80x83xe2x80x83(II)
wherein
R2 is a divalent group linking the oxyalkylene unit to the siloxane chain, preferably CpH2p wherein p equals 2-8, preferably 2-6 and particularly 3-6;
R3 is a monovalent end group for the oxyalkylene unit, for example H, OH, C1-C6-alkyl, aryl, C1-C6-alkoxy, C1-C6-acyloxy, but preferably OH,
n is a numeral from 2 to 4, and preferably 2 or 3, and
m is a numeral denoting at least unity, the sum of m for all oxyalkylene groups being about 10 or higher.
Suitable silicone surfactants are commercially available, for example DC 3225 C, DC Q2-5220, DC 193, DC 190 or DC Q4-3667 from Dow Corning, Silwet(copyright) L-7200 from OSI Specialties, Abil(copyright) B8830, Abil(copyright) B8851, Abil(copyright) B8863 or Abil(copyright) EM97 from Goldschmidt, SF-1 188 from General Electric or KF 353A from Shin Etsu.
The hydrophobic nonsurfactant-silicone compound (B) is preferably present in an amount from 5 to 30 wt. %, particularly from 7.5 to 25 wt. % and more preferably from 10 to 20 wt. %. Suitable in principle are all silicone compounds with hair conditioning properties and which are insoluble in the aqueous phase. Said silicone compounds may be highly volatile and of low molecular weight or low-volatile and of high molecular weight. In a preferred embodiment, the hair conditioner contains at least one low-molecular-weight, highly volatile and at least one high-molecular-weight, nonvolatile or low-volatile silicone. Nonvolatile silicones in the sense of this application are silicones with no or only low vapor pressure at normal ambient conditions (1 atmosphere, 25xc2x0 C.). These silicones remain on the hair after they have been applied. Volatile silicones, on the other hand, vaporize after they have been applied to the hair, which under normal ambient condition typically occurs within a period of about 2 hours. The high-molecular-weight silicone, however, can also be a silicone polymer (silicone resin, silicone gum) dissolved in a low-molecular-weight liquid silicone. The viscosity of low-molecular-weight silicone oils is preferably from 100 to 1000 mPa s, and that of high-molecular-weight silicone oils from more than 1000 to 2,000,000 mPa s at 25xc2x0 C., measured with a Haake, model VT 501, rotational viscometer at a shear rate of 12.9 per second. Suitable hydrophobic silicones are, in general, cyclic polydimethylsiloxanes (INCI designation: cyclomethicones), for example octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, linear polydimethylsiloxanes (INCI designation: dimethicones), polydiethylsiloxanes, phenyl-substituted siloxanes (INCI designation: phenyltrimethicones), polymethylphenylsiloxanes, hydroxy-substituted siloxanes (INCI designation: dimethiconols) or mixtures thereof.
The nitrogen-containing hair-conditioning compound (C) is preferably present in an amount from 0.01 to 10 wt. %, particularly from 0.1 to 5 wt. % and more preferably from 0.2 to 3 wt. %. The hair-conditioning compound is a substance which because of the primary, secondary, tertiary or quaternary amino groups exhibits substantivity to human hair. Suitable hair-conditioning compounds are those selected from among cationic surfactants, betaine surfactants, amphoteric surfactants, cationic polymers, cationically derivatized proteins or protein hydrolyzates, betaine and nitrogeh-containing silicone compounds. Particularly preferred are the hair conditioners of the invention which contain at least one cationic silicone-free surfactant and at least one nitrogen-containing silicone compound.
Suitable cationic surfactants are those containing a quaternary ammonium group. Such surfactants can be the cationic or amphoteric betaine surfactants. Cationic surfactants are particularly preferred as the cationic substance (A). Suitable cationic surfactants contain amino groups or quaternized hydrophilic ammonium groups which in solution bear a positive charge and are represented by general formula (III)
N(+)R1R2R3R4 X(xe2x88x92)xe2x80x83xe2x80x83(III)
wherein
R1 to R4 independently of each other denote aliphatic groups, aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylamido groups, hydroxyalkyl groups, aryl groups or alkaryl groups, each with 1 to 22 carbon atoms, and
X(xe2x88x92) denotes a cosmetically compatible anion, for example a halogen, acetate, phosphate, nitrate or alkylsulfate, but preferably chloride.
For the compound to exhibit surfactant properties, at least one of the R1 to R4 groups must have at least 8 carbon atoms. In addition to the carbon atoms and hydrogen atoms, the aliphatic groups can also contain crosslinks or other groups, for example other amino groups.
