5756 5760.output

* GB786164 (A)

Description: GB786164 (A) ? 1957-11-13

Improvements in pneumatic tyres

Description of GB786164 (A)

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We, DUNLOP RUBBER COMPANY LIMITED, a British Company, of 1 Albany Street, London, N W 1, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - This invention relates to pneumatic tyres and more particularly relates to pneumatic tyres comprising a body of natural rubber or other suitable resilient material and a reinforcement embedded therein and comprising a length of cord or like material arranged in such a manner that, on inflation of the tyre, the edges thereof tend to be forced radially inwardly. In the Specification of our co-pending cognate Application No 6023/54, 20636/54 and 23854/54 (Serial No 786,162), a pneumatic tyre is described comprising a body of natural rubber or other suitable resilient material containing, as an internal reinforcement, a winding

of cord arranged in the form of at least one double layer in which the cord of one layer crosses the cord of the other layer to form a lattice and the cord is each layer extends in a series of unit waves progressing continuously around the tyre in the same direction, each unit wave of cord being completely embedded in the resilient material and consisting of two substantially diagonally-opposite arcuate portions, each extending through and being substantially confined to one bead of the tyre, alternating with portions passing through the side walls and crown of the tyre which leave and approach the arcuate portions substantially tangentially and take a path which is substantially a geodesic with respect to the surface defined by the layer, the arcuate portions of cord in the unit waves i 'C -'% being sufficiently long to ensure that, on inflation of the tyre, each of the beads thereof will tend to contract in diameter over a major portion of the transverse dimension of the foot of the bead as a result of the tension imposed on the cord. The object of the present invention is to provide an alternative form of pneumatic tyre having the same rim-gripping properties. According to the present invention a pneumatic tyre comprises a body of natural rubber or other suitable resilient material containing, as an internal reinforcement, a winding of cord arranged in the form of at least one double layer in which the cord of one layer crosses the cord of the other layer to form a lattice and the cord in each layer extends in a series of turns progressing continuously around the tyre in the same direction, each turn comprising two axiallyaligned arcuate portions extending one around each edge of the tyre and two Ushaped loops each loop extending substantially tangentially from an edge of the tyre and passing through the side walls and crown of the tyre and joining the other axially-aligned edge of the tyre substantially tangentially, the arcuate portions of cord in each turn being sufficiently long to ensure that, on inflation of the tyre, the edges thereof will tend to contract in diameter as a result of the tension imposed on the cord. Preferably the arcuate portions of cord intermediate the loops subtend at the centre of the tyre an angle of the order of 500, as it has been found that, on inflation of the tyre, an arcuate length of this nature is most suitable to move the edges of the tyre radially inwardly on inflation sufficiently for them to grip an associated wheel rim However the arcuate portions may subtend any 7865164 PATENT SPECIFICATION Inventor:-HENRY WILLIAM TREVASKIS. Date of filing Complete Specification: Oct 19, 1955. Application Date: Nov 6, 1954 No 32174154. Complete Specification Published: Nov 13, 1957.

Index at Acceptance:-Class 144 ( 2), C( 3 B 5: 5 F). International Classification:-B 62 g. COMPLETE SPECIFICATION. Improvements in Pneumatic Tyres. 786,164 angle between 40 ' and 3000, preferably between 40 ' and 90 % and still be effective. The cord comprising the reinforcement is firmly embedded in the tyre so that, on inflation and on tensioning of the portions of cord forming the loops, no slippage of the cords occurs Each U-shaped loop is preferably symmetrical about the median plane of the tyre. IQ In order that the invention may be more fully described, reference is made to the accompanying drawing, which shows in perspective the configuration of the cord reinforcement in a pneumatic tyre. In this embodiment of the invention the tyre is indicated at 1 and comprises an inner layer of natural rubber, a double layer of cord reinforcement and an outer layer of rubber which is provided with a tread The axis of the tyre is indicated by the spigots 2. The reinforcement comprises a double layer of cord, the cord of one layer crossing the cord of the other layer over the side-walls and crown of the tyre to form a closelymeshed lattice Each layer of cord comprises a plurality of turns, and said turns progress continuously around the tyre Each turn of cord extends substantially tangentially from a location 3 at one edge of the tyre and in a U-shaped loop 4 across the side-walls and crown of the tyre and symmetrical about the median plane of the tyre and approaches the other edge of the tyre substantially tangentially at a location 5 axially-aligned with said location 3 The cord then extends in an arc around said edge to a location 6 and leaves said location substantially tangentially in another loop 7, identical with loop 4, which also extends across the side-walls and crown of the tyre and back to a location 8 at the original edge which it approaches substantially tangentially The cord then extends in an arc, axially-aligned with the arcuate portion at the other edge of the tyre, which extends to a location 9 adjacent the originating location 3 The next turn of cord commences at location 9 and is laid alongside the first turn and the turns thus progess around the tyre to provide a closely meshed lattice of two layers of cord over the side walls and crown of the tyre and a thickened cord reinforcement at the edges of the tyre. Viewing the completed tyre reinforcement sideways, the two loops of each turn are set at an angle of the order of 130 ' to one another and the arcuate portions of cord of the order of 50 ' When the tyre is insubtend at the centre of the tyre an angle flated the loops of cord are tensioned and the arcuate portions of cord tend to move radially inwardly towards the centre of the tyre, thus tending to force the

edges of the tyre into engagement with a wheel rim. The cord may be made of steel or of a 6 d suitable natural or artificial textile material, e.g cotton, rayon, nylon or the polyester made from terephthalic acid and ethylene glycol and sold under the Registered Trade Mark "Terylene" and preferably consists of 77) a number of twisted strands, each of which consists of a number of twisted filaments. The cord is preferably coated with rubber or suitable resilient material before incorporation in the tyre g a Whilst the loops formed by the cords are preferably symmetrical about the median plane of the tyre they need not necessarily be so For example, they may be asymmetric about said plane and distorted to one SO side or the other This may provide an improved pattern of latticed cord. The arcuate portions of the cord which together form the reinforcement for the edges of the tyre, may each subtend at the 55 centre of the tyre an angle as low as 40 or it may subtend an angle of the order of, e.g 3000, i e almost an entire wrapping around the edge of the tyre, preferably the angle should be between 40 and 900 o

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* GB786165 (A)

Description: GB786165 (A) ? 1957-11-13

Apparatus for adjusting tension in cord wound from one package to another



FR1119899 (A) FR1119899 (A) less

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COMPLETE SPECIFICATION Apparatus for Adjusting Tension in Cord Wound from one Package to Another We, DUNLOP RUBBER COMPANY LIMITED, a British Company of 1, Albany Street, London, N.W.1, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to an apparatus for adjusting tension in textile cord and like continuous material as it is wound from one pack age to another and more particularly relates to means for adjusting and reducing the tension in textile cord when being wound on to a tyre-building former in a method of pneumatic tyre manufacture more fully described in our co-pending Applications Nos. 6023/54, 20636/54 and 23854/54, (Serial No. 786,162). In our co-pending Applications Nos. 6023/ 54, 20636/54 and 23854/54 (Serial No. 786,162), a method of making a pneumatic tyre cover is described comprising winding a length or lengths of textile cord continuously around a collapsible former. The former is slowly rotated during This winding process so that there is built up on the former an enve- lope of cord which forms the carcass of the tyre. This method, and the apparatus for putting it into effect, is more fully described in our said co-pending Applications. The cord is wound off a spool and through a rubber extruder which extrudes a thin coating of rubber around the thread. A force, which may be of the order of 31b. or more, is necessary to draw the 'cord through the extruder and this force may vary according to such factors as the temperature and degree of plasticity of the rubber. On the other hand a tension in the cord of a much lower value, e.g. of the order of 11b, is preferable for actually winding the cord around the former, and this winding tension must rbe less than 'that produced by

