A kit for universal use with standard bicycles includes an electrical motor which is mountable to the pedal axle of a bicycle, the electric motor having permanent magnets, an electronic control for these motor magnets, batteries and a reduction gear based upon the motor""s number of revolutions per minute. The kit uses special sensors which register the pedal rotation rate and the pressure exerted by the bicyclist upon the pedals, which information is processed by a control device which controls actuation of the electric motor as such is required by the bicyclist.

This invention relates generally to bicycles and other pedal vehicles. More particularly, it relates to a motor-assisted apparatus in the form of an assembly, or kit, which may be added to any existing bicycle to convert the bicycle from one which moves by pedal power alone to one which moves by pedal power, by motor-assisted power or by a combination of both. Use of this kit with a conventional bicycle serves to aid the bicyclist in negotiating steep gradients and other road situations with a lesser degree of effort given the normal physical conditions of the average bicyclist.
Bicyclists frequently encounter steep gradients and other road situations which can require exceptional physical strength to negotiate and which can be extremely difficult for cyclists who are not physically well trained. Such situations can over-burden the bicyclist""s muscles and cardiovascular system. In the experience of this inventor, there are a number of different applications which utilize auxiliary electrical motors added to a typical bicycle. For example, one such system affixes the electrical motor inside the wheel hub. This system requires that the electrical motor which is utilized be a small one, due to obvious space limitations. This, in turn, results in the motor providing a relatively low power level and a reduced static torque. It also results in an excessive weight burden on the wheel.
Another application known to this inventor affixes the electrical motor to the rear wheel axle of the bicycle. The electrical motor is utilized with a worm screw reduction gear which causes a considerable drop in efficiency under stress. Additionally, the motor and the batteries which are used in such an application create a considerable amount of weight on the bicycle""s rear axle. This tends to make the bicycle off-balance and renders any over-dimensioning of the bicycle chassis totally useless. Insofar as the bicycle chassis must carry out this difficult task, it results in further unbalancing of the bicycle""s manoeuverability.
Yet another application known to this inventor affixes the electrical motor between the bicycle""s pedals. In this fashion, the motor""s rotation axle is aligned generally perpendicularly to the bicycle pedals"" axle, with the 90xc2x0 return towards the transmission, by means of worm screws. This configuration makes it unfeasible for the motor to recover energy during braking of the bicycle. This is because the transmission""s worm screw decrease in revolutions allows the axle to effect a return rotation in a single direction only, i.e. from the motor to the wheel and not vice-versa. Additionally, the mounting of the motor in this fashion requires that only motors having a small circumference be used due to the problem posed by the limited space available. Such motors, in the experience of this inventor, have a very low torque and a low revolution rate.
Still another application known to this inventor affixes the motor with a direct hold on the wheel roller. In this fashion, the transmission roller is required to exercise great pressure on the bicycle""s tire, with resulting wearing down of the tire, and fairly high levels of wasted energy. Also encountered are problems related to clutch slippage such as where dust and water are present on the tire, a condition frequently encountered by bicyclists who travel on unpaved or wet roads.
It is, therefore, a principal object of this invention to provide a new, useful, and uncomplicated apparatus in the form of an assembly, or universal kit, which can be mounted to virtually any bicycle and which provides auxiliary electrical power to the bicyclist for reducing the need for exceptional physical strength on the part of the cyclist. It is another object to provide such an apparatus which utilizes the rate of pedal rotation and the pressure exerted by the cyclist on the bicycle pedals to actuate this auxiliary electrical power. It is yet another object of the present invention to provide such an apparatus which is discreet in appearance and does not interfere with the bicycle""s original aesthetics. It is still another object to provide such an apparatus which aids the cyclist in pedaling and which allows the cyclist to attain an autonomy of more than 35 kilometers or so which allows the cyclist to have a pleasant and serene bicycle ride. And it is yet another object of the present invention to provide such an apparatus which is easily assembled, which has a high level of efficiency in its use and which can be made such that its cost to the end user is relatively low.
The present invention has obtained these objects. It provides for a new, useful and uncomplicated assembly or kit which includes an electrical motor which is mountable to the pedal axle of a typical bicycle, the electric motor having permanent magnets, an electronic control for these motor magnets, batteries and a reduction gear based upon the motor""s number of revolutions per minute. The assembly also uses special sensors which register the pedal rotation rate and the pressure exerted by the bicyclist upon the pedals, which information is processed by a control device which controls actuation of the electric motor as such is required by the bicyclist. That is, the control notices how much current is being absorbed by the motor and reacts accordingly. For example, if the cyclist is riding slowly on level ground, the control reads this and sends very little energy to the motor as it is not needed. If, instead, the cyclist is on a steep incline, the number of rotations of the pedal may be the same as on level ground. However, the pressure exerted on the pedal by the cyclist is greater and the electronic control senses this additional pressure. Additional electric current is sent to the motor as more assistance is needed for the cyclist.
The assembly or kit of the present invention is also universal. That is, it can be easily affixed to any type of bicycle, regardless of whether it is presently in use or still remains to be built. The assembly or kit can be affixed to the gear box of the original pedals, with the electrical motor placed between the pedals and the rotation axle which allows the motor to have a larger circumference and, in turn, allows the device to achieve a considerable increase in low revolution torque. This lower number of revolutions is achieved by use of a chain reduction gear, both by the motor in relation to the return axle as well as in relation to the bicycle""s transmission rim. Use of the device does not alter the basis upon which any bicycle may be designed or built. That is, the device is fully functional notwithstanding the bicycle""s original cost, simplicity of construction or its level of efficiency. Furthermore, maintaining the bicycle""s original chain transmission system means that the cyclist can take advantage of the bicycle""s standard gear box ratio with a further gearing-down of the motor/wheel ratio.
A further advantage provided by the kit which is the subject of this invention is that it is functionally adapted to be attached to a single place on the bicycle. In this fashion, it can be made to oscillate and thus react, as previously alluded to, both to the pressure exerted on the pedals as well as to the counter-reaction of the rear wheel (by virtue of its resistant torque). This permits special sensors to interpret the situation to which the bicyclist finds himself or herself, namely, the type of start, the gradient, and the level area, thereby making the device take the appropriate action in real time by modulating the motor""s electrical current. Additionally, if the bicyclist wishes to increase his or her mileage autonomy, the cyclist can activate a pulley block by means of a magnetic friction on the return axle. This will enable the cyclist to recoup energy, both in braking as well as in climbing, insofar as the kinetic energy from the rear wheel to the motor will be transformed into electrical energy by the motor itself. This partially recharges the batteries, thus resulting in a decrease in the batteries"" electrical stress and a lengthening of their useful life. The foregoing and other features of the device of the present invention will be apparent from the detailed description which follows.

Universal kit for the application of an electric motor on a standard bicycle transforming same bicycle into a bicycle with pedal assist from the electric motor


A communication system provides integrated email, telephone and instant messenger communication including a common address book, a common log of communication history and shared presence information. A user can respond to a communication according to any format, email, telephone or instant messenger, with a response using the same format or any other format. The response may be initiated by a single command.

This application relates to communication and in particular relates to integration of existing communication formats in a manner that provides additional functionality to a user.
Various communication formats are commonly used for electronic communication. In particular, email and instant messenger formats are commonly used for communication through a personal computer (PC) or other device. Telephone communication is generally performed using a dedicated telephone device (desktop telephone, cell phone, or other device). In some cases Voice over Internet Protocol (VoIP) may allow telephone communication using a PC or similar device. VoIP may also use dedicated hardware such as a desktop IP phone or cell phone. Generally, some additional hardware is needed to use a PC in this way (e.g. an IP handset). Email, instant messenger and telephone communication, where they are provided on a single PC, are often provided by different applications. Such applications use different address books and maintain different communication logs. Thus, when communication between two or more people takes place using different communication formats, responding may require consulting the right address book and sometimes copying and pasting an address to another application, or even manually entering address information. When reviewing past correspondence, two or more different logs may need to be reviewed in order to see the full details of correspondence. Such logs may be reviewed entry-by-entry to determine the order in which individual communications occurred (e.g. from time stamp information). Separate communication formats generally require separate configuration. For example, a user may have an email account set up on an email server and separately have a telephone account set up on a telephone server. Thus, providing and maintaining multiple communications systems is inefficient and often inconvenient.

This patent is subject to a terminal disclaimer.