Examples of suitable cationic surfactants are the chloride or bromide salts of alkyldimethyl-benzylammonium or alkyltrimethylammonium, for example cetyltrimethylammonium chloride or bromide, tetradecyltrimethylammonium chloride or bromide, alkyldimethylhydroxyethylammonium chlorides or bromides, dialkyldimethylammonium chlorides or bromides, the alkylpyridinium salts, for example laurylpyridinium or cetylpyridinium chloride, alkylamidoethyltrimethylammonium ether sulfate, and compounds of a cationic character, such as the amine oxides, for example alkylmethylamine oxides or alkylaminoethyldimethylamine oxides. Particularly preferred are cetyltrimethylammonium chloride, sold, for example, in the form of a 26% aqueous solution under the tradename Dehyquart(copyright) A by Cognis and under the tradename Genamin(copyright) CTAC by Clariant, and in the form of a 50% solution in isopropanol under the tradename Arquad(copyright) 16-50 by Akzo Nobel.
Suitable amphoteric surfactants are the derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds of formula (IV)
wherein
R5 is a linear or branched alkyl, alkenyl or hydroxyalkyl group with 8 to 18 carbon atoms, from
0 to about 10 ethylene oxide units and from 0 to 1 glycerol units,
Y denotes an N-, P- or S-containing group,
R6 denotes an alkyl or monohydroxyalkyl group with 1 to 3 carbon atoms,
x equals 1 when Y is a sulfur atom and it equals 2 when Y is a nitrogen or phosphorus atom,
R7 denotes an alkylene or hydroxyalkylene group with 1 to 4 carbon atoms, and
Z(xe2x88x92) denotes a carboxylate, sulfate, phosphonate or phosphate group.
Other amphoteric surfactants such as the alkylbetaines are also suitable for the hair conditioner of the invention. Examples of betaines are C8-C18-alkylbetaines, such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylalphacarboxyethylbetaine, cetyidimethyl-carboxymethylbetaine, oleyldimethylgammacarboxypropylbetaine and laurylbis-(2-hydroxypropyl)-alphacarboxyethylbetaine; C8-C18-sulfobetaines, such as cocodimethylsulfopropylbetaine, stearyidimethylsulfopropylbetaine, lauryidimethylsulfoethylbetaine, laurylbis-(2-hydroxyethyl)-sulfopropylbetaine; the carboxyl derivatives of imidazole, the C8-C18-alkyldimethylammonium acetates, the C8-C18-alkyldimethylcarbonylmethylammonium salts and the C1-C18-fatty acid alkylamidobetaines, for example the coco fatty acid amidopropylbetaine which, for example, in the form of a 30% aqueous solution is sold by Goldschmidt AG under the tradename Tego(copyright) Betaine L7, and the N-coco fatty acid amidoethyl-N-[2-carboxymethoxy]ethyllglycerol (CTFA1 name: cocoamphocarboxyglycinate) which, for example, in the form of a 50% aqueous solution is sold by Miranol Chemical Co., Inc. under the tradename Miranol(copyright) C2M.
1 CTFA=Cosmetic, Toiletry and Fragrance Associationxe2x80x94Translator
The suitable cationic polymers are preferably hair-fixing or hair-conditioning polymers. Suitable cationic polymers preferably contain quaternary amino groups. The cationic polymers can be homopolymers or copolymers in which the quaternary nitrogen groups are located either in the polymer chain or preferably as substituents on one or several of the monomer units. The ammonium groups-containing monomers can be copolymerized with noncationic monomers. Suitable cationic monomers are unsaturated compounds capable of undergoing free radical-initiated polymerization and bearing at least one cationic group, particularly ammonium-substituted vinyl monomers, for example trialkylmethacryloxyalkylammonium, trialkylacryloxyalkylammonium, dialkyldiallylammonium and quaternary vinylammonium monomers with cyclic, cationic, nitrogen-containing groups, such as pyridinium and imidazolium, or quaternary pyrrolidones, for example alkylvinylimidazolium, alkylvinylpyridinium, or alkylvinylpyrrolidone salts. The alkyl groups of these monomers are preferably lower alkyl groups, for example C1-C7-alkyl groups and particularly C1-C3-alkyl groups.