the force to draw the cord through the extruder. This tension must not greatly fluctuate since otherwise an aeymmet- rical and uneven casing could Ibe produced. Moreover, on removing the wound carcass from the former, the edges are required to have a predetermined diameter corresponding with the final bead diameter of the moulded tyre. The object of the invention, therefore, is to provide apparatus for reducing the tension in a textile cord or like material and maintaining it at a predetermined value during winding on a package or like support. According to the invention an apparatus for reducing the tension in a textile cord or like material and maintaining it at a predetermined value during winding on la package or other support comprises a driven drum. to draw the material from a source, means comprising a clutch mechanism for driving the drum and spring loaded means to produce a predetermined tension in the material between the drum and the support and movable in response to variations in said tension to en gage or disengage the clutch mechanism if the tension in the material rises substantially above or falls substantially below respectively rhe required value. Preferably the spring loaded means comprises an arm angularly 'movable under the action of an adjustable spring. The cord, having left the drum, passes round a pulley at one end of said arm and the arrangement is such that, if the tension in the cord between the drum and the support increases above a predetermined value, i.e. suitable for winding around a former in a tyre-building operation, the arm will engage the clutch to ease the tension and when the tension has decreased slightly below said value the arm disengages the clutch to allow the tension to rise again. The clutch is of the plate type and comprises a driving clutch plate, a clutch plate axially-displaceable by the thrust race and a drum peripherally grooved to be engaged by the cord as it travels from the rubber extruder to the tyre-building machine. In order that the invention may be more fully described, reference is made to the accompanying drawings, of which: Figure 1 is a plan view of apparatus constructed in accordance with the present invention, and Figure 2 is a side view of Thgure 1. The apparatus comprises a base plate 1 having mounted thereon a fractional horse power electric motor (not illustrated) which drives a

clutch plate 2 rotatable about an axis parallel wkh the base plate. The clutch plate 2 is provided with a co-axial extension on one side thereof on which an annular drum 3 is freely rotatable on roller bearings 4, the drum being grooved at the outer periphery thereof to accommodate a textile cord. 0n the other side of the drum and co-axial therewith is an axially slidable clutch plate 5 which is driven by said co-axial extension land mounted adjacent said slidable clutch plate is a thrust plate 6 and thrust race 7, whereby the slideable clutch plate may be forced into contact with the drum, which in turn is forced into contact with the driving clutch plate. The adjacent faces of the clutch, comprising the driving plate, the floating plate and the feed roller, are all ground flat so that when the clutch is engaged the driving-plate and the floating plate drive the drum. The peripheral speed of the drum must fez be greater than the required speed of the cord at the winding end. Idler pulleys 8, 9 and 10 are provided to guide an associated cord around the underneath of said drum in non-slip engagement therewith and said pulleys are mounted for convenience on a support bar 11 located horizontally above the base plate 1. Three further idler pulleys 12, 13 and 14 are provided, said pulleys being co-planar and being mounted in a plane parallel with the base plate and pulleys 12 and 14 are arranged to take said cord away in a straight line from pulley 10 whilst pulley 13 is offset to one side of said line and is mounted for rotation at one end of a lever arm 15. The lever arm, support bar 11, idler pulleys and the like, are all mounted a short distance above the base plate on uprights 16. The lever arm 15, which is very light to reduce inertia, lies alongside the support bar 11 and the end thereof remote from the pulley 13 is pivotally associated with a member 117 secured to the base plate so that the arm 15 is angularly movable about said member. A bracket 18 constrains the arm to move in a plane parallel to the base plate. The thrust plate 6 6 is provided centrally with a recess to accommodate one end of a pin 19 the other end of which is located within a recess in the lever arm 15 intermediate the ends thereof and adjacent to said member 17 about which the arm pivots. The ratio of the lever is about 35:1. A leaf-.type spring 20 is secured at one end to said support bar 11 and the other end is provided with a bearing 21 which is pressed against the lever arm 15 at the end thereof adjacent the pulley 13, thereby to reduce friction. A spring adjuster 22, screwed through the support bar, is adapted to vary the force of the spring on the lever arm Rayon cord, unwound from a spool is passed through a rubber-extruding machine, which continually coats it with a thin coating of rubber. The

rubber-covered cord then passes over pulley 8, under the drum 3 of the clutch mechanism, over pulley 9 and under pulley 10. It then passes around pulleys 12, 13 and 14 and thence to the tyre winding machine. The operation of the apparatus is as follows. A steady and constant tension in the cord of the order of llb. is required at the winding machine whilst the force which is necessary to pull the cord through the rubber extruder is variable and may, e.g. be of the order of 31b. or more. The clutch must therefore be arranged to exert a pully of just llb. less than the force necessary to draw the cord through the extruder, so that the tension in the cord between the clutch and the winding machine is of the order of lib. i.e. the value imposed by the spring4oaded arm. The spring adjustor is therefore adjusted so that the spring exerts a force of 21b. on the lever arm. The tension in the cord between the winding machine and the clutch is thus 11b. The remainder of the force necessary to draw the cord through the extruder must therefore be supplied by the clutch and the arrangewent is such that with a substantially lib. winding tension the clutch is in continuous operation, hunting on and off so rapidly that it draws the cord through the extruder with a force such that the desired tension of llb. only is left in the cord between the clutch and the winding machine. The ground faces of the clutch plates permit a very rapid engagement and disengagement so that although the desired tension in the cord fluctuates slightly above and slightly below lib. the indicated tension is just lib. This rapid hunting of the clutch gives a rapidly oscillating force which is absorbed in the length of cord between the drum and the winding machine. If the friction in the rubber extruder should increase so that a force in excess of, e.g. 31b. is required to draw the cord therethrough, then the tension in the cord on the winding machine side of the clutch will tend bo increase above the desired llb. This will angularly move the lever arm against the spring to so operate the clutch mechanism that it exerts a greater force tcy draw the cord through the extruder, thus allowing the winding tension to revert to llb. Similarly, if the force to draw the cord through the extruder falls below 31b. then the lever arm is moved in the other direction by the spring so that the clutch exerts a lesser drawing force. Whilst the invention has been described in particular relation to a method and apparatus for building a tyre by continuously winding rubberised cord around la former it is not restricted to this and may he used in conjunction with any method and apparatus for unwinding 'cord from one support and onto another support where it is required to adjust or reduce the tension in the cord. The rubberized cord provides a non-slip engagement between it and the

clutch drum. If non-rubberized cord is used the periphery of the drum may be rubber-covered or the cord could be given one or more complete turns around the drum to ensure a positive non-slip drive. The clutch mechanism, including the motor to drive the clutch, may be designed to overcome any value of friction between the unwinding spool and the clutch, whilst the winding tension may be easily varied by varying the force of the spring on the lever arm. What we claim is: 1. Apparatus for reducing the tension in a textile !cord or like material and maintaining It at a predetermined value during winding on a package or other support comprising a driven drum. to draw the material from la source, means comprising a clutch mechanism for driving the drum and spring loaded means to produce a predetermined tension in the material between the drum and the support and movable in response to variations in said tension to engage lolr disengage the clutch mechanism if the tension in the material rises substantially above or falls substantially below tespectively the required value. 2. Apparatus according to claim 1 wherein said spring-loaded means comprises an angularly movable lever arm pivotable about one end thereof. 3. Apparatus according to claim 2 wherein the clutch mechanism comprises a driving clutch plate and an axtally-inovable clutch plate on ,opposite sides of said drum and thrust-race actuated by angular movement of the lever arm to force said plates and drum together, thereby driving the drum. 4. Apparatus according to claim 3 wherein the end of the arm remote from the pivot is provided with a pulley adapted to be engaged by said cord, said am and pulley being offset to one side of the general line of direction of the cord. 5. Apparatus according to claim 4 wherein a leaf spring is provided to urge said arm angularly away from said general line of direction and adjustment means are provided for varying the spring load on said arm. 6. Apparatus for adjusting tension in cord or like material substantially as herein described and illustrated in the accompanying drawings.

* GB786166 (A)

Description: GB786166 (A) ? 1957-11-13

Improvements in electronic counters


We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, of Imperial Chemical House, Millbank, London, SW 1, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to improvements in electronic counters. Electronic devices comprising polycathode counters are used to count electric pulses. These counters normally comprise a central anode and a plurality of cathodes spaced round the anode; the count is indicated by a glow in the region of a particular cathode. The glow is produced by the flow of elec. tricity between the anode and that particular cathode As each pulse is fed into such a counter the flow of electricity between the anode and a cathode of the counter is caused to be replaced by a flow of electricity between the anode and a cathode adjacent to the former cathode For convenience, this change in the direction of the flow of elec. tricity is referred to hereinafter as the movement of the glow. This movement is achieved by the manipulation of the voltage on pairs of guides between each cathode, alternate guides being connected to each other in series The guides are normally at a higher potential than the cathodes and thereby localise the glow upon a particular cathode With each pulse the potential of the guides to one side of the cathodes is depressed to below that of the cathodes and then this depression of potential is transferred to the other guides. In this way, with each pulse, the flow of electricity is transferred from the cathode to which it flowed, to one guide, then to the next, and with the termination of the pulse lPrice 3 s 6 d l to the next cathode Delaying circuits are used between guides to provide the necessary time sequence for pulses The guides to which pulses are first directed when the count is advanced are hereinafter referred to as the first guides and the other guides are hereinafter referred to as the second guides. Pulses directed to the second guide before the first guide result in