Systems and methods for providing unified collaboration systems with combined communication log


A liquid non-aqueous detergent is presented containing a nonionic surfactant, a builder, a bleaching agent, and a cationic stabilizer of formula I, II or III:

1. Field of the Invention
This invention relates to non-aqueous liquid detergents which contain nonionic surfactant(s), builder(s) and bleaching agent and which show increased stability of the bleaching agent. The present invention also relates to the use of special stabilizers for stabilizing bleaching agents in non-aqueous liquid detergents.
2. Discussion of Related Art
Liquid detergents are enjoying increasing popularity among consumers because they are easier to dose and generally dissolve better and faster. However, these advantages are offset by technical difficulties which have to be overcome in the production and storage of the detergents. Thus, it is almost impossible to incorporate a bleaching system in aqueous detergents because the bleaching agents steadily lose activity as a result of hydrolysis, so that the effectiveness of the detergents in removing bleachable soils is reduced. However, the incorporation of bleaching agents and bleach activators in non-aqueous liquid detergents is also problematical. Thus, even so-called xe2x80x9cwater-freexe2x80x9d detergents still contain small residues of water, which cause the hydrolysis problems mentioned above, or absorb these quantities of water during storage and use. In addition, the decomposition of bleaching agents is catalyzed by the presence of traces of heavy metals which can even be found in the non-aqueous solvents on which the xe2x80x9cwater-freexe2x80x9d detergents are based.
There are several proposed solutions in the prior art for increasing the stability of bleach-containing non-aqueous liquid detergents, these proposed solutions generally involving the use of certain stabilizers. Thus, EP 340 989 (Colgate), for example, describes the use of C5-21 fatty acids, fatty acid salts or fatty acid glyceryl monoesters or diesters as stabilizers in non-aqueous liquid detergents containing bleaching agent and bleach activator. The use of vicinal hydroxy compounds for this purpose is disclosed in EP 344 909 (Colgate).
WO 93/06201 (Henkel) describes a non-aqueous liquid or paste-form detergent containing 5 to 20% by weight of hydrated zeolite A, 50 to 80% by weight of anionic and/or nonionic surfactant, 5 to 20% by weight of bleaching agent, up to 6% by weight of bleach activator and up to 6% by weight of a complexing agent for heavy metals.
WO 96/10072 (Procter and Gamble) discloses a process for the production of non-aqueous bleach-containing liquid detergents which show high chemical and physical stability and produce excellent washing and bleaching results, characterized in that fine-particle detergent components are suspended in a non-aqueous liquid matrix of alcohol ethoxylates.
The use of other complexing agents and/or radical scavengers for stabilizing bleaching agents is widely described in the prior art.
However, the effect of the measures described in the prior art for stabilizing bleaching agents in non-aqueous liquid detergents is unsatisfactory. In the event of prolonged storage, the bleaching agents undergo decomposition, despite the use of the stabilizers mentioned, while the detergents lose washing power.
Now, the problem addressed by the present invention was to provide a stable bleach-containing liquid detergent which would contain the solid bleaching agents in the form of a stable dispersion. The bleaching agents would not undergo any loss of activity, even in the event of prolonged storage of the detergent.
The solution to this problem is characterized in that certain cationic compounds are incorporated as stabilizers in the non-aqueous liquid detergents.
Accordingly, the present invention relates to a non-aqueous liquid detergent containing nonionic surfactant(s), builder(s) and bleaching agent, characterized in that it contains as stabilizer one or more cationic compounds corresponding to formula I, II or III:
in which the groups R1 independently of one another are each selected from C1-6 alkyl, alkenyl or hydroxyalkyl groups, the groups R2 independently of one another are each selected from C8-28 alkyl or alkenyl groups, R3 has the same meaning as R1 or represents (CH2)nxe2x80x94Txe2x80x94R2, R4 has the same meaning as R1 or R2 or represents (CH2)nxe2x80x94Txe2x80x94R2, T represents xe2x80x94CH2xe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94 or xe2x80x94COxe2x80x94Oxe2x80x94 and n is an integer of 0 to 5.
The expression xe2x80x9cnon-aqueousxe2x80x9d in the context of the present invention is understood to apply to detergents which only contain small quantities of free water, i.e. water which is not bound as water of crystallization or in any other way. Since even non-aqueous solvents and raw materials (particularly those of technical quality) have certain water contents, entirely water-free compositions can only be produced with great difficulty and at high cost on an industrial scale. Accordingly, small quantities of free water of less than 5% by weight and preferably less than 2% by weight, based on the final detergent, are tolerable in the xe2x80x9cnon-aqueousxe2x80x9d detergents according to the present invention.
The liquid detergents according to the present invention can be produced within a broad viscosity range. Thus, it is possible to produce not only low viscosity, readily pumpable detergents according to the invention, but also high-viscosity or even paste-like detergents with relatively high viscosities. Paste-form detergents may even have a spreadable or cuttable consistency. Even in detergents such as these, the use of the cationic stabilizers leads to the bleach-stabilizing effects according to the present invention.
The cationic stabilizers may be introduced into the detergents according to the invention in varying quantities. The content of cationic stabilizers corresponding to the above formulae in the detergents according to the invention is normally from 0.5 to 10% by weight, preferably from 1 to 6% by weight and more preferably from 2 to 4% by weight.
Preferred cationic stabilizers are obtained by esterification of triethanolamine with long-chain fatty acids and subsequent quaternization. Both the esterification step and the quaternization step are carried out in known manner, dimethyl sulfate preferably being used as the quaternizing agent. Preferred detergents contain a quaternized triethanolamine ester as cationic stabilizer.
Other preferred cationic stabilizers are compounds which are derived from formula I above and in which the groups R1 independently of one another are each selected from methyl, ethyl and 2-hydroxyethyl groups; the groups R2 independently of one another are each selected from C8-28 alkyl or alkenyl groups, preferably from C10-20 alkyl or alkenyl groups and more preferably from C12-18 alkyl or alkenyl groups, T represents Oxe2x80x94COxe2x80x94 and n is the number 1, 2 or 3. Cationic stabilizers such as these are commercially available, for example, under the names of Stepantex(copyright) VA 90, Stepantex(copyright) VS 90 (trademarks of the Stepan Company) and Dehyquart(copyright) AU 46 and Dehyquart(copyright) AU 57 (trademarks of Henkel/Pulcra).
The cationic stabilizers to be used in accordance with the invention may be used either on their own or in combination with other stabilizers known from the prior art. The stabilizers described in the prior art can be divided into three large groups, namely: antioxidants, drying agents and complexing agents.
Suitable antioxidants are, for example, phenols, bisphenols and thiobisphenols substituted by sterically hindered groups. Other classes of antioxidants are aromatic amines, preferably secondary aromatic amines, and substituted p-phenylenediamines, phosphorus compounds containing trivalent phosphorus, such as phosphines, phosphites and phosphonites, compounds containing enediol groups, so-called reductones, such as ascorbic acid and derivatives thereof, organic sulfur compounds, such as the esters of 3,3xe2x80x2-thiodipropionic acid with C1-18 alkanols, more especially C10-18 alkanols, metal ion deactivators which are capable of complexing autoxidation-catalyzing metal ions, for example copper, such as EDTA, nitrilotriacetic acid etc. and mixtures thereof. A large number of examples of such antioxidants can be found in DE 196 16 570 (BASF AG)xe2x80x94the antioxidants mentioned there may readily be used in combination with the cationic stabilizers for the purposes of the present invention.
Drying agents which may be used in combination with cationic stabilizers in accordance with the present invention are, for example, inorganic salts which are capable of hydrate formation and which thus bind free water. Water-free magnesium and sodium sulfate are mentioned as examples. Overdried silicates and aluminium silicates, such as aerogels for example, and overdried zeolites also belong to this class of compounds. Organic drying agents may of course also be used, examples of such drying agents being substances which swell by taking up water, but which do not release the water taken up under the conditions prevailing in the non-aqueous liquid detergent. This class includes, for example, cellulose and starch and derivatives thereof, such as carboxymethyl cellulose and carboxymethyl starch, hydroxypropyl cellulose and hydroxypropyl starch, etc.
The group of complexing agents includes, for example, the alkali metal salts of ethylenediamine tetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes, such as polyacrylates, polymaleates and polysulfonates. Low molecular weight hydroxycarboxylic acids, such as citric acid, tartaric acid, malic acid or gluconic acid and salts thereof are also suitable. Suitable complexing agents may also be selected from organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri(methylene phosphonic acid) (ATMP), diethylenetriamine penta(methylene-phosphonic acid) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM). These complexing agents may be introduced into the detergents according to the invention in quantities of, for example, 0.1 to 5% by weight and preferably in quantities of around 1% by weight.