1 CTFA=Cosmetic, Toiletry and Fragrance Associationxe2x80x94Translator
The ammonium groups-containing monomers can be copolymerized with noncationic monomers. Suitable comonomers are, for example, acrylamide, methacrylamide, alkyl- and dialkylacrylamide, alkyl- and diacrylmethacrylamide, alkyl acrylate, alkyl methacrylate, vinylcaprolactone, vinylcaprolactam, vinylpyrrolidone, vinyl esters, for example vinyl acetate, vinyl alcohol, propylene glycol or ethylene glycol, the alkyl groups of these monomers preferably being C1-C7-alkyl groups and particularly C1-C3-alkyl groups.
Suitable polymers with quaternary amino groups are, for example, the polymers described in the CTFA Cosmetic Ingredients Dictionary under the polyquaternium names, such as methylvinylimidazolium chloride/vinylpyrrolidone copolymer (polyquaternium 16) or the quaternized vinylpyrrolidone/dimethyl-aminoethyl methacrylate copolymer (polyquaternium 11), and the quaternary silicone polymers or oligomers, such as, for example, the silicone polymers with quaternary end groups (quaternium 80).
Suitable cationic polymers that can be contained in the hair conditioners of the invention include, for example, vinylpyrrolidone/dimethylaminoethyl methacrylate methosulfate copolymer sold by ISP under the tradenames Gafquat(copyright) 755 N and Gafquat(copyright) 734, of which Gafquate 734 is particularly preferred. Other cationic polymers are, for example, the copolymer of polyvinyl pyrrolidone [sicxe2x80x94vinylpyrrolidone seems to be meantxe2x80x94Translator] and imidazolimine methochloride, sold by BASF, Germany, under the tradename LUVIQUAT(copyright) HM 550, the terpolymer of dimethyldiallylammonium chloride, sodium acrylate and acrylamide, sold by Calgon/USA under the tradename Merquat(copyright) Plus 3300, the terpolymer of vinylpyrrolidone, dimethylaminoethyl methacrylate and vinylcaprolactam sold by ISP/USA under the tradename Gaffix(copyright) VC 713 and the vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloride copolymer sold by ISP under the tradename Gafquat(copyright) HS 100.
Suitable cationic polymers derived from natural polymers are the cationic derivatives of polysaccharides, for example the cationic derivatives of cellulose, starch or guar. Also suitable are chitosan and chitosan derivatives. Cationic polysaccharides have the general formula (V)
Gxe2x80x94Oxe2x80x94Bxe2x80x94N+RaRbRc Xxe2x88x92xe2x80x83xe2x80x83(V)
wherein
G is an anhydroglucose radical, for example starch anhydroglucose or cellulose anhydro-glucose,
B is a divalent linking group, for example alkylene, oxyalkylene, polyoxyalkylene or hydroxyalkylene,
Ra,Rb,Rc are independently of each other alkyl, aryl, alkylaryl, arylakyl, alkoxyalkyl or alkoxyaryl, each with up to 18 carbon atoms, the total number of carbon atoms in Ra, Rb and Rc preferably being at the most 20;
xxe2x88x92 is a common counteranion, has the same meaning as in formula (III) and is preferably chloride.
A cationic cellulose is sold by Amerchol under the name Polymer JR and has the INCI designation polyquaternium 10. Another cationic cellulose has the INCI designation polyquaternium 24 and is sold by Amerchol under the tradename Polymer LM-200. A suitable cationic guar derivative is sold under the tradename Jaguar(copyright) R and has the INCI designation guar hydroxypropyltrimonium chloride. Particularly preferred cationic substances are chitosan, chitosan salts and chitosan derivatives. The chitosans used according to the invention are completely or partially deacetylated chitins. The preferred starting material for preparing chitosan is the chitin contained in the shell residues of crustaceans and which is available in large amounts as an inexpensive and natural raw material. The molecular weight of chitosan can be distributed over a broad range, for example from 20,000 to about 5 million g/mol. Suitable is, for example, a low-molecular-weight chitosan with a molecular weight of 30,000 to 70,000 g/mol. Preferably, however, the molecular weight is higher than 100,000 g/mol and particularly ranges from 200,000 to 700,000 g/mol. The degree of deacetylation is preferably 10 to 99% and particularly 60 to 99%.