subtraction in the counters Consequently when addition is required the pulses to effect addition are each directed to the first guide and after a delay to the second guide; and when subtraction is required, the pulses to effect subtraction are each directed to the second guide and after delay to the first guide. the counters may be set to zero by momentarily giving the cathode representing zero in each counter a _ negative charge greater than its normal value. It will be appreciated that by reversing charges such polycathode counters may be used as polyanode counters and it is to be understood that such reversal of charges is within the intention of the invention desk cribed heremiafter. An object of the present invention is to provide an electronic apparatus that can add pulses provided to be added, and when the total count is positive subtract pulses provided to be subtracted, without limitation to the number of significant figures added dr subtracted. According to the present invention we provide a counting apparatus for use in combination with a means for generating pulses to be added and pulses to be subtracted comprising at least two polycathode counters of the kind hereinbefore described, in which apparatus the carry between a lower counter and the next higher counter is effected by allowing a pulse through a first gate to the i' h-4 < -4d i; -I ? 786,166 PATENT SPECIFICATION Inventor: -JAMES HAY LOUDON McAUSLAN. ate of filing Complete Specification: Sept 16, 1955. Application Date: Sept 17, 1954 No 26980154. Complete Specification Published: Nov 13, 1957. Index at Acceptance -Class 106 ( 1), A( 10: 20: 5 X: 8 A 10 B: 100: 1 OF). International Classification-f GO 6 f. COMPLETE SPECIFICATION. irnprovements in Electronic Counters. So & 5 SO 786,166 next higher counter to cause addition in that counter when any pulse to be added or any pulse coincident therewith overlaps in said first gate the trailing edge or a pulse derived a from the trailing edge of the signal leaving the cathode preceding the zero cathode of said lower counter, and by allowing a pulse through a second gate to the higher counter to cause subtraction in that counter when any pulse to be subtracted or any pulse coincident therewith overlaps in said second gate the trailing edge or a pulse derived from the trailing edge of the signal leaving the zero cathode of said lower counter, any pulse to operate the next higher counter passed by said gates or derived from a pulse passed by said gates being not longer in time than the pulse time, as hereinafter defined, of pulses to be

counted supplied at the maximum rate of counting and at least as long as the minimum time taken to transfer a signal from a cathode to the adjacent guide in said next higher counter. By pulse time we mean the time interval between the leading edges of incoming pulses to be counted. It will be appreciated that the amount of overlap between the trailing edge of the signal leaving the zero cathode (or the pre:3 Q ceding cathode) and the signal to be counted will be very small and that any signal emerging from the gate as a result of this overlap, should generally be shaped to ensure that the time of the emerging pulse lies between 3 the hereinbefore described limits For simplicity of circuitry we prefer that the pulse to be added should overlap a pulse derived from the trailing edge of the signal leaving the cathode preceding the zero cathode, and that the pulse to be subtracted should overlap a pulse derived from the trailing edge of the signal leaving the zero cathode, each of the derived pulses lying within the hereinbefore described limits and preferably of approximately the same length as the pulses to be added or subtracted so that the overlapping pulses are substantially coincident. If desired, a train of pulses comprising pulses to be added and pulses to be subtracted may each be fed to both of said gates provided that a third substantially coincident signal is also fed to said gates, the third signal being set according to the nature of the pulses, so that when pulses are to be added the third signal is fed to the first gate, and when the pulses are to be subtracted the third signal is fed to the second gate. The counting apparatus of our invention may be used, for example, to measure the movement of a shaft, particularly a shaft that may reverse direction, or hunt or oscillate. In order that our invention may be more 635 fully understood, reference will now be made to the drawings attached to the Provisional Specification It is to be understood that our invention is in no way limited by the specific embodiments illustrated. Figure 1 is a block diagram illustrating 70 one arrangement for operating our apparatus. Figure 2 is a block diagram illustrating a second arrangement for operating our invention. Figure 3 is a full circuit diagram of the 75 arrangement illustrated in Figure 2. Figures-4 and 5 illustrate the waveforms obtained in various parts of the circuit illustrated in Figure 3. In Figure 1, 10 is a disc that is coupled to 80 a shaft (not shown) whose movement it is desired to measure When it rotates, the disc 10 causes two overlapping trains of pulses to be emitted by any suitable

known method in which the character of the pulse 85 train varies according to the direction of movement of the disc For example, the disc may have radial markings that interrupt a light beam directed on to a photosensitive device A second photosensitive device is l,' mounted, angularly separated from the first by an amount equal to one half the width of a radial marking, so that a pulse train is emitted that consists of a signal emitted by the first photosensitive device with a signal 95 emitted by the second photosensitive device degrees out of phase with the first signal. When the disc reverses direction of movement, the phase relationship changes A convenient method of generating a train of 1 o O pulses is described in our co-pending Application 30445/53 (Specification No 757,922). In the arrangement illustrated, two polycathode counters Cl and C 2 are shown, each having 10 cathodes, Cl providing the 105 units and C 2 the tens count G 1 and G 2 represent the first and second guides respectively, and KO and K 9 the zero and ninth cathodes respectively, in each counter It will be appreciated that the provision of a 110 hundreds and a thousands counter merely involves duplication of the circuits illustrated, and for this reason are not shown. The pulse train generated by 10 is fed to a commutator 11 comprising a bi-stable 115 trigger circuit having an output signal when the disc rotates clockwise that is fed in parallel to the coincidence gates 12 and 13, and an output signal when the disc rotates anticlockwise that is fed in parallel to the co 120 incidence gates 14 and 15 Commutator 11 is a routing switch of known kind into which two similar trains of pulses generated by rotation of disc 10 are fed, one train being out of phase with respect to the other The 125 commutator gives an output signal from one of its two positions depending upon the phase relationship of the input signal Thus when the disc 10 changes direction, the phase relationship of the input signals to 11 130 some other circuit and thereby control some further apparatus, e g an automatic filling device For example if our apparatus indicates 0999, further additive pulse causes 1000 to be indicated, the glow in each of 70 the four counters moving on to the cathodes representing 1000 at practically the same instant. In the second arrangement illustrated in Figure 2, the pulses to be counted are pro 75 duced by the method described in our copending Application No 30445/53 (Specification No 757,922) in which two out-ofphase but otherwise identical trains of pulses are generated by rotation of a shaft, and in 80 which one train is squared and differentiated to provide alternating pulses of opposite sign, and the other original pulse train is used to gate pulses of a particular sign of the differentiated pulse train, so that the residual 85 pulses are

of a particular sign according to the direction of rotation of the shaft that generates the original trains of pulses By reason of the change in sign of the residual pulses when the shaft changes its direction of 90 rotation, the residual pulses are arranged to be fed from one of two different sources according to the direction of rotation of the shaft The additive pulses are fed to the first guide G 1 of the units counter Cl, and 95 in parallel to the coincidence gate 20 and after delay through an appropriate circuit (not shown) to the second guide G 2 The subtractive pulses are fed to the second guide G 2 of Cl and to the coincidence gate 104 21, and after delay through an appropriate circuit (not shown) to the first guide G 1. The trailing edge of the signal that leaves cathode 9 (K 9) in Cl as a result of the introduction of a new pulse to be added, is de 105 layed to provide a pulse that is substantially coincident with the pulse to be counted, is fed to 20, so that when Cl is adding and the glow leaves K 9, the signals in 20 overlap to the required extent and a signal is fed to 110 G 1 in the tens counter and a delayed version of the same signal is fed to G 2 through an appropriate circuit (not shown), causing the count to be advanced The delayed trailing edge of the signal leaving KO is similarly 115 arranged to be substantially coincident with the pulse to be counted and which causes the signal to leave KO, so that when the glow is on the zero -cathode in Cl and a subtractive pulse is fed in, there is the required 120 overlap in 21 of the subtractive pulse and the delayed trailing edge of the signal leaving the zero cathode The signal from 21 thus causes the glow in C 2 to move back on to the next preceding cathode 125 Figure 3 sets out in greater detail the circuit arrangement corresponding to the block diagram of Figure 2, for effecting the carry from one counter to the next higher counter. In Figure 3, Cl and C 2 are the units and 130 changes, and 11 switches over to its other position The pulses to be counted are taken from one of the two pulse trains generated by rotation of disc 10, that is, they are generated by the same photosensitive device irrespective of the direction of rotation of the disc 10, and fed through a pulse shaper 16 in parallel to the gates 12, 13, 14 and 15 The output signal from 11 consists of pulses from either of its two output positions depending on the direction of rotation of disc 10, that are coincident with the shaped pulses fed from 16 The circuits of the coincidence gates 12, 13, 14 and 15 are such that when coincident signals are received in 12 (or 14) from 11 and 16, a purse to be counted is fed to the guide G 1 of Cl (or G 2 of Cl) and a delayed, version of this pulse (delayed by a normal delaying circuit, not shown in Figure 1) is fed to the second guide G 2 of Cl (or G 1 of Cl); when such signals are received in 13 from 11, 16 and K 9 of Cl, or in 15 from 11, 16 and