The detergents according to the invention contain one or more nonionic surfactant(s) as a crucial ingredient. Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, more especially primary alcohols preferably containing 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or, preferably, methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the form of the mixtures typically present in oxoalcohol radicals. However, alcohol ethoxylates containing linear radicals of alcohols of native origin with 12 to 18 carbon atoms, for example coconut oil, palm oil, tallow fatty or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C12-14 alcohols containing 3 EO or 4 EO, C9-11 alcohol containing 7 EO, C13-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C12-18 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C12-14 alcohol containing 3 EO and C12-18 alcohol containing 5 EO. The degrees of ethoxylation mentioned represent statistical mean values which, for a special product, can be a whole number or a broken number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO may also be used, examples including tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO.
Other nonionic surfactants suitable for use in accordance with the invention are alkyl glycosides corresponding to the general formula RO(G)x, where R is a primary linear or methyl-branched, more especially 2-methyl-branched, aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G is a glycose unit containing 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is a number of 1 to 10, preferred values for x being 1.2 to 1.4.
Another class of preferred nonionic surfactants which may be used either as sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably containing 1 to 4 carbon atoms in the alkyl chain, more especially the fatty acid methyl esters which are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in International patent application WO-A-90/13533.
Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethyl-amine oxide, and the fatty acid alkanolamide type are also suitable. The quantity in which these nonionic surfactants are used is preferably no more than the quantity in which the ethoxylated fatty alcohols are used and, more particularly, no more than half that quantity.
Other suitable surfactants are polyhydroxyfatty acid amides corresponding to formula (IV):
in which RCO is an aliphatic acyl group containing 6 to 22 carbon atoms, R5 is hydrogen, an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group containing 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid amides are known substances which may normally be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
The group of polyhydroxyfatty acid amides also includes compounds corresponding to formula (V):
in which R is a linear or branched alkyl or alkenyl group containing 7 to 12 carbon atoms, R6 is a linear, branched or cyclic alkyl group or an aryl group containing 2 to 8 carbon atoms and R7 is a linear, branched or cyclic alkyl group or an aryl group or an oxyalkyl group containing 1 to 8 carbon atoms, C1-4 alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxy-alkyl group, of which the alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of that group.
[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds may then be converted into the required polyhydroxyfatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst, for example in accordance with the teaching of International patent application WO-A-95/07331.
According to the invention, preferred non-aqueous liquid detergents are those which contain 5 to 70% by weight, preferably 15 to 65% by weight and more preferably 20 to 60% by weight of one or more nonionic surfactants from the group of alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, alcohols and/or carboxylic acids containing 8 to 28, preferably 10 to 20 and more preferably 12 to 18 carbon atoms.
In addition to the nonionic surfactants, the detergents according to the invention may contain anionic surfactants. Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C9-13 alkyl benzenesulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxy-alkane sulfonates, and the disulfonates obtained, for example, from C12-18 monoolefins with an internal or terminal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Other suitable surfactants of the sulfonate type are the alkane sulfonates obtained from C12-18 alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of xcex1-sulfofatty acids (ester sulfonates), for example the xcex1-sulfonated methyl esters of hydrogenated coconut oil, palm kernel oil or tallow fatty acids, are also suitable.
Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters in the context of the present invention are the monoesters, diesters and triesters and mixtures thereof which are obtained where production is carried out by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
Preferred alk(en)yl sulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid semiesters of C12-18 fatty alcohols, for example cocofatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C10-20 oxoalcohols and the corresponding semiesters of secondary alcohols with the same chain length. Other preferred alk(en)yl sulfates are those with the chain length mentioned which contain a synthetic, linear alkyl chain based on a petrochemical and which are similar in their degradation behavior to the corresponding compounds based on oleochemical raw materials. C12-16 alkyl sulfates, C12-15 alkyl sulfates and C14-15 alkyl sulfates are preferred from the point of view of washing technology. Other suitable anionic surfactants are 2,3-alkyl sulfates which may be produced, for example, in accordance with U.S. Pat. No. 3,234,258 or U.S. Pat. No. 5,075,041 and which are commercially obtainable as products of the Shell Oil Company under the name of DAN(copyright).
The sulfuric acid monoesters of linear or branched C7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-11 alcohols containing on average 3.5 moles of ethylene oxide (EO) or C12-18 fatty alcohols containing 1 to 4 EO, are also suitable. In view of their high foaming capacity, they are only used in relatively small quantities, for example in quantifies of 1 to 5% by weight, in detergents.
Other preferred anionic surfactants are the salts of alkyl sulfosuccinic acid which are also known as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and, more particularly, ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols which, considered in isolation, represent nonionic surfactants (for a description, see below). Of these sulfosuccinates, those of which the fatty alcohol residues are derived from narrow-range ethoxylated fatty alcohols are particularly preferred. Alk(en)yl succinic acid preferably containing 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof may also be used.
Other suitable anionic surfactants are, in particular, soaps. Suitable soaps are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and soap mixtures derived in particular from natural fatty acids, for example coconut oil, palm kernel oil or tallow fatty acids.
The anionic surfactants, including the soaps, may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts and, more preferably, in the form of their sodium salts.
Preferred liquid detergents additionally contain anionic surfactants, preferably from the group of alkyl sulfates, alkyl sulfonates, alkyl benzenesulfonates and fatty acid soaps.
Besides surfactants and the cationic stabilizer, the non-aqueous liquid detergents according to the invention contain builders. Any of the builders normally used in detergents may be introduced into the press-agglomerated detergents, including in particular zeolites, silicates, carbonates, organic co-builders and alsoxe2x80x94providing there are no ecological objections to their usexe2x80x94phosphates.
Suitable crystalline layer-form sodium silicates correspond to the general formula Na2MSixO2x+1. y H2O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4. Crystalline layer silicates such as these are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. Both xcex2- and xcex4-sodium disilicates Na2Si2O5. y H2O are particularly preferred, xcex2-sodium disilicate being obtainable, for example, by the process described in International patent application WO-A-91/08171.
Other useful builders are amorphous sodium silicates with a modulus (Na2O:SiO2 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash cycle properties. The delay in dissolution in relation to conventional amorphous sodium silicates can have been obtained in various ways, for example by surface treatment, compounding, compacting or by overdrying. In the context of the invention, the term xe2x80x9camorphousxe2x80x9d is also understood to encompass xe2x80x9cX-ray amorphousxe2x80x9d. In other words, the silicates do not produce any of the sharp X-ray reflexes typical of crystalline substances in X-ray diffraction experiments, but at best one or more maxima of the scattered X-radiation which have a width of several degrees of the diffraction angle. However, particularly good builder properties may even be achieved where the silicate particles produce crooked or even sharp diffraction maxima in electron diffraction experiments. This may be interpreted to mean that the products have microcrystalline regions between 10 and a few hundred nm in size, values of up to at most 50 nm and, more particularly, up to at most 20 nm being preferred. So-called X-ray amorphous silicates such as these, which also dissolve with delay in relation to conventional waterglasses, are described for example in German patent application DE-A-44 00 024. Compacted amorphous silicates, compounded amorphous silicates and overdried X-ray-amorphous silicates are particularly preferred.
The finely crystalline, synthetic zeolite containing combined water used in accordance with the invention is preferably zeolite A and/or zeolite P. Zeolite MAP(copyright) (Crosfield) is a particularly preferred P-type zeolite. However, zeolite X and mixtures of A, X and/or P are also suitable. According to the invention, it is also possible to use, for example, a commercially obtainable co-crystallizate of zeolite X and zeolite A (ca. 80% by weight zeolite X) which is marketed by CONDEA Augusta S.p.A. under the name of VEGOGOND AX(copyright) and which may be described by the following formula:
nNa2O (1xe2x88x92n)K2Oxc2x7Al2O3xc2x7(2-2.5)SiO2xc2x7(3.5-5.5) H2O
Suitable zeolites have a mean particle size of less than 10 xcexcm (volume distribution, as measured by the Coulter Counter Method) and contain preferably 18 to 22% by weight and more preferably 20 to 22% by weight of combined water. The zeolites may also be used as overdried zeolites with relatively low water contents and are then suitable by virtue of their hygroscopicity for removing unwanted residual traces of free water.
The generally known phosphates may of course also be used as builders providing their use should not be avoided on ecological grounds. The sodium salts of the orthophosphates, the pyrophosphates and, in particular, the tripolyphosphates are particularly suitable.
Useful organic builders are, for example, the polycarboxylic acids usable, for example, in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, amino-carboxylic acids, nitrilotriacetic acid (NTA), providing their use is not ecologically unsafe, and mixtures thereof. Preferred salts are the salts of the polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof, sodium citrate being particularly preferred.