A suitable chitosan is sold, for example, by Kyowa Oil and Fat, Japan, under the tradename Flonac(copyright). It has a molecular weight of 300,000 to 700,000 g/mol and is 70 to 80% deacetylated. A preferred chitosan salt is chitosoniumpyrrolidone carboxylate sold, for example, by Amerchol, USA, under the tradename Kytamer(copyright) PC. The chitosan contained in this material has a molecular weight of about 200,000 to 300,000 g/mol and is 70 to 85% deacetylated. Suitable chitosan derivatives are the quaternized, alkylated or hydroxyalkylated derivatives, for example hydroxyethylchitosan or hydroxybutylchitosan.
The chitosans or chitosan derivatives are preferably in neutralized or partly neutralized form. The degree of neutralization of chitosan or a chitosan derivative is preferably at least 50% and particularly between 70 and 100%, based on the number of free basic groups. In principle, all cosmetically compatible inorganic or organic acids can be used as the neutralization agent, for example formic, tartaric, malic, lactic, citric, pyrrolidonecarboxylic or hydrochloric acid and the like. Among these, pyrrolidonecarboxylic acid is particularly preferred.
Other suitable cationic hair-care compounds are the cationically modified protein derivatives or cationically modified protein hydrolyzates known, for example, under the INCI designations lauryldimonium hydroxypropyl hydrolyzed wheat protein, lauryldimonium hydroxypropyl hydrolyzed casein, lauryldimonium hydroxypropyl hydrolyzed collagen, lauryldimonium hydroxypropyl hydrolyzed keratin, lauryidimonium hydroxypropyl hydrolyzed silk, lauryidimonium hydroxypropyl hydrolyzed soy protein or hydroxypropyltrimonium hydrolyzed wheat, hydroxypropyltrimonium hydrolyzed casein, hydroxypropyltrimonium hydrolyzed collagen, hydroxypropyltrimonium hydrolyzed keratin, hydroxypropyltrimonium hydrolyzed rice bran protein, hydroxypropyltrimonium hydrolyzed silk, hydroxypropyltrimonium hydrolyzed soy protein and hydroxypropyltrimonium hydrolyzed vegetable protein.
Suitable cationically derivatized protein hydrolyzates are mixtures of substances obtainable, for example, by reaction of a protein hydrolyzed with an alkali, acid or enzyme and glycidyltrialkyl-ammonium salts or 3-halo-2-hydroxypropyltrialkylammonium salts. The proteins used as starting materials for the protein hydrolyzates can be of vegetable or animal origin. Common starting materials are, for example, keratin, collagen, elastin, soy protein, rice protein, milk protein, wheat protein, silk protein or almond protein. Hydrolysis affords mixtures of substances with molecular weights in the range from about 100 to about 50,000. The average molecular weights are usually in the range from about 500 to about 1000. Advantageously, the cationically derivatized protein hydrolyzates contain one or two long C8-C22-alkyl chains and, correspondingly, two or one short C1-C4-alkyl chain. Compounds containing one long alkyl chain are preferred.
Suitable cationically active silicone compounds are the cationic silicones, betaine silicones or amino-substituted silicones. They contain either at least one amino group or at least one ammonium group. Suitable silicone polymers with amino groups are known under the INCI designations amodimethicone and trimethylsilylamodimethicone. These are polydimethylsiloxanes with aminoalkyl groups. The aminoalkyl groups can be lateral or terminal. Suitable aminosilicones are those of general formula (VI)
R8R9R10Sixe2x80x94(OSiR11R12)xxe2x80x94(OSiR13Q) yxe2x80x94OSiR14R15R16xe2x80x83xe2x80x83(VI)
wherein
R8, R9, R14 and R16 independently of each other are equal or different and denote C1-C10 -alkyl, phenyl, hydroxyl, hydrogen, C1-C10-alkoxy or acetoxy, preferably C1-C4-alkyl and particularly methyl,
R10 and R16 independently of each other are equal or different and denote xe2x80x94(CH2)axe2x80x94NH2 where a equals 1 to 6, C1-C10-alkyl, phenyl, hydroxyl, hydrogen, C1-C10-alkoxy or acetoxy, preferably C1-C4-alkyl and particularly methyl,
R11, R12, R13 independently of each other are equal or different and denote hydrogen, a C1-C20-hydrocarbon group which can contain O- and N-atoms, but preferably C1-C10-alkyl or phenyl, particularly C1-C4-alkyl and especially methyl,
Q denotes xe2x80x94Axe2x80x94NR17R18, or xe2x80x94Axe2x80x94N+R17R18R19 where A stands for a divalent C1-C20-alkylene linking group which can also contain O- and N-atoms and OH groups, and R17, R18 and R19 independently of each other are equal or different and denote hydrogen, a C1-C22 hydrocarbon group and preferably C1-C4 alkyl or phenyl. The preferred Q radicals are xe2x80x94-(CH2)3-NH2, xe2x80x94(CH2)3NHCH2CH2NH2, xe2x80x94CH2CH(CH3)CH2NHCH2CH2NH2, xe2x80x94(CH2)3OCH2CHOHCH2NH2, xe2x80x94(CH2)3N(CH2CH2OH)2, xe2x80x94(CH2)3-NH3+ and xe2x80x94(CH2)3OCH2CHOHCH2N+(CH3)2R20, where R20 is a C1-C22-alkyl radical that can also contain OH groups,
x is a numeral from 1 to 10,000, preferably from 1 to 1000, and
y denotes a numeral between 1 and 500 and preferably between 1 and 50.