KO of Cl, i e when the glow in Cl is moving from K 9 to KO or from KO to K 9, an output signal is fed from the gate receiving the coincident signals, to the appropriate guide of C 2, and after passing through normal delaying circuits (not shown) to the other guide The trailing edges of the signals leaving K 9 and KO in Cl are shaped by known shaping circuits to give pulses that are substantially coincident with the pulses from 11 and 16. It will be appreciated that the pulses from any one of the coincidence gates 12, 13, 14 and 15, are fed to the appropriate guide of Cl or C 2 as shown in Figure 1, and delayed versions of these pulses, for example by means of a resistive capacitive integrating circuit, to the other guide of the same counter For example, a single pulse from 12 is fed to G 1 of Cl, and a delayed version of the same pulse is fed to G 2 of Cl. Our invention has the advantage that when the glow is on cathode 9 in Cl and an additive pulse is fed in, the signal that causes the glow in the tens counter C 2 to move, is formed as the glow leaves cathode 9 in Cl Therefore, the glow arrives on the new cathode in C 2 at practically the same instant that it arrives on the zero cathode in Cl This is true however many counters there are in the apparatus Similarly, when the count is subtractive, any changes consequent upon the movement of the glow from the zero cathode to the ninth cathode in the lowest counter, take place simultaneously with the movement of the glow in the lowest counter The advantage of obtaining an instantaneous indication of the count in the apparatus, is that there is no danger for a particular indication being missed when the apparatus is being used to control a further apparatus by using the circuit corresponding to a particular count to complete 786,166 786,166 tens counters respectively, and Gl and 02 the first and second guides respectively of each counter V 2 and V 5 are delay units. which take the form of monostable flip-flops. The coincidence gates are shown at V 3 and V 6 and are pentode thermionic valves, each having a short suppressor and control grid bases They are hfield in the cut-off condition by a standing bias on the cathode, and when both signals on the suppressor and control grids overcome this bias a negative signal is obtained from the anode Xl, X 2, X 3 and X 4 are blocking diodes In each of the counters Cl and C 2, three cathodes are shown, K representing the cathodes from i to 9, K 9 the ninth cathode and KO the zero cathode. The input circuit to the guides G 1 and G 2 of the units counter Cl is not shown but is arranged so that when a pulse indicating a positive count is fed to G 1 it also passes. after being delayed by means of a resistivecapacitive integrating circuit, to the second guide G 2 Similarly when a pulse indicating 2 a

negative count is fed to G 2, it also passes, after being delayed by a similar circuit, to the-first guide G 1 Such delaying circuits are well known in the operation of polycathode counters. When the count is additive the pulses to be counted are fed to G 1 before G 2 in Cl, and also to the gate V 6 via the point 30. As the glow moves clockwise from cathode to cathode in Cl a second signal is sent to V 6 only when the glow leaves K 9 in CL. The trailing edge of the signal l Waving K 9 (illustrated at A in Figure 4) is delayed in V 5 to form the pulse shown at B in Figure 4, which is fed into V 6 This pulse is fed into V 6 at the same time as the pulse which causes the units counter to operate (C in Figure 4), and since the two pulses overlap to the required extent in V 6, there is a negative output pulse from V 6 (D in Figure 4), which is fed to the first guide G 1 of the tens counter, and after passing through the normal delaying circuit the delayed pulse (E in Figure 4) is fed to the second guide in the tens counter Therefore, as the glow moves from cathode 9 to the zero cathode in Cl, the glow in C 2 moves forward on to the next cathode at the same instant. When the count is additive, the only signal fed into the gate V 3 is the pulse derived from the trailing edge of the signal leaving the zero cathode Consequently there cannot be an output signal from V 3 when the counter is adding. When the count is subtractive, the pulses that effect the subtraction are fed to G 2 before G 1 in Cl, and also to the gate V 3 via the point 31 As the glow moves anticlockwise from cathode to cathode in Cl, a second signal is sent to V 3 only when the _ 5 glow leaves KO in Cl The trailing edge of the signal leaving KO (F in Figure 5) is delayed in V 2 to form the pulse shown at G in Figure 5, which is fed to V 3 This pulse is fed into V 3 at the same time as the pulse that causes the uilits counter to operate (H 7 P in, Fihure 5), and since the two pulses overlap in V 3, there is a negative output pulse from the gate (I in Figure 5), which is fed to the second guide 02 i of the tens counter C 2, and after passinzg through the normal 75 delaying circuit, the delayed pulse (J in Figure 5) is fed to the second guide of C 2. As the glow moves from the zero cathode to cathode 9 in CI, the glow in C 2 moves back to the next preceding cathode at the same $ 4 instant. There is no output signal from V 6 when the count is subtractive because the only signal fed to V 6 during subtraction is the pulse derived from the trailing edge of the S) signal leaving the ninth cathode. Although in the specific embodiment described we have referred to the counters as the units and tens counters respectively, it will be

appreciated that the method of carry 941 and the apparatus described therefor, apply equally to the carry from any counter to the next higher counter. The pulses to be counted are preferably obtained in the form of a train of pulses, each 95 of which overlaps a pulse of a second train of pulses, the amount of overlap being such that on reversal the phase relationship changes and the, combined waveform is therefore direction sensitive Such direction l Ot sensitive trains of pulses may be conveniently obtained by the interruption of a beam of light directed on to two photo-electric cells so disposed that one photo-electric cell produces one of said trains of pulses and the 105 other photo-electric cell produces the other of said trains of pulses when the beam of light is interrupted, as for example hereinbefore described. Where our apparatus is used for measuring 1 lo the net movement of a shaft or disc and pulses are generated in this way, we prefer that the pulse to be counted, both additive and subtractive, should be generated by the movement of the same line or series of lines 115 of the moving disc since under these conditions the possibility of introducing a cumulative error when the shaft hunts or oscillates is removed The use of two different reference lines, one for addition and one for sub 12 't traction, might cause errors if oscillation occurred about one line, and the amplitude of oscillation was insufficient to include the second line. Our apparatus may usefully be employed 13, in combination with the equipment described in our cognate co-pending Applications 4221152, 7339/52 and 31068152 (Specification No 771,052) to provide improved equipment for determining gross, tare and net l 3 to be added or a pulse coincident therewith overlaps in said first gates the trailing edge or a pulse derived from the trailing edge of the signal leaving the cathode pre 65 ceding the zero cathode of said lower counter and a third pulse substantially coincident with said pulse to be added, and a pulse is passed through said second gate when any pulse to be subtracted or a pulse 70 coincident therewith overlaps in said second gate the trailing edge or a pulse derived from the trailing edge of the signal leaving the zero cathode of said lower counter, and a third pulse substantially coincident with 75 said pulse to be subtracted, said third pulse being fed to said first gate only when addition is required and to said second gate only when subtraction is required. A counting apparatus according to any 80 of the preceding claims comprising means for generating pulses to be counted in the form of a train of pulses each pulse of which overlaps corresponding pulses of a second train of pulses, the amount of overlap being 85 such that on reversal the phase relationship of the overlapping pulses changes.

6 A counting apparatus according to


* GB786167 (A)

Description: GB786167 (A) ? 1957-11-13

Improvements in or relating to the preparation of basic oil-solublepolyvalent metalsalts of organic acids and solutions of said basic salts inoils, and the resultingsalts



DE1086701 (B) FR1136852 (A) US2865956 (A) DE1086701 (B) FR1136852 (A) US2865956 (A) less Translate this text into Tooltip



PATENT SPECIFICATION 7 E Inventors: -GLYN ELLIS, JAMES HARTLEY and JOHN CAMPBELL MOSELEY. Date of filing Complete Specification: Aug 19, 1955. 0 4 Application Date: Sept 27, 1954 No 27853 /54. Complete Specification Published: Nov 13, 1957.