The builder content of the detergents according to the invention is normally from 1 to 30% by weight and preferably from 10 to 25% by weight. Preferred non-aqueous liquid detergents contain water-soluble builders, preferably from the group of oligo- and polycarboxylates, carbonates and crystalline and/or amorphous silicates, as builders. Among these compounds, the salts of citric acid have proved to be particularly suitable, the alkali metal salts being preferred and the sodium salts particularly preferred.
The non-aqueous liquid detergents according to the invention contain one or more bleaching agents. Among the compounds yielding H2O2 in water which serve as bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecane dioic acid. The content of bleaching agents in the detergents according to the invention is normally above 10% by weight, preferably between 15 to 35% by weight and more preferably between 20 and 30% by weight, based on the detergent as a whole.
In addition to the ingredients mentioned above, the detergents according to the invention may contain other detergent ingredients, for example from the group of bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescing agents, dyes, foam inhibitors, silicone oils, redeposition inhibitors, optical brighteners, discoloration inhibitors, dye transfer inhibitors and corrosion inhibitors.
In order to obtain an improved bleaching effect where washing is carried out at temperatures of 60xc2x0 C. or lower, bleach activators may be incorporated in the detergents according to the invention. The bleach activators may be compounds which form aliphatic peroxocarboxylic acids containing preferably 1 to 10 carbon atoms and more preferably 2 to 4 carbon atoms and/or optionally substituted perbenzoic acid under perhydrolysis conditions. Substances bearing O- and/or N-acyl groups with the number of carbon atoms mentioned and/or optionally substituted benzoyl groups are suitable. Preferred bleach activators are polyacylated alkylenediamines, more particularly tetraacetyl ethylenediamine (TAED), acylated triazine derivatives, more particularly 1,5-diacetyl-2,4-dioxohexa-hydro-1,3,5-triazine (DADHT), acylated glycolurils, more particularly tetraacetyl glycoluril (TAGU), N-acylimides, more particularly N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride, acylated polyhydric alcohols, more particularly triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
In addition to or instead of the conventional bleach activators mentioned above, so-called bleach catalysts may also be incorporated in the detergents according to the invention. Bleach catalysts are bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt-, iron-, copper- and ruthenium-amine complexes may also be used as bleach catalysts.
The content of bleach activators or bleach catalysts in the detergents according to the invention may be between 1 and 15% by weight and is preferably between 2 and 12% by weight and more preferably between 5 and 10% by weight.
Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus, are particularly suitable. Proteases of the subtilisin type are preferred, proteases obtained from Bacillus lentus being particularly preferred. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or of protease, lipase and cellulase, but especially cellulase-containing mixtures, are of particular interest. Peroxidases or oxidases have also proved to be suitable in some cases. The enzymes may be adsorbed to supports and/or encapsulated in shell-forming substances to protect them against premature decomposition. The percentage content of the enzymes, enzyme mixtures or enzyme granules in the detergents according to the invention may be, for example, from about 0.1 to 10% by weight and is preferably from 0.5 to about 5% by weight.
In addition, the detergents according to the invention may also contain components with a positive effect on the removability of oil and fats from textiles by washing (so-called soil repellents). This effect becomes particularly clear when a textile which has already been repeatedly washed with a detergent according to the invention containing this oil- and fat-dissolving component is soiled. Preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers, such as methyl cellulose and methyl hydroxypropyl cellulose containing 15 to 30% by weight of methoxyl groups and 1 to 15% by weight of hydroxypropoxyl groups, based on the nonionic cellulose ether, and the polymers of phthalic acid and/or terephthalic acid known from the prior art or derivatives thereof, more particularly polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
The non-aqueous detergents may contain derivatives of diaminostilbenzenedisulfonic acid or alkali metal salts thereof as optical brighteners. Suitable optical brighteners are, for example, salts of 4,4xe2x80x2-bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)-stilbene-2,2xe2x80x2-disulfonic acid or compounds of similar composition which contain a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted diphenyl styryl type, for example alkali metal salts of 4,4xe2x80x2-bis-(2-sulfostyryl)-diphenyl, 4,4xe2x80x2-bis-(4-chloro-3-sulfostyryl)-diphenyl or 4-(4-chlorostyryl)4xe2x80x2-(2-sulfostyryl)-diphenyl, may also be present. Mixtures of the brighteners mentioned above may also be used.
Dyes and fragrances are added to the detergents according to the invention to improve the aesthetic impression created by the products and to provide the consumer not only with the required washing performance but also with a visually and sensorially xe2x80x9ctypical and unmistakablexe2x80x9d product. Suitable perfume oils or fragrances include individual fragrance compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.butyl cyclohexyl acetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, xcex1-isomethyl ionone and methyl cedryl ketone; the alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenyl ethyl alcohol and terpineol and the hydrocarbons include, above all, the terpenes, such as limonene and pinene. However, mixtures of various fragrances which together produce an attractive fragrance note are preferably used. Perfume oils such as these may also contain natural fragrance mixtures obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are clary oil, camomile oil, nettle oil, melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
The fragrances may be directly incorporated in the detergents according to the invention, although it can also be of advantage to apply the fragrances to supports which strengthen the adherence of the perfume to the washing and which provide the textiles with a long-lasting fragrance through a slower release of the perfume. Suitable support materials are, for example, cyclodextrins, the cyclodextrin/perfume complexes optionally being coated with other auxiliaries.
In order to improve their aesthetic impression, the detergents according to the invention may be colored with suitable dyes. Preferred dyes, which are not difficult for the expert to choose, have high stability in. storage, are not affected by the other ingredients of the detergents or by light and do not have any pronounced substantivity for textile fibers so as not to color them.
As already mentioned, the non-aqueous liquid detergents according to the invention may be adapted in their viscosity to meet the particular requirements of different applications. Thus, it is possible to formulate low-viscosity and readily pumpable detergents and also to produce more viscous to paste-form detergents which are known commercially as gels. Detergents which do not flow under the influence of gravity, i.e. cannot be poured and have a spreadable or cuttable consistency, can also readily be produced in accordance with the present invention. The viscosity of the detergents for a number of applications is normally in the range from 500 to 50,000 mPas, preferably in the range from 1,000 to 10,000 mPas and more preferably in the range from 3,000 to 5,000 mPas (T=70xc2x0 C., shear rate 100 sxe2x88x921). For applications requiring a non-pourable consistency (for example detergent pastes for automatic dispensers in institutional dishwashing machines), a considerably higher viscosity may be appropriate, which can lead as far as dimensionally stable compounds that no longer have a viscosity in the above sense.
The detergents according to the invention are produced in known manner by mixing the ingredients in stirred tanks. If required for a given end product, the solids present in the detergents according to the invention can be further size-reduced by a wet grinding step in order further to increase the separation stability of the detergents. Operations such as these, which are familiar to the expert, may be carried out for example in colloid mills, roller mills or annular-gap or stirred ball mills.
The cationic stabilizers to be used in accordance with the invention may be added at any stage of such a routine production process. For example, the bleaching agent may be coated with the cationic stabilizers and the resulting coated particles of bleaching agent may be added to the other ingredients in a stirred tank which, of course, may again be followed by a grinding mill. The cationic stabilizers may also readily be added as a solid or paste-form pure substance or as a solution both before and after a grinding step. The bleaching agent and bleach activators are normally not incorporated in the detergent together before the grinding step because the intimate contact which the materials undergo during grinding can promote decomposition. If the bleach activators are added after a grinding step, the cationic stabilizers may be added in this stirring and homogenizing step. It is of course also possible to coat the bleach activators with the cationic stabilizers.
The present invention also relates to the use of cationic stabilizers corresponding to formula I, II or III:
in which the groups R1 independently of one another are each selected from C1 6 alkyl, alkenyl or hydroxyalkyl groups, the groups R2 independently of one another are each selected from C8-28 alkyl or alkenyl groups, R3 has the same meaning as R1 or represents (CH2)nxe2x80x94Txe2x80x94R2, R4 has the same meaning as R1 or R2 or represents (CH2)nxe2x80x94Txe2x80x94R2, T represents xe2x80x94CH2xe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94 or xe2x80x94COxe2x80x94Oxe2x80x94 and n is an integer of 0 to 5, for stabilizing bleaching agents in non-aqueous detergents. The use of the compounds mentioned leads to liquid detergents which show increased stability of the bleaching agent and which retain this property over long periods of storage.