The molecular weight of the aminosilicones is preferably between 500 and 100,000. The amine content (meq/g) is preferably in the range from 0.05 to 2.3 and particularly from 0.1 to 0.5.
Suitable silicone polymers with two terminal quaternary ammonium groups are known under the INCI designation quaternium 80. These are dimethylsiloxanes with two terminal aminoalkyl groups. Suitable quaternary aminosilicones are those of general formula (VII)
R21R22R23N+xe2x80x94Axe2x88x92SiR8R9xe2x80x94(OSiR11R12)nxe2x80x94OSiR8R9xe2x80x94Axe2x80x94N+R21R22R23 2Xxe2x88x92xe2x80x83xe2x80x83VII
wherein
A has the same meaning as indicated hereinabove for formula (VI) and is preferably xe2x80x94(CH2)3OCH2CHOHCH2 in combination with the N+(CH3)2R20 group, where R20 is a C1-C22-alkyl radical which can also contain OH groups,
R8,R9,R11,R12 have the same meaning as indicated hereinabove for formula (VI) and preferably denote methyl,
R21,R22, R23 independently of each other denote C1-C22-alkyl radicals which can contain hydroxyl groups and wherein preferably at least one of the radicals contains at least 10 carbon atoms and the remaining radicals contain from 1 to 4 carbon atoms, and
n is a numeral from 0 to 200 and preferably from 10 to 100.
Such diquaternary polydimethylsiloxanes are sold by Goldschmidt under the tradenames Abil(copyright) Quat 3270, 3272 and 3274.
The nonionic, silicone-free surfactant (D) is preferably present in the hair conditioner in an amount from 0.01 to 5 wt. %, particularly from 0.1 to 2 wt.0h and most preferably from 0.2 to 1 wt. %. Suitable nonionic surfactants are, for example, those described in the xe2x80x9cInternational Cosmetic Ingredient Dictionary and Handbookxe2x80x9d, 7th edition, vol. 2, in the chapter on xe2x80x9cSurfactantsxe2x80x94Emulsifying Agentsxe2x80x9d. Suitable nonionic surfactants are preferably selected from among ethoxylated fatty acids with 10 to 26 carbon atoms, ethoxylated monohydric or polyhydric alcohols with 1 to 6 carbon atoms, ethoxylated fatty alcohols with 10 to 26 carbon atoms, ethoxylated hydrogenated or nonhydrogenated castor oil, alkylpolyglucosides, glyceride alkoxylates, fatty acid glyceride polyalkylene glycol ethers or fatty acid partial glyceride polyalkylene glycol ethers, each with less than 30 alkylene glycol units. Examples of these are polyethylene glycol(7) glyceryl cocoate, polyglycolamides, fatty acid sugar esters, ethoxylated fatty acid sugar esters and partial glycerides. The degree of ethoxylation of the ethoxylated surfactants is usually from 1 to 400, particularly from 2 to 200 and most preferably from 3 to 25. Preferred nonionic surfactants are, in particular, the fatty alcohol ethoxylates. Suitable are, for example, alcohols with 10 to 18 and preferably with 10 to 16 carbon atoms, and a preferred degree of ethoxylation of 2 to 200 and particularly 3 to 25. The nonionic surfactants preferably have a relatively high HLB2 value of at least 9.