Index at Acceptance:-Classes 2 ( 3), C 3 A 7 (A 2 El: G 1), C 3 A 1 OA( 4 E 4 F: 5 A 1), C 3 B 13 B 2 (A 4: C: Dl, C( 3 B: 310 3 X): and 91, F( 1: 2 X. International Classification:-Cl Om. COMPLETE SPECIFICATION. Improvements in or relating to the Preparation of Basic Oil-Soluble Polyvalent Metal Salts of Organic Acids and Solutions of said Basic Salts in Oils, and the Resulting Salts. We, "SHELL" RESEARCH LIMITED, a British Company, of St Helen's Court, Great St Helen's, London, E C 3, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention is concerned with basic oil-soluble polyvalent metal salts of organic acids, particularly but not exclusively the basic oil-soluble polyvalent metal salts of for example alkyl hydroxy benzoic acids, petroleum sulphonic acids and naphthenic acids, and with their solutions in oils (i e. liquids which are not miscible with water). The present invention is also concerned with the preparation of such basic polyvalent metal salts and solutions thereof in oils for example as hydrocarbon solvents. It is well known, in preparing a metal salt or soap of an organic acid by reacting the acid with a base such as the oxide, hydroxide or carbonate of the desired metal, that the use of an excess of the base may result in a product which contains an amount of metal which is in excess of that theoretically reouired to replace the acidic hydrogen atom or atoms of the organic acid For many uses, for example as additives for lubricants, desirable results are obtained by the use of these so-called basic salts or soaps. Hitherto it has been proposed to prepare basic salts or soaps of organic acids such as petroleum sulphonic acids and alkyl hydroxy benzoic acids by using a large excess of the base in a more or less conventional process for producing the salts or soaps, but it has been found that there is a definite upper limit to the basicity of the resulting basic salts or soaps. An object of the present invention is to provide a process which may be used forpreparing highly basic oil-soluble polyvalent metal salts of organic acids, particularly basic polyvalent metal organic acid salts having a basicity of the order of 200 % or more, and solutions thereof in oils. Basicity is defined herein as the ratio (expressed as a percentage) of the number of equivalents of polyvalent metal per unit weight of the basic polyvalent metal salt of an organic acid in excess of the

stoichiometric amount required to form the neutral polyvalent metal salt thereof to the number of equivalents of combined organic acid' per unit weight of the basic salt Thus if the basic salt contains M equivalents of metal and E equivalents of organic acid per grams of basic salt, then the basicity is: M -( 1 x 100 % E According to the present invention a process for preparing a solution of a basic oilsoluble polyvalent metal salt of an organic acid in an oil (as hereinbefore defined) comprises reacting at a temperature between C and 70 C an oil-soluble polyvalent metal salt of the organic acid, in the presence 16,167 ' 786,167 of said oil and a water-miscible, oxygencontaining organic solvent, with a polyvalent metal carbonate which is formed in situ in the reaction mixture The resulting mixture is then worked up to remove said water-miscible, oxygen-containing organic solvent, together with water Preferably the reaction mixture contains a small amount not exceeding 10 % by volume of water other than water formed during the reaction; e g about 0 1 % to 10 % by volume of the water-miscible organic solvent is usually sufficient depending on the basicity of the salt to be prepared The reaction mixture is also preferably stirred or otherwise agitated so as to prevent any substantial separation into more than one liquid phase during the course of the reaction. Also according to the invention a process for preparing a basic polyvalent metal salt of an organic acid comprises removing oil from an oil solution of said basic salt obtained by the process just defined The present invention also includes the resulting basic oil-soluble polyvalent metal salts and solutions thereof in oils, which oils may be different from those present during the preparation of the basic polyvalent metal salts. The oil-soluble polyvalent metal salt of an organic acid which is used as starting material will usually be first formed in situ in the reaction mixture by reacting the free organic acid (or a salt thereof other than a polyvalent metal salt) with a compound of said polyvalent metal, which compound is preferably the hydroxide thereof but may be the carbonate or a mixture of the carbonate and the hydroxide Thus usually said polyvalent metal salt will be formed as a first step in carrying out the present process. The aforesaid polyvalent metal salt of said organic acid which is reacted with the polyvalent metal carbonate to form the desired basic polyvalent metal salt of said organic acid may itself be a basic salt of said organic acid with said polyvalent metal Thus for example an oil-soluble polyvalent metal basic salt of an organic acid produced by the process of the invention may be further reacted in accordance with the invention with the carbonate of said polyvalent metal to produce a still more basic polyvalent metal salt of said acid.

5; According to the present invention the polyvalent metal carbonate is formed in situ in the reaction mixture and in this Specification this expression is intended to mean that the polyvalent metal carbonate is formed in the reaction mixture either by reacting a polyvalent metal base such as the oxide, hydroxide or an allkoxide with carbon dioxide or carbonic acid or by a reaction which involves the interaction of polyvalent 6.5 metal ions and carbonate (CO,,) ions to form the polyvalent metal carbonate. Although the polyvalent metal carbonate is preferably prepared in situ in the reaction mixture by the first method referred to above, the second method may equally well 70 be used, thus the polyvalent metal carbonate may be formed in situ by reacting a salt of the polyvalent metal, for example the chloride with an alkali metal or ammonium carbonate Thus for example calcium 7,5 carbonate may be formed in situ in the reaction mixture by the interaction of methanol or aaueous solutions of sodium carbonate and calcium chloride. The process of the present invention is 80 carried out at a temperature between about C and 70 ' C, though temperatures between about 30 ' C and 5 O C are preferred when preparing 200 % basic salts such as calcium alkyl salicylates and somewhat 85 higher temperatures are preferred when preparing basic salts of higher basicity: for example temperatures above 50 ' C are preferred when preparing 1,000 % basic naphthenates In general the actual tern 9 l perature employed in any particular case will depend on the basicity of the highly basic product being prepared. The present invention is applicable to the preparation of highly basic organic acid ' salts and solutions thereof in oils of a large number of polyvalent metals including the alkaline earth metals, i e calcium, barium, strontium, and magnesium and heavy metals such for example as copper, zinc, manganese, 10) cobalt and lead. In general the oil-soluble organic acids which can be employed in the practice of the present invention include substituted and unsubstituted aliphatic, cycloaliphatic and 105 aromatic acids comprising the carboxylic acids, sulphur-containing acids such for example as sulphonic acids, phosphoric acids and the corresponding thio-acids Phenols and also partial esters of sulphur-containing 110 and phosphorus-containing acids can also be employed. The sulphonic acids (or salts thereof) which can be employed include the aliphaticsubstituted cyclic sulphonic acids in which 115 the aliphatic substituent or substituents contain at least twelve carbon atoms, for example alkylaryl sulphonic acids, alkylcycloaliphatic sulphonic acids and alkylheterocyclic sulphonic acids for example: 120 petroleum sulphonic acids and cycloaliphatic sulphonic acids such as petroleum naphthane sulphonic acids The process of the present

invention is also applicable to cyclic carboxylic acids such 125 as those containing a benzenoid structure i e, benzene, naphthalene, etc, and an oil-solubilising radical or radicals having a total of at least about twelve carbon atoms, such for example, as the mono or poly-wax 130 786,167 substituted benzoic or na Dhthoic acids, and particularly the long-chain alkyl salicylic acids Cycloaliphatic carboxylic acids such as the petroleum naphthenic acids may also be employed. The phosphorus acids which can be employed in the process of the present invention include tri and pentavalent organic phosphorus acids (and the corresponding thio-acids) such, for example, as the aliphatic, cyclo-aliphatic and aromatic phosphoric and thiophosphoric acids having at least twelve carbon atoms per molecule. The phenols which may be used in carrying out the present process include the octylphenols, dodecylphenols, octadecylphenols, diisopropylphenols, dihexylphenols and the condensation products of phenols with aldehydes or ketones such as the condensa2 ( 1 tion products of octyl phenol and formaldehyde. Of the various oil-soluble organic acids which can be used, it is preferred to employ as the starting material, the oil-soluble alkyl 2 5 hydroxy benzoic acids; petroleum naphthenic acids; and petroleum sulphonic acids obtained by sulphonating petroleum hydrocarbons, particularly petroleum lubricating oil fractions It will be understood that mixtures of basic organic acid salts can be prepared in accordance with the present invention by using mixtures of different organic acids as starting material. A preferred procedure in carrying out the process of the present invention includes, as a first stage, contacting a solution of the organic acid starting material in a hydrocarbon solvent (preferably an aromatic hydrocarbon or a hydrocarbon fraction rich in aromatics) with the solid material obtained as a sludge in the subsequent working up of the reaction product and thereafter with sufficient polyvalent metal hydroxide to form a reaction mixture comprising a hydrocarbon slurry containing the polyvalent metal salt of said organic acid having a basicity of up to about 50 % and an excess of said polyvalent metal hydroxide The overall amount of polyvalent metal base added in the first stage will depend on the basicity required in the resulting highly basic product For example 3 5 equivalents of base are required per equivalent of organic acid when preparing a 200 % basic product. This first stage reaction is preferably effected at between 50 and 600 C and it may be carried out in the presence of the aforesaid water-miscible, oxygen-containing organic solvent Alternatively all of said organic solvent or a further quantity thereof can be added to the slurried reaction mixture subsequently but prior to the second stage (carbonation stage) of the process which involves an interaction