Non-aqueous bleach-containing liquid detergents

Abstract: where the groups R1 independently of one another are C1-6 alkyl, alkenyl or hydroxyalkyl groups, the groups R2 independently of one another are C8-28 alkyl or alkenyl groups, R3 has the same meaning as R1 or represents (CH2)nxe2x80x94Txe2x80x94R2, R4 has the same meaning as R1 or R2 or represents (CH2)nxe2x80x94Txe2x80x94R2, T represents xe2x80x94CH2xe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94 or xe2x80x94COxe2x80x94Oxe2x80x94 and n is an integer of from 0 to 5. The solid bleaching agents in the stabilized non-aqueous liquid detergent retain their activity after prolonged storage.


A cable assembly includes a sleeve body of plastic material; a protective tube extending in the sleeve body; a cable element disposed within the protective tube; and a transverse port provided in the wall of the protective tube. The plastic material extends through the transverse port into the protective tube and cross-sectionally seals the protective tube water tight in a region of the transverse port.

This application claims the priority of German Patent Application Serial No. 199 58 431.1, filed on Dec. 3, 1999, the subject matter of which is incorporated herein by reference.
The present invention relates to a cable assembly and a method of making the same.
For the production of cable assemblies or cable harnesses, a plurality of elongated cable elements, such as electrical and optical strands, are normally laid out along a desired path and plastic material is then foamed, poured or sprayed around them. Following the cooling and hardening of the plastic material, the cable elements are combined as bundles following a predetermined path inside a hardened plastic sleeve body and are secured in this way. During the manufacture of the sleeve body or the outer sleeve shell the thermally sensitive cable elements, such as optical wave guides, can be damaged by the hot plastic material and excessively high temperatures. Furthermore, the bundling and/or predetermined specific layout of the respective cable element involves the danger that mechanically sensitive cable elements are subjected to an excessively high lateral pressure or are excessively bent or kinked, thus subjecting them to an impermissibly high mechanical stress.
A design using a molded plug to render a cable assembly longitudinally watertight is disclosed in German Offenlegungsschrift (application published without examination) No. 37 42 731, while a method of guiding conductors through a cable assembly within a protective tube is known from published British Application No. 21 81 605.
It is an object of the invention to provide an improved arrangement for producing cable assemblies easily and in a more reliable manner.
This object is achieved according to the invention with a cable assembly of the aforementioned type in that the cable assembly comprises at least one protective tube which accommodates at least one cable element to protect it against thermal and/or mechanical stresses. The protective tube is furthermore provided with at least one transverse port on the inside tube wall. Plastic material used for the sleeve body flows during manufacture through the transverse port from the outside to the inside, such that the protective tube is filled watertight in the longitudinal direction in the region where the material flows in.
By providing at least one protective tube inside the plastic material of the sleeve body for the mechanically and/or thermally sensitive cable elements, such as optical wave guides, it is ensured that such sensitive cable elements are protected against excess thermal and/or mechanical stresses. The protective tube therefore provides a thermal barrier or screen for the cable elements it surrounds during the production of the sleeve body by virtue of pouring on or foaming on the plastic material. Thus, the cable element inside the protective tube is not directly subjected to the hot plastic material used for producing the sleeve body. The protective tube at the same time represents a mechanically reinforced passage inside the plastic material of the sleeve body, which provides additional mechanical protection for the cable assembly against bending stresses. Furthermore, if two groups of different thermally and/or mechanically sensitive cable elements are to be combined by a cable assembly, the protective tube makes it possible to accommodate the more sensitive cable elements inside the protective tube and thus separate them from the thermally and/or mechanically less sensitive cable elements. In addition, the protective tube ensures to a high degree that lateral pressure forces, that may be due to the bundling of several cable elements or the clamping of the beginning and the end of the bundle to direct the cable elements onto a desired path, can substantially be kept away from the cable elements inside the protective tube.
Liquid plastic material can penetrate into the protective tube during the production of the sleeve body since at least one transverse port is provided in the wall of at least one longitudinal section of the protective tube. The protective tube is therefore cross-sectionally filled so as to be substantially watertight in the longitudinal direction in the region of the transverse port. The protective tube is thus longitudinally sealed at the same time as the sleeve body is produced and as part of the same step. Thus, no additional operation is needed for providing a longitudinal watertight seal for the protective tube.
A further feature of the invention provides that the transverse port inside the protective tube is advantageously dimensioned such that the protective tube is filled with the inflowing plastic material so as to render it watertight, but only over a partial tube length. Thus, first, there is effected a targeted metering of the plastic material into the protective tube, so that the amount of the inflowing plastic material is sufficient to ensure a tight longitudinal sealing of the protective tube. Second, the flow of hot plastic material is simultaneously regulated to allow only enough plastic material to enter the protective tube to ensure that an excess thermal stressing of the sensitive cable elements inserted therein is substantially avoided. The protective tube therefore is not filled along the entire tube length with the plastic material, but only locally, along a partial section of its total length.

Cable assembly and method of making the same


A condensation polymer, obtained through reaction of an alkanolamide and a cyclic anhydride to form a hydroxyalkylamide, followed by polycondensation of the hydroxyalkylamide, has at least two carboxylic acid end groups connected to an alkylamide groups via an ester linkage. The polymers may be used in powder paint compositions.