2 HLB=hydrophilic-lipophilic balancexe2x80x94Translator
The water content preferably ranges from 15 to 50 wt. %, particularly from 15 to 40 wt. % and most preferably from 15 to 39 wt. %. The aqueous phase of the hair conditioner of the invention contains as a cosolvent at least one cosmetically compatible polyhydric alcohol. Suitable polyhydric alcohols are, in particular, those with 2 to 4 carbon atoms, for example, ethylene glycol or propylene glycol, but also sorbitol, with glycerol being particularly preferred. The polyhydric alcohols are preferably used in an amount from 5 to 50 wt. %, particularly from 10 to 40 wt. % and most preferably from 15 to 39 wt. %. Moreover, the hair conditioner can also contain lower monohydric alcohols with 1 to 4 carbon atoms commonly used for cosmetic purposes, for example ethanol and isopropanol.
The hair conditioner of the invention is preferably in the form of a microemulsion. To achieve a particularly clear product, the refractive indices of the oil phase and the aqueous phase are adjusted to be essentially equal. Particular characteristics of the hair conditioner of the invention are its outstanding clarity and transparency. Hence, the hair conditioner is advantageously packaged in optically attractive containers made of transparent or translucent material. Suitable packaging materials are, in particular, glass and transparent or translucent plastics, for example polyethylene terephthalate.
For increased emulsion stability, the hair conditioner of the invention contains water-soluble electrolytes, for example sodium chloride or sodium sulfate. The electrolytes are preferably used in an amount from 0.01 to 5, particularly from 0.1 to 4 and most preferably from 0.5 to 1.5 wt. %. The pH of the hair conditioner of the invention is preferably in the acid range, for example between 2.0 and 6.0. Particularly preferred is the pH range of 3.5-4.5. The pH can be adjusted with suitable organic or inorganic acids, for example with formic, tartaric, malic, maleic, fumaric, pyrrolidone-carboxylic, citric, lactic, sulfuric, acetic, hydrochloric, phosphoric and glyoxylic acid, among others.
The hair conditioner of the invention can also contain the usual additive components for hair-care compositions, for example fixing or nonfixing nonionic, anionic, cationic, zwitterionic or amphoteric polymers as well as combinations thereof, preferably in an amount of 0.01 to 10 wt. %, the polymer possibly being synthetic or of natural origin; perfume oils preferably in an amount from 0.01 to 5 wt. %; other wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or nonionic surface-active substances, preferably in an amount from 0.01 to 10 wt. %; moisturizing agents, preservatives, bactericidal and fungicidal agents, for example 2,4,4-trichloro-2-hydroxydiphenyl ether, parabens or methylchloroisothiazolinone in an amount from 0.01 to 1.0 wt. %; buffering agents, for example sodium citrate or sodium phosphate, in an amount from 0.1 to 1.0 wt. %; colorants, for example fluorescein sodium salt, in an amount from about 0.1 to 1.0 wt. %; cosmetic care agents, for example plant and herb extracts, protein and silk hydrolyzates, lanolin derivatives, in an amount from 0.1 to 5 wt. %, and furthermore sunscreen agents, antioxidants, free-radical scavengers, anti-dandruff agents, fatty alcohols, luster-imparting agents, vitamins and fat-restoring agents, in an amount from 0.01 to 10 wt. %.
The hair conditioner can be in the form of a lotion or a thickened lotion of varying viscosity or in the form of a highly viscous or fluid gel or a liquid gel.
If the hair conditioner is in the low-viscosity form, it can also be sprayed onto the hair to achieve especially good distribution. The hair conditioner according to the invention is then used in conjunction with a suitable mechanically actuated spraying device. By mechanical spraying device is meant a device permitting the spraying of a liquid without the use of a propellant. A suitable mechanical spraying device is, for example, a spray pump or a spray valve-bearing elastic container into which the hair conditioner of the invention is introduced under pressure causing the container to expand. When the valve is opened, the hair conditioner is steadily released as a result of the contraction of the elastic container.
The hair conditioner can be used as a rinse-off or as a leave-on product. A typical application as rinse-off product involves distributing an amount of hair conditioner, sufficient to achieve a desired conditioning effect after washing the hair, into or onto wet or moist, towel-dried hair. The amount to be used depends on the fullness of the hair and typically ranges from 1 to 25 g and preferably from 3 to 10 g. After a sufficient exposure time of, for example, 1 to 15 minutes, the hair is rinsed. If only a gentle conditioning effect is desired, the rinsing may also be done immediately. The hair is then optionally combed or formed into a hair style and dried. For use as a leave-on product, 0.5 to 3 g of the product is preferably worked into the dry hair. As a result, the cuticulae are smoothed out, the undesirable entanglements are removed, and luster, stylability, control and structure are conferred to the hair.

Transparent water-silicon hair conditioning agent