between the said polyvalent metal salt of the organic acid and the polyvalent metal carbonate which is formed in situ in the reaction mixture by reaction between the excess polyvalent metal hydroxide in the feed to the second stage and carbon dioxide During the course of 70 the carbonation reaction the dissolved carbon dioxide reacts with the polyvalent -metal hydroxide to form the polyvalent metal carbonate in situ in the reaction mixture, which carbonate becomes associated 75 in some way (not at present fully understood) with the polyvalent metal salt of the organic acid during formation of the highly basic salt. The product of the carbonation stage com 80 prises the desired highly basic polyvalent metal salt of the organic acid, the basicity of which will depend inter alia on the amount of polyvalent metal hydroxide in the feed and the duration of the carbon 85 dioxide treatment, together with solids comprising any unused polyvalent metal hydroxide by by-product polyvalent metal carbonate in the solid state, i e not solubilised in association with the highly basic 90 polyvalent metal salt of the organic acid, and liquids comprising said hydrocarbon solvent, said water-miscible, oxygen-containing organic solvent and water This mixture is then clarified for example by centri C 5 fuging to remove the solid material in the form of a sludge which, since it contains a small proportion of the desired highly basic organic acid salt, is recycled to the first stage referred to above, an occasional 100 bleed of sludge usually being sufficient to prevent the build-up of impurities in the system The by-product solid polyvalent metal carbonate is decomposed by the organic acid starting material in the first stage 105 The clarified mixture is then subjected to phase separation to yield an organic solvent phase containing water and a hydrocarbon solvent phase containing the desired highly basic organic acid salt The hydrocarbon 110 solvent phase is conveniently further worked up by adding a light mineral oil thereto and steam distilling the resulting mixture under reduced pressure to remove as overhead the hydrocarbon solvent together with the 115 remaining water-miscible organic solvent and water The resulting concentrated solution of the desired highly basic organic acid salt in mineral oil is preferably contacted for a sufficient time, e g an hour, with filter 120 aid prior to being subjected to a final filtration treatment, and the organic solvent phase and steam distillation top product are further processed to separate the water-miscible organic solvent and the hydrocarbon solvent 125 for re-use in the Drocess The mineral oil concentrate of the highly basic polyvalent metal salt of the organic acid is suitable for use as an additive for lubricating oils. Alternatively the solid highly basic poly 130 valent metal salt of the organic acid can be isolated from the hydrocarbon solvent phase by

evaporation of the solvent under reduced pressure or by precipitation of the solid by the addition of excess wvater-miscible oxygencontaining organic solvent prior to the remnoval of the solvents. The process of the present invention is particularly suitable for the preparation of I-\ highly basic alkaline earth metal salts of alkyl hydroxy benzoic acids, particularly alkyl salicylic acids containing at least twelve carbon atoms in the alkyl group, having a basicity of for example 200 % or 1.5 more, and to the preparation of highly basic petroleum sulphonates and highly basic naphthenates such as calcium, strontium, barium, zinc, copper, manganese, cobalt and lead naphthenates. The oil component of the reaction mixture is preferably hydrocarbon solvent such as xylene or gasoline, though mineral oil fractions having a relatively low viscosity so that subsequent filtration of the basic product is facilitated, and where the resulting mineral oil concentrate of the basic product is to be used as an additive for lubricating oil compositions, also having a relatively low volatility, may also be used. Lubricating oil fractions having a viscosity of from about 100 to about 400 seconds Saybolt Universal at 380 C are suitable and the concentration of the oil-soluble organic acid starting material in the mineral oil 3,5 solution may be between about 10 % and about 50 % by weight However, it will be appreciated that many other low viscosity oils which do not contain polar groups in their molecules and which are not capable of reacting with carbon dioxide under reaction conditions or with the resulting basic salts may be used in carrying out the process of the invention For example, the reaction mixture may contain as the oil component carbon tetrachloride, benzene, toluene, cyclohexane, iso-octaine or decane, and where the low viscosity oil is removed at the end of the reaction and replaced by a liquid of higher viscosity the latter may be a synthetic lubricant such as a polymerised olefin, or an alkylated aromatic hydrocarbon, or a liquid polysiloxane or fluorocarbon, or an ester type lubricant such as di( 2-ethylhexyl) sebacate or adipate and trioctyl phosphate or a fatty oil such as castor oil. The water-miscible oxygen-containing organic solvent employed in the process of the present invention is preferably one which boils below about 1400 C The term "water-miscible, oxygen-containing organic solvent" is used herein to include those solvents which are capable of forming homogeneous mixtures with up to about 10 % by volume of water in addition to those cruanic solvents which are miscible with water in higher proportions, for example at least 50 %' by volume Solvents which are miscible with water in all nronortions are however preferred

Preferably aliphatic alco 7 I hols containing not more than 5 carbon atoms such as methanol and ethanol and also the water-miscible polyhydric alcohols such as ethylene glycol or ketones containing not more than six carbon atoms for example 7 acetone are used, although other watermiscible, oxygen-containing organic solvents such as ethers for example di-isopropyl ether, methyl and ethyl ethers of the ethylene glycol 1,3-dioxane and 1,4-dioxane; and St} esters for example ethyl lactate may also be used. In carrying out the process of the present invention with the organic acid starting material dissolved in a hydrocarbon solvent, s the reaction mixture preferably contains at least about 5 % (by weight of the hydrocarbon solution of the organic acid) of the water-miscible oxygen-containing organic solvent, for exam Dle between 5 and 100 % 9 P by weight Good results have been obtained using a lower aliphatic alcohol, particularly methanol, for example commercial anhydrous ( 99 %y methanol, or a ketone such as acetone 9 as In the case of methanol although relatively small amounts between about 5 % and about 10 % by weight based on the oil solution of the oil-soluble organic acid are effective, larger amounts of methanol for 104) example about 50 % by weight of the oil solution of the organic acid are preferred when producing a 200 %O basic product and amounts up to 100 % or more may be used. A small amount preferably not exceeding 105 % by volume (e g 0 1 % to 10 % by volume of the water-miscible solvent) of water may be present initially, particularly when high methanol concentrations of the order of 50 % or more are employed, 110 although as will be appreciated, some water is formed during the course of the-reaction when the polyvalent metal base used is a hydroxide Also the organic solvent, for example methanol, will usually contain a 115 small amount of water particularly if it is recycled from a solvent recovery stage. Thus for example 100 %, (by weight of the hydrocarbon solution of the organic acid) of %,o aqueous methanol may be used When 120 highly basic organic acid salts having basicities up to 1,000 %,' are prepared, it is preferable to employ even higher concentrations of the water-miscible organic solvent, for example between 100 and 300 % of 125 methanol by weight of the hydrocarbon solution of the organic acid. The alkyl salicylic acids used as starting material in a preferred application of the invention may be prepared by first reacting 130 786,167 product, which will usually have unsatisfactory oil-solubility (blend stability) properties, may be said to be "overcarbonated". The amount of carbon dioxide which the reaction mixture is allowed to absorb is 70 therefore controlled to avoid such overcarbonation and local overcarbonation due to localised excess carbon dioxide

concentrations in the reaction mixture is minimised by effective agitation of the reaction mixture 75 and also by using an adequate quantity of the water-miscible organic solvent Carbonation can be effected with pure carbon dioxide or with a mixture of carbon dioxide and a gas which is inert with respect to the re 80 action mixture, for example air or nitrogen, and the reaction is preferably carried out with the carbon dioxide or carbon dioxide/ air mixture under slight superatmospheric pressure, for example about one pound per 85 square inch gauge although higher pressures may be employed if desired. The preparation of highly basic alkaline earth metal alkyl salicylates having a basicity of the order of 200 % and using 90 xylene as the oil and methanol as the watermiscible, oxygen-containing organic solvent, is preferably carried out at a temperature of about 30 ' C, although higher temperatures, for example about 500 C are usually more 95 suitable for preparing alkaline earth metal alkyl salicylates of higher basicities of the order of 1,000 % Cooling of the reaction mixture will generally be necessary in order to absorb the excess heat of reaction and the 100 reaction vessel can be jacketed and/or provided with an internal cooling coil or an external cooler for the reaction mixture for this purpose The reaction mixture should be thoroughly stirred during the course of 105 the reaction in order to allow the maximum rate of carbon dioxide absorption to take place, and also to maintain a substantially homogeneous reaction mixture It has been found that, providing there is a small excess 110 of polyvalent metal base present in the reaction mixture at the end of the carbonation reaction, a small increase in basicity of the reaction product may occur if the reaction mixture is allowed to stand for a period, 115 e.g 1 to 4 hours, after absorption of carbon dioxide is complete It is believed this may be due to dissolution of suspended base. However, if no excess base is present in the reaction mixture the basicity of the product 120 may fall slightly Such degradation, which appears similar to overcarbonation in its effect, can usually be avoided by ensuring that excess base is Dresent if the reaction mixture is allowed to stand for any length 125 of time prior to working up. When preparing 200 % basic alkaline earth metal alkyl salicylates, the alkyl salicylic acid starting material is preferably in the form of a 65-70 % solution in xylene, a more con 130 the corresponding alkyl phenols with an alkali metal hydroxide (the phenation stage) and thereafter reacting the resulting alkali. metal alkyl phenates with carbon dioxide to produce the alkali metal alkyl salicylates (the carboxylation stage), which salicylates are then acidified with mineral acid to liberate the free alkyl salicylic