The invention relates to a condensation polymer having at least one carboxylic acid endgroup connected to an alkylamide group via an ester linkage.
Preferably, the polymer contains at least two groups according to formula (I):
in which
H, (C1-C20)(cyclo)alkyl,
or (C6-C10)aryl,
B=(C2-C24), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical,
R1, R2, R3, R4, R5 and R6 may, independently of one another, be the same or different, H, (C6-C10)aryl or (C1-C8)(cyclo)alkyl radical and
n=1-4.
More preferably the polymer contains at least two groups according to formula (II):
in which
H, (C1-C20)(cyclo)alkyl,
or (C6-C10)aryl,
B=(C2-C24), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical, and
R1, R2, R3, R4, R5 and R6 may, independently of one another, be the same or different, H, (C6-C10)aryl or (C1-C8)(cyclo)alkyl radical.
According to another preferred embodiment, the polymer containing hydroxyalkylamide groups is a polymer according to formula (III):
in which:
H, (C1-C20)(cyclo)alkyl or
(C6-C10)aryl
A=OH,
B=(C2-C24), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical,
R1, R2, R3, R4, R5 and R6 may, independently of one another, be the same or different, H, (C6-C10)aryl or (C1-C8)(cyclo)alkyl radical or CH2xe2x80x94OX2.
In formulas (I), (II) and (IlI) R groups may together or with neighbouring carbon atoms form part of a cycloalkyl group.
According to another preferred embodiment of the invention, the polymer containing xcex2-esteralkylamide-acid groups is a polymer according to formula (IV):
in which:
H, (C1-C20)(cyclo)alkyl or
(C6-C10)aryl,
B=(C2-C24), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical,
R3=H or (C6-C10)aryl or (C1-C8)alkyl radical and
R6=H or (C6-C10)aryl or (C1-C8)alkyl radical.
The weight average molecular mass of the polymer according to the invention generally ranges between 500 and 50,000, and is preferably between 600 g/mol and 10,000 g/mol.
The number average molecular mass may range between 400 and 10,000 and is preferably between 500 and 2000.
The esteralkylamide-acid functionality may range between 2 and 250 and is preferably between 3 and 50.
The functionality is the average number of reactive groups of the specific type per molecule in the polymer composition.
According to another preferred embodiment of the invention the polymer""s carboxyl group functionality of the polymer is xe2x89xa73 and the polymer containing esteramide acid groups is a polymer represented by formula (V):
in which:
B=(C2-C12), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical,
R3=H or (C6-C10)aryl or (C1-C8)(cyclo)alkyl radical and
R6=H or (C6-C10)aryl or (C1-C8)(cyclo)alkyl radical
Preferably R3 and R6 are (C1-C4)alkyl.
According to another preferred embodiment of the invention R3 and R6 are methyl or ethyl.
B may be saturated or unsaturated.
B may be substituted with, for example, a (C1-C26)alkyl group, which may be saturated or unsaturated; or with a carboxylic acid.
B may be for example a (methyl)-1,2-ethylene, octenyl- or dodecenyl-1,2-ethylene, (methyl-)1,2-ethylidene, 1,3-propylene, (methyl-)1,2-cyclohexyl, 4-carboxyl-1,2-phenylene, (methyl-)1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,3-norbornyl, 2,3-norbornen-5-yl and/or (methyl-)1,2 cyclohex-4-enyl radical.
Depending on the starting monomers chosen, the variables B, R1, R2, R3, R4, R5 and R6 in the molecule or mixture of molecules can be selected to be the same or different per variable.
The polymer composition according to the invention may be a composition comprising higher and lower oligomers, which usually contains less than 50 wt. %, preferably less than 30 wt. %, of oligomers having a molecular weight smaller than 400.
The polymer according to the invention may, for example, be obtained through polycondensation of an hydroxyalkylamide-acid and an esteralkylamide diacid derived from an alkanolamine.
The hydroxyalkylamide-acid of an alkanolamine may have the formula (VI):
and the esteralkylamidediacid of an alkanolamine generally can be represented by formula (VII):
wherein
R1, R2, R3 and R4 may, independently of one another, be the same or different, H, (C6-C10)aryl or (C1-C8)(cyclo)alkyl radical and
Consequently a lineair polymer according to the invention generally comprises the amide and the ester groups alternating along the chain as follows:
E-A-E-A-E-E-A-E-A-E
wherein one or more diesters are coupled with alternating ester (E)xe2x80x94amide (A) groups or
E-A-E-A-E-A-E-A-E
wherein ester and amide groups are perfectly alternating throughout the polymer.
A branched polymer according to the invention generally comprises the amide and the ester groups alternating along the main and side chains as follows:
wherein one or more diestersare coupled with alternating ester (E)xe2x80x94amide (A) groups or
wherein ester and amide groups are perfectly alternating through the polymer.
Generally, the molar amount of amide bonds in the chain is lower than the amount of ester bonds.
The polymer according to the invention comprises at least 60% by weight of the products represented by the formulas (III)-(V).
According to a preferred embodiment of the invention the polymer is obtained in a one-step procedure by reacting an alkanolamine and a molar excess of cyclic anhydride, at a temperature between, for example, about 20xc2x0 C. and about 100xc2x0 C., to form a hydroxyalkylamide, after which, at a temperature between, for example, 120xc2x0 C. and 250xc2x0 C., a polyesteramide is obtained through polycondensation. Optionally water may be removed through distillation.
The removal of water through distillation may take place at a pressure higher than 1 bar, in a vacuum or azeotropically.
The reaction may take place without a solvent, but it is also possible that the reaction takes place in water or in an organic solvent.
Preferably, the cyclic anhydride is an anhydride according to formula (VIII):
in which B has the meaning specified above.
Examples of suitable cyclic anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, naphtalenic dicarboxylic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornene-2,3-dicarboxylic anhydride, naphtalenic dicarboxylic anhydride, 2-dodecene-1-yl-succinic anhydride, maleic anhydride, trimellitic anhydride, (methyl, octyl or dodecenyl)succinic anhydride, glutaric anhydride, 4-methylphthalic anhydride, 4-methylhexahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride and the maleinised alkylester of an unsaturated fatty acid.
Preferably the alkanol is an alkanolamine according to formula (IX):
in which:
or (C1-C20)(cyclo)alkyl,
R1, R2, R3, R4, R5 and R6 may, independently of one another, be the same or different, H, (C6-C10)aryl or (C1-C8)(cyclo)alkyl radical or CH2OH and n=1-4.
More preferably n=1.
The alkanolamine may be a monoalkanolamine, a dialkanolamine, a trialkanolamine or a mixture hereof.
If monoalkanolamines are used in one of the possible polymer syntheses, linear polymers with a functionality of 2 can be obtained. Depending on the application desired, a linear or an entirely or partly branched polymer can be selected, in which case the degree of branching can be set via the alkanolamines chosen.
If a highly branched structure with a high functionality is desired, di- or trialkanolamines can be used, also carboxylic acid substituted anhydrides in combination with monoalkanolamines can be used as a starting compound.
Examples of suitable mono-xcex2-alkanolamines include ethanolamine, 1-(m)ethyl ethanolamine, n-butyl ethanolamine, 1-(m)ethyl isopropanolamine, isobutanolamine, xcex2-cyclohexanolamine, n-butyl isopropanolamine and n-propanolamine.
Examples of suitable di-xcex2-alkanolamines are 3-amino-1,2-propanediol, 2-amino-1,3-propanediol diisobutanolamine (bis-2-hydroxy-1-butyl)amine), di-xcex2-cyclohexanolamine and diisopropanolamine (bis-2-hydroxy-1-propyl)amine).
A suitable trialkanolamine is, for example, tris(hydroxymethyl)aminomethane.
Preferably a xcex2-alkyl-substituted xcex2-hydroxyalkylamide is used. Suitable examples include (di)isopropanolamine, cyclohexyl isopropanolamine, 1-(m)ethyl isopropanolamine, (di)isobutanolamine, di-xcex2-cyclohexanolamine and/or n-butyl isopropanolamine.
These polymer compositions show an improved resistance to hydrolysis.
Most preferable diisopropanolamine and/or diisobutanolamine are applied.
The anhydride:alkanolamine equivalent ratio is generally between 2.0:1.0 and 3.0:1.0. Preferably, this ratio is between 2,1:1.0 and 2,8:1.0.
The compound according to the invention may also be obtained via a reaction between an alkanolamine, as for example described above, and a molar excess of a compound containing one acid group and one activated acid group after which a polyesteramide is obtained through polycondensation. The ratio may be between for example 2.0;1.0 and 3.0:1.0.
The compound containing an acid group and an activated acid group is preferably a compound according to formula (X):
in which
B has the meaning specified above and
in which R7 is a (C1-C12) branched or linear alkyl group.
Examples of suitable compounds containing one acid group and one activated acid group are alkyl esters, such as, for example, mono(m)ethyl adipate and mono(m)ethyl sebacate, anhydrides and thioesters.
The compound according to the invention may also be obtained via a reaction between a cyclic anhydride, as for example described above, and an alcohol, after which the obtained reaction product reacts in situ with an alkanolamine. A polyesteramide may be subsequently obtained through polycondensation.
Examples of suitable alcohols are (C1-C10) alcohols.
Preferably, methanol or ethanol is used.
In addition to carboxyl groups, the polymer may also contain hydroxyalkylamide groups, in amounts of between 0.01 and 2.0 mg equivalent/gram of polymer. The number of hydroxyalkylamide present in the polymer can be controlled via the anhydride/alkanolamine ratio and via the degree of conversion. If an anhydride excess is used and the polycondensationreaction is (almost) complete, less than 0.2 mg equivalent OH/gram of polymer is usually present. If hydroxyalkylamide groups are present, they may in a subsequent step react with compounds containing one or more groups that can react with xcex2-hydroxyalkylamide, such as for example anhydrides, carboxylic chlorides, activated esters or carboxylic acid groups. The amount of hydroxyalkylamide is preferably as low as possible, for example between 0.01 and 0.2 mg equivalent/gram of polymer.
The degree of branching and the functionality of the polymer are dependent on the starting materials and the molecular weight of the polymer. A molecular weight higher than 3000 and the use of di- and/or trialkanolamines generally lead to highly branched structures with a functionality of xe2x89xa76.
Due to the presence in amounts of less than 10% by weight (of the total amount of anhydrides) of bis- and dianhydrides instead of the anhydrides according to formula (VIII) it is possible that the polymer does not comprise only products according to formulas (III)-(V).
The invention also relates to entirely or partly modified polymers.
The modification may, for example, take place via a reaction between the polymer according to any one of formulas (III), (IV) or (V) with a monomer, oligomer or polymer containing reactive groups that can react with the carboxylic acid groups. Depending on the reaction components a catalyst can be selected.
Examples of suitable reactive groups include alcohol groups, oxazoline groups, alkyl halide groups, epoxy groups, strained ring olephinic groups, epoxychlorohydrine groups, amine groups, 1,2-diene groups, for example butadiene, and combinations hereof.
Preferably the monomer, oligomer or polymer contains only one group that can react with hydroxylalkylamide, as a result of which no crosslinking takes place during the modification.
The polymer according to formula (III), (IV) or (V) has preferably been modified with a compound containing an epoxy group, oxazolidine group, strained ring olephinic group or alcohol group. Synthesis of the modified polymer can take place in a two-step process or in a one step process.
The two-step process comprises in a first step the preparation of the condensation polymer having carboxylic acid end groups and in a second step the modification reaction.
In the one step process the starting materials are polycondensed and reacted simultaneously. Preferably, the one-step procedure is applied because the viscosity is lower in the overall process and hence the processability of the product is improved.
A modified polymer can for example be represented by one of the formulas (III), (IV) or (V) in which
in whichxe2x80x94Oxe2x80x94Z is derived from a monomeric, oligomeric or polymeric alcohol.
Suitable expoxides are, for example, saturated aliphatic (C1-C26) epoxides and esters or ethers derived from glycidol.
Examples of suitable aliphatic epoxides are ethylene oxide, propylene oxide, 1,2-epoxy butane, 1,2-epoxy octane, 1,2-epoxydodecane, 1,2-epoxy cyclohexane and 4-vinyl-1,2 epoxy cyclohexane.
Examples of suitable glycidic esters and ethers are allylglycidylether, benzyl glycidylether, glycidyl acrylate, glycidyl methacrylate and glycidyl versatate (Cardura E(trademark), Shell Chemicals).
Suitable oxazolines are, for example, saturated or unsaturated aliphatic (C3-C29) oxazolines derived from (C1-C26) aliphatic or (C7-C20) aromatic carboxylic acids, and ethanolamine or isopropanolamine, such as 2-(m)ethyloxazolidine, fatty acid (soy bean, tall, palmitic sunflower) oxazolidines, 2-phenyloxazoline and 2-vinyloxazolidine.
Suitable alcohols are, for example, linear or banched (C1-C26) (cyclo)aliphatic alcohols.
Examples of suitable linear aliphatic alcohols include (m)ethanol, butanol, (do)decanol, octanol and fatty acid alcohols, 2-ethylhexanol, 2,5,7-octatrienol and 1-vinyl-hexa-3,5-dienol.
Examples of suitable strained ring olephinic group containing compounds are dicyclopenta-diene (DCPD), dimethylcyclopentadiene, norbornene and pinene. Preferably DCPD is used.
Examples of suitable cycloaliphatic alcohols include cyclohexanol, DCPD-alcohol and cholesterol.
Z can be selected from, for example, a saturated or unsaturated (C1-C40)alkyl or aromatic group, a polymer or an oligomer. Examples of suitable polymers are polyesters, polyethers and poly(capro)lactones.
Z can be substituted with for example ester groups, ether groups, amide groups and alcohol groups.
The modified polymer may consist of the same or different Z groups.
The (modified) polymers according to the invention may be very widely used in technically different fields, both in thermosetting and in thermoplastic applications. Examples are powder paint compositions, coating systems based on water or solvent, can- or coil-coating systems, radiation-curable coating compositions, alkyd resins for coatings, unsaturated resins for construction purposes (for example putties, sealants, castings, compounds and molding compounds), inks, toner compositions, film formers for glass fibre sizings, adhesives, hot melts and in rubber compositions.
Unmodified or partly modified polymers according to the invention can generally be used in powder paint systems, in can- or coil-coating systems and in solvent-based coating systems.
If the modification has been realized with the aid of for example fatty acid alcohols, the polymer obtained can be used as an airdrying system.
A modification with radically curable compounds offers possibilities in the technical fields of radiation-curable coatings and construction resins. A modification of the polymer according to the invention with glycidyl methacrylate and/or dicyclopentadiene results in a suitable product to be applied in radiation curable coatings.
Considering the many possibilities of modification of the polymer according to the invention, modification can be directed at any of a wide range of technical applications.
According to a preferred embodiment of the invention the polymers according to the invention are applied in thermosetting powder paint compositions and in toner compositions.
Thermosetting powder paints have a better resistance to chemicals than thermoplastic powder paints. As a result of this, intensive efforts have for a long time been made to develop crosslinkers and polymers for thermosetting powder coatings. Attempts are still being made to find binder compositions for thermosetting powder paints with a good flow behaviour, good storage stability and a good reactivity. A thermosetting powder-paint binder composition generally contains more than 50 wt. % polymer and less than 50 wt. % crosslinker.
The polymer according to the invention can be used in a powder-paint composition as a polymer and as a crosslinker.
The glass transition temperature (Tg) of the polymer according to the invention lies between 0xc2x0 C. and 150xc2x0 C., preferably between 50xc2x0 C. and 110xc2x0 C., depending on the selected starting materials and the molecular weight.
Preferably a compound according to any one of formulas (I), (II), (III), (IV) or (V) is used in powder-paint compositions. It is also possible to use a polymer in which up to for example 50 wt. %, preferably less than 30 wt. %, of the acid groups are modified.
A coating that is ultimately obtained with a powder paint must meet many varying requirements. Various systems are known. Some systems release volatile components during the curing. These systems present the drawback that they form coatings with bubbles and/or that undesirable emissions are released. As far as the latter is concerned, the volatile component, if organic in origin, may cause undesirable environmental or health problems. It has moreover been found that all the desired properties of the powder paint or powder coating are not always realized.
In other systems use is made of polyesters and the usual crosslinkers containing an epoxy group, for example a bisphenol-A-epoxy resin. No volatile components are generally released from these systems.
It has been found that use of the polymer according to the invention in binder compositions in combination with bisphenol-A-epoxy-resin for powder paints results in a combination of highly desirable properties such as for instance good resistance to chemicals, desired gloss or matt appearance without bubble formation at the surface up to and including layer thicknesses of at least 120 xcexcm, a high resistance to boiling water and salt spray, a high resistance to scratching, good mechanical properties, good powder stability and good colour stability of the powder coating.
It is surprising that use of the highly functional crosslinkers according to the invention results in a good cure behaviour in combination with epoxide group containing polymers without use of trimellitic acid(anhydride) as one of the raw materials. Generally a polyester having carboxyl endgroups has a reduced reactivity towards epoxy groups in the absence of trimellitic acid(anhydride) as one of the raw materials.
The preparation of thermosetting powder coatings in general and the chemical reactions for curing powder paints to form cured coatings are described by Misev in Powder Coatings, Chemistry and Technology (1991, John Wiley) on pp. 42-54, pp. 148 and 224-226. A thermosetting binder composition is generally defined as the resinous part of the powder paint consisting of polymer and crosslinker.
If so desired, the usual additives can be used in the binder composition and in the powder-paint system according to the invention, such as for example pigments, fillers, degassing agents, flow agents and stabilizers. Suitable pigments are for example inorganic pigments, such as for example titanium dioxide, zinc sulphide, iron oxide and chromium oxide, and also organic pigments such as for example azo compounds. Suitable fillers are for example metal oxides, silicates, carbonates and sulphates.
Primary and/or secondary antioxidants, UV stabilizers such as quinones, (sterically hindered) phenolic compounds, phosphonites, phosphites, thioethers and HALS compounds (hindered amine light stabilizers) can for example be used as stabilizers.
Examples of degassing agents are benzoin and cyclohexane dimethanol bisbenzoate. The flow agents include for example polyalkylacrylates, fluorohydrocarbons and silicone fluids. Other suitable additives are for example additives for improving tribocharging, such as sterically hindered tertiary amines that are described in EP-B-371528.
Powder paints according to the invention can be applied in the usual manner, for example by electrostatically spraying the powder onto an earthed substrate and curing the coating by exposing it to heat at a suitable temperature for a sufficient length of time. The applied powder can for example be heated in a gas oven, an electric oven or with the aid of infrared radiation.
Thermosetting coatings of powder-paint (coating) compositions intended for industrial applications are described further in a general sense in Powder Coatings, Chemistry and Technology, Misev, pages 141-173 (1991).
Compositions according to the present invention can be used in powder paints for use on, for example, metal, wooden and plastic substrates. Examples are industrial coatings, coatings for machines and tools, household applications and parts of buildings. The coatings are also suitable for use in the automotive industry for coating parts and accessories.
The invention will be elucidated with reference to the following non-limiting examples.