acids The resulting alkyl salicylic acids are usually associated with unreacted alkyl phenol: the crude acids can, however, be used as such in carrying out the present process If desired, carboxylate leaving the carboxylation stage may be re-processed through the phenation and carboxylation stages or alternatively a portion of the carboxylate which acts as an emulsifying agent may be recycled to the phenation stage in order to permit the use of aqueous sodium hydroxide in the phenation reaction Processes for producing alkyl salicylic acids suitable for use as starting material in the process of the present invention are described in more detail in for example our co-pending British Patent Snecifications Nos 734,598; 734,622 and 738,359. The references herein to alkyl salicylic acids are intended to cover the individual acids and also mixtures of acids having different alkyl substituents, for example a mixture of alkyl salicylic acids having alkyl groups containing between 14 and 22 carbon atoms, for example a mixture of C 14-C,8 mono and di-alkyl salicylic acids Mixtures of such acids, usually containing some unreacted alkyl phenol, will generally be used in practice and in many cases are to be preferred. The process may be operated as a batch process or preferably as a continuous process In batch operation the carbon dioxide absorption rate is substantially constant over the course of the reaction and the flow of carbon dioxide is stopped when the required amount has been absorbed For continuous operation the feed rates of the slurried reaction mixture and the carbon dioxide to the reaction vessel are maintained in a predetermined fixed ratio which is determined by the composition of the slurry, reaction mixture being withdrawn continuously from the reaction vessel at a rate which will provide an average residence time therein of the desired duration. In the preparation of highly basic polyvalent metal salts in accordance with the present invention and in particular the highly basic alkaline earth metal salts of alkyl salicylic acids, it is found that the introduction of carbon dioxide into the reaction mixture causes the basicity thereof to increase steadily until it reaches a maximum with free polyvalent metal base still present On further introduction of carbon dioxide thl basicity drops sharply and the 786,167 centrated solution being less easy to handle due to its higher viscosity When preparing more highly basic products e g 1,000 % basic calcium alkyl salicylates a more dilute acid in xylene solution may be desirable in some cases. The reaction mixture at the end of the carbonation reaction may be worked up by centrifuging to remove as a sludge the bulk of the solids comprising unreacted polyvalent metal base and polyvalent metal carbonate The resulting liquid mixture which will form two liquid phases on settling, namely aqueous methanol and highly basic salt in

xylene, may be subjected to phase separation to remove aqueous methanol and then distillation to remove the remaining methanol and water together with some xylene The remaining xylene solution of the highly basic salt may then be clarified to remove traces of inorganic material and may be used as such for many applications of the basic salt, if desired after further concentration of the solution by distilling off excess xylene, or the xylene may be removed to give a solid oil-soluble, highly basic product. Preferably, however, the two phase liquid mixture obtained by removal of solids from the reaction mixture is worked up by first removing aqueous methanol by phase separation and then adding an oil (e g. spindle oil) and steam distilling the resulting mixture to remove the remaining :35 methanol and water and all the xylene to give a solution of the highly basic product in the oil suitable for use as an additive for lubricating and fuel oils In carrying out this preferred working-up procedure the aqueous methanol from the phase separation is conveniently combined with the methanol/water/xylene distillate from the steam distillation and subjected to phase separation, if necessary after addition of further water, to yield an upper xylene layer for recycling and a lower aqueous methanol layer which can be rectified to give methanol for re-use in the process. The process of the present invention will be further described with reference to the accompanying drawing which shows diagrammatically a plant for the continuous manufacture of highly basic calcium alkyl salicylates uas a ckbncentragted solution in spindle oil It will be appreciated, however, that the same plant is readily adapted to the manufacture of other oil-soluble highly basic polyvalent metal, particularly alkaline earth metal, salts of organic acids 630 such as naphthenic acids, petroleum sulphonic acids and alkyl hydroxy benzoic acids as solutions in organic solvents of which spindle oil is only one example. Referring to the drawing, the plant com655 prises a "neutralisation" vessel 1 having a stirrer 2 and to which a solution of alkyl salicylic acids in a hydrocarbon solvent such as xylene is fed through a line 3 The vessel 1 is also provided with a line 4 for introducing a slurry of calcium hydroxide in 7. xylene and a line 5 through which a sludge comprising calcium carbonate and unused calcium hydroxide together with some entrained highly basic salt removed from the liquid carbonation product is returned to 75the neutralisation stage. A slurried reaction mixture comprising approximately 50 % basic calcium alkyl salicylates in xylene and containing excess calcium hydroxide passes continuously from SO the vessel 1 through a line 6 to a carbonation vessel 7 having a stirrer 8 and a perforated pipe ring 9

at the bottom through which carbon dioxide is introduced into the reaction mixture The vessel 7 is also pro S 5 vided with an input line 10 for methanol and a draw-off line 11 at the bottom of the vessel which leads to a centrifugal clarifier 12 in which solids are removed from the carbonation product withdrawn continuously 94 from the carbonation vessel 7, the solids being recycled through line 5 Carbon dioxide is circulated through the mixture in the carbonation vessel 7 by means of a pump 13 -and lines 14 and 15, make-up carbon l, dioxide being supplied through a line 16 at a rate equal to that at which carbon dioxide is absorbed by the reaction mixture. The clarified liquid leaving the clarifier 12 passes through a line 17 to a phase l OG separator 18 in which it forms a lower xylene layer containing the highly basic calcium alkyl salicylates, together with some water and methanol and an upper methanol layer containing most of the water The upper 105 layer is withdrawn through a line 19 and passes to a solvent recovery stage which being of conventional design is not shown in the drawings The lower xylene layer is withdrawn through a line 20, mixed with 110 spindle oil added through a line 21 and passed to a stripping column 22 in which the xylene and the remaining methanol and water is steam-stripped and removed as overhead through a line 23 The resulting 113 spindle oil solution of the highly basic calcium alkyl salicylates removed as bottoms through a line 24 passes to a mixing vessel having a stirrer 26 in which it is contacted with filter aid introduced through a 120 line 27, for example 1 % Hyflo Supercel, (the name "Hyflo-Supercel" is a Registered Trade Mark) to remove traces of solid material which would otherwise form a slimy coating on the subsequent filter 125 The mixture of basic salt solution in spindle oil and filter aid passes from the vessel 25 through a line 28 to a filter 29 in which the spent filter aid is removed and the clear solution leaving the plant through 131) 786,167 pentane-diluted solution which was clear and bright. The highly basic product was found to have a basicity of about 226 %; its total base and acid contents being 3 87 and 1 19 milliequivalents per gram respectively. EXAMPLE II. The process of Example I was repeated using 10 %, by weight of the acid solution, of methanol and a reaction temperature of 603 C, other conditions remaining substantially the same, except that carbon dioxide was bubbled into the reaction mixture for minutes and the volume of carbon dioxide absorbed was 38 litres. A highly basic product having a basicity of about 266 % and a total base and acids content of 3 85 and 1 05 milli-equivalents per gram respectively was obtained The resulting mineral oil concentrate had excellent blend stability with lubricating oils, the pentane-diluted