Condensation polymer containing esteralkylamide-acid groups


An isotonic drink that is especially designed for children between the ages of 6 and 12 years. The drink contains water, carbohydrates including fruit juice, a calcium source and vitamin C. The drink has an osmolality of about 300 to about 380 mOsm/kg and a pH of between about 3 and about 4.5. The drink improves hydration compliance when consumed by children.

This invention relates to an isotonic, fruit juice based drink which is intended for children in the 6 to 12 year old age category. The invention also relates to a method for providing fluid to children in the 6 to 12 year old age category and for improving hydration compliance.
It is well known that the combination of exercise and exposure to sunlight and heat can result in dehydration and heat related conditions such as heat syncope, heat exhaustion, dehydration syndrome, and heat stroke. Children are particularly prone to dehydration related problems because they are generally very active; often in conditions of raised temperatures and sunlight. Also, children drink when they are thirsty and not to prevent dehydration. However, by the time a child is thirsty, the child is already in the initial stages of dehydration. Thirst is not a good indicator of whether or not a child should drink.
If the exposure to heat is accompanied by exercise, a marked increase in glucose utilization takes place. Some of the glucose needed for energy comes from liver glycogen stores. With prolonged exercise, liver glycogen stores are depleted and the rate of glucose production fails to keep pace with glucose utilization, resulting in a fall in the blood glucose concentration. Several physiological responses may then occur; such as increased body temperature, perspiration and pulse rate, decreased blood volume, and biochemical changes associated with the metabolism of compounds to produce energy.
Some of these adverse effects may be avoided by consuming water; especially maintaining body temperature and blood volume. However, it is better to consume fluids which contain saccharides, electrolytes and water. Many products which contain saccharides, electrode and water are commercially available. One well known example of this type of product is GATORADE(copyright) which is commercialized by The Quaker Oats Company. The composition of this product is described in British Patent No. 1,252,781.
PCT patent publication WO97/45026 discloses a creatine-containing isotonic beverage that can be fruit flavoured. It does not suggest that actual fruit juice may be included, teaching instead that carbohydrates should be avoided.
Canadian patent No. 896,486 discloses an isotonic drink, again excluding real fruit juice, despite aiming to meet palatability requirements for oral tolerance. Artificial sweetening agents are preferred.
A sports drink is the subject of EP 0 587 972, but is specifically omits reference to vitamin C as a component. This drink has high concentrations of fruit juice, apparently to provide the requisite sweetening power and to balance the pH for acceptable palatability.
Moreover, these products are not designed for children in the 6 to 12 year old age category. Key to preventing dehydration is stimulating people to drink more fluid voluntarily. Most commercially available products use their sodium and glucose content to stimulate people to drink more fluid voluntarily. However, taste is an important stimulant and most commercially available products are not directed to childrens"" tastes. Also, children are dependent upon what their parents make available and most commercially available products often are not products which parents would purchase for children. Also, most commercially available products are formulated for the physiological needs of children.
Therefore, there is a need for an isotonic drink which is suitable for as a rehydration beverage children in the 6 to 12 year old age group, and this is satisfied by the present invention.
Accordingly, in a first aspect this invention provides an isotonic drink for children, the drink comprising: water; electrolytes; a carbohydrate source including at least about 7% by weight of the drink of fruit juice; a calcium source, and vitamin C. Advantageously, the drink has an osmolality of about 300 to about 380 mOsm/kg and a pH of about 3.5 to about 4.2.
This drink offers the advantages that it is based upon fruit juice and therefore attractive to both children and their parents. Children may be stimulated people to drink more fluid voluntarily and parents may be stimulated to make the drink available. Further, the drink contains calcium and vitamin C; both of which are necessary for children. Also, the beverage has an osmolality which is better aligned to the osmotic pressure in children.
Preferably, the carbohydrate source provides less than about 8% by weight of carbohydrate.
In another aspect, this invention provides a method for improving hydration compliance in an active child of 6 to 12 years age, the method comprising providing a sweetened isotonic drink which contains fruit juice, a calcium source, and vitamin C.
The invention provides an isotonic drink which is especially formulated for children. The drink has a taste and image which encourages children to drink but which provides the electrolytes and carbohydrates necessary to keep children hydrated. The drink is based upon water; electrolytes; and a carbohydrate source which includes fruit juice. A calcium source and vitamin C are also included.
The carbohydrate source may be any suitable carbohydrate source; particularly a combination of fruit juice and other saccharides. The fruit juice is preferably in the form of a concentrate and may be of any flavor. For example, the fruit juice may be apple juice concentrate, orange juice concentrate, pear juice concentrate, cranberry juice concentrate and the like. The other saccharides may be any saccharides suitable for inclusion in drinks. Suitable examples include sucrose, glucose, fructose, high fructose corn syrup, and maltodextrin.
The fruit juice is preferably present in an amount that it provides at least about 7% by weight of the drink; more preferably about 8% to about 12% by weight. For example, the fruit juice may provide about 10% by weight of the drink.
The total carbohydrate content of the drink, including that provided by the fruit juice, is preferably less than about 8% by weight. At carbohydrate concentrations more than about 8% by weight, fluid absorption becomes reduced. Preferably, the drink contains about 5% to about 7.5% by weight of carbohydrate.
If the carbohydrate source does not provide sufficient sweetness, artificial sweeteners such as saccharin, cyclamates and aspartame may be added in an amount sufficient to provide a sweet flavor.
The drink contains the electrolytes sodium and potassium. The sodium and potassium may be provided by suitable sodium and potassium salts such as sodium chloride, sodium citrate, and potassium citrate. The drink preferably contains about 60 mg/l to about 250 mg/l of sodium; more preferably about 80 mg/l to about 125 mg/l. For example, the drink may contain about 105 mg/l of sodium. The drink preferably contains about 60 mg/l to about 150 mg/l of potassium; more preferably about 190 mg/l to about 230 mg/l. For example, the drink may contain about 210 mg/l of potassium.
The drink contains a source of dietary calcium. The calcium source may be any suitable food-grade calcium salt of organic and inorganic compounds. The calcium source should be capable of being solubilized such that a clear solution at a pH of about 4.5 and below may be obtained. Calcium sources which adversely affect flavor, calcium absorption or biological functions are to be avoided. Suitable inorganic calcium sources include the oxide, hydroxide, carbonate, and orthophosphate(s) (mono-, di- and tricalcium phosphate). Suitable organic calcium sources include calcium lactate, calcium gluconate, calcium citrate, calcium acetate, calcium ascorbate, calcium tartarate, calcium malate and the like. Calcium lactate is preferred.
The calcium source is preferably present in an amount such that at least about 20% of the recommended daily value for calcium is provided per liter; more preferably about 30% to about 60% of the recommended daily value for calcium. For example, the drink may contain about 40% of the recommended daily value for calcium per liter.
The drink also contains vitamin C. Preferably sufficient vitamin C is provided such that the drink contains at least 300% of the recommended daily value for vitamin C per liter; more preferably about 350% to about 500% of the recommended daily value for vitamin C per liter.
The drink preferably contains an acid to provide a pH in the range of about 3 to about 4.5. Any food grade acid may be utilized to adjust the pH of the drink. For example, citric acid, phosphoric acid, fumaric acid, adipic and malic acid may be used without developing off taste. Hydrochloric acid is less preferred as the chlorine ion can be nutritionally disadvantageous. Preferably, the acid used for acidification is citric acid. The pH is more preferably in the range of about 3.5 to about 4.2; for example about 3.7 to about 3.9.
The drink has an osmolality of about 300 mOsm/kg to about 380 mOsm/kg; more preferably about 340 mOsm/kg to about 370 mOsm/kg. For example, the drink may have an osmolality of about 360 mOsm/kg. Osmolalities in this range are better suited to the needs of children.
The drink may also include other ingredients normally found in soft drinks such as clouding agents, natural or artificial coloring, preservatives and the like. However, preservatives are not necessary and in fact may be undesirable. The provision of the clear drink allows for the controlled clouding and coloring of the drink, can be added as desired. The drinks may also include other vitamins and minerals as desired.
The drink may be manufactured by mixing the calcium source with any other dry ingredients to form a dry mix. Water and the fruit juice may then be added to the dry mix and the ingredients dispersed. After dispersion, the pH is adjusted as desired with acids. Any additional ingredients may then be added as desired. The volume is adjusted to the appropriate level and the drink bottled and pasteurized according to good manufacturing techniques. The drink is preferably bottled in PET containers under hot filling conditions.