solution being clear and bright. line 30 may be used as a concentrated additive for lubricating oils. It will be appreciated that the process of the invention may be carried out in other ways either continuously or as a batch process For example the carbonation reaction can be effected by injecting carbon dioxide into the reaction mixture which is cycled through a line by means of a pump, the circuit including a vessel in which the mixture is stirred to maintain intimate contact between the components thereof. EXAMPLE I. A mixture of highly basic calcium alkyl salicylates (C,,-C,, mono and di-alkyl salicylates) was prepared using a reaction vessel fitted with a stirrer a reflux condenser and means for bubbling carbon dioxide through a reaction mixture. At the commencement of the process 1,500 parts by weight of a 70 % solution of alkyl salicylic acids in xylene (C,4-C,, monoand di-alkyl salicylic acids containing some unreacted alkyl phenol and the solution hav215 ing an acid value about 50 mg KOH/g) were placed in the reaction vessel, together with 5 %, by weight of the acid solution of methanol and 200 Darts, by weight (i e. four equivalents Per equivalent of alkyl salicylic acids} of calcium hydroxide The resulting mixture was then heated to 60 C. with vigorous stirring ( 1,500-2,000 r p m) and maintained at that temperature for hour, whereupon carbon dioxide was bubbled through the reaction mixture for 47 minutes, which was maintained at 60 C and stirred vigorously throughout The volume of carbon dioxide absorbed was 33 9 litres. The reaction mixture was then centrifuged to remove unreacted calcium hydroxide and also solid calcium carbonate produced during the course of the reaction and not utilised in producing the highly basic product, and the resulting liquid was distilled to remove the methanol, the water produced in the course of the reaction and some of the xylene The remaining xylene solution was clarified by filtration and a quantity of spindle oil was then added to the clarified solution and the xylene removed therefrom by distillation leaving a cencentrated spindle oil solution of the highly basic calcium alkyl salicylates. The resulting mineral oil concentrate was used as an additive for lubricating oils with which it was found to have excellent blend stability Blend stability may be assessed by diluting a sample of the xylene solution with about 25 Darts by volume of pentane. Blend stable material gives a completely clear and bright solution in this test The highly basic calcium alkyl salicylates produced in the foregoing process yielded a SO EXAMPLE III.

A mixture of highly basic calcium alkyl salicylates (C 14-Cl, mono and di-alkyl salicylates) was prepared by a continuous 90 process using two reaction vessels each fitted with a stirrer and a reflux condenser and connected in series with an intermediate surge vessel The second reaction vessel was also provided with means for bubbling 95 carbon dioxide through the reaction mixture therein. A slurry comprising a 70 % solution in xylene of C 14-CQ, mono and di-alkyl salicylic acids containing some unreacted 100 alkyl phenol, 5 % (by weight of the acid solution) of methanol and four equivalents of calcium hydroxide per equivalent of alkyl salicylic acid was charged into the first reaction vessel in which the temperature of 105 the slurried reaction mixture was raised to 600 C and maintained at that temperature for 1 hour, with constant vigorous stirring. The resulting mixture, which contained basic calcium alkyl salicylates of about 50 % 110 basicity, was then passed to the surge vessel from which it was fed continuously into the second reaction vessel in which the highly basic product was Droduced, in accordance with the invention, by forming calcium 115 carbonate in situ in the reaction mixture by bubbling in carbon dioxide with constant vigorous stirring The feed rate of the reaction mixture from the surge vessel to the second reaction vessel was 0 35 volumes per 120 second and carbon dioxide was bubbled through at hte rate of 6 9 volumes per second. the reaction mixture being maintained at S C Reaction mixture was withdrawn continuously from the second reaction vessel 125 786,167 at a rate such that the average residence time therein was -i hour. A highly basic product having a basicity of about 208 % was obtained The reaction mixture was worked up in the manner described in Example I to give a mineral oil concentrate having excellent blend stability with lubricating oils. EXAMPLE IV. The continuous process of Example III was repeated using 10 %, by weight of the acid solution, of methanol and a reaction temperature of 60 65 ' C in both reaction vessels The reaction mixture was fed from the surge vessel to the second reaction vessel at the rate of O 51 volumes per second and carbon dioxide was fed thereto at the rate of 8 3 volumes per second. A highly basic product having a basicity of about 2020 % O was obtained The reaction mixture was worked Un in the manner described in Example I to give a mineral oil concentrate having excellent blend stability with lubricating oils. The various highly basic calcium alkyl salicylates produced in accordance with the foregoing Examples I to IV were subjected to engine performance tests as additives in Cardon HV 1 170 base lubricating oil which is a mineral lubricating oil having a viscosity

of about 170 seconds Redwood 1 at 1400 F. and a high viscosity index Good results were obtained in the Chevrolet engine L-4 test which is described in the "Co-ordinating Research Council Handbook" published in 1946 on page 394 In addition these highly basic calcium alkyl salicylates were found to have excellent compatibility and blend stability at 1000 C with a number of different lubricating oils both in the absence and in the presence of other additives, for example octol formol and Anglamol 304 (the name "Anglamol" is a Registered Trade Mark). EXAMPLE V. A mixture of highly basic calcium alkyl salicylates (Ci 4-C,, mono and di-alkyl salicylates) was prepared using a reaction vessel fitted with a stirrer, a reflux condenser and means for circulating a mixture of carbon dioxide and air through the reaction mixture. At the commencement of the process 1,000 parts by weight of a 70 % solution of alkylsalicylic acids (C 14-C 1, mono and di-alkyl salicylic acids containing some unreacted alkyl phenol and the solution having an acid value of 57 mg KOH/g) in xylene were placed in the reaction vessel together with 10 %, by weight of the acid solution, of methanol (i e 100 parts by weight) and 532 parts by weight of calcium hydroxide (i.e 14 equivalents per equivalent of alkyl salicylic acids) The resulting mixture was stirred for 30 minutes during which the temperature rose to 30 C A mixture of air and carbon dioxide containing 40 %' (vol) of carbon dioxide was then circulated through the reaction mixture, at the rate of about 300 litres/hour, the reaction mixture being vigorously stirred ( 1800 r p m) and carbon dioxide being added to the cycling gas at the same rate as carbon dioxide was absorbed by the reaction mixture The absorption was continued for 34 minutes during which time the reaction mixture absorbed 67 litres of carbon dioxide and its temperature rose from 30 to 60 C The mixture was then stirred for 24 hours before diluting with xylene and centrifuging to remove the untreated solids The resulting liquid was distilled to remove the methanol, the water produced in the reaction and some of the xylene The remaining xylene solution was filtered and the xylene removed by distillation leaving the highly basic calcium alkylsalicylates. The highly basic product was found to have a basicity of about 512 %; its total base and acid contents being 5 12 and 0.836 millbequivalents per gram rsepectively. EXAMPLE VI. The process of Example V was repeated using 575 parts by weight of the 70 %O acid solution, 517 parts by weight of methanol, t)5 58 parts of water and 88 Darts of calcium hydroxide, ( 4 equivalents per equivalent of alkyl salicylic acids) The reaction mixture was first

stirred for 30 minutes during which time the temperature rose to 25 C, where luo upon a 20 % carbon dioxide/air mixture was circulated through the reaction mixture at the rate of 600 litres/hour for 16 minutes. During this period 12 litres of carbon dioxide were absorbed and the temperature 11 Xu 3 of the reaction rose to 32 C The reaction mixture was stirred for a further 24 hours and the unreacted solids removed by centrifuging The remaining liquid separated into two phases and the lower xylene phase con I 10 taining the highly basic calcium alkyl salicylates was distilled to remove methanol vat er and some xylene The remaining xylene solution was filtered, a quantity of spindle oil was added and the remaining 11 xylene was then removed leaving a concentrated spindle oil solution of highly basic calcium alkyl salicylates having a basicity of 226 '. EXAMPLE VII 12 " The process of Example V was repeated using 971 parts by weight of the acid solution, 97 Darts by weight of methanol and 151 parts by weight of calcium hydroxide ( 4 equivalents per equivalent of alkyl 1 '-l salicylic acids) The reaction mixture was. XZSi 1 W__ _ _ _ (j 5 e S(" 786,167 thenates in oil The basicity of the product was about 1000 %. EXAMPLE X. 66 parts by weight of naphthenic acids having an acid value 170 mg KOH/g were dissolved in 600 parts by weight of xylene and were mixed with a slurry comprising 72.7 parts of barium oxide and 70 parts of methanol in a reaction vessel as described in Example I After mixing with continuous high speed stirring for 2 hours the system was flushed free from air and 0 323 cu ft of carbon dioxide at 100 cm Hg. pressure and 20 C was bubbled through the reaction mixture during a period of 12 minutes The temperature during the carbon dioxide treatment was about 30 ' C. The resulting reaction product was then filtered at room temperature through a filter precoated with "Clarcel" filter aid to remove suspended solids and the resulting xylene solution of highly basic barium naphthenates was found to have a basicity of 252 %. heated to 50 C and stirred at this temperature for 5 minnutes A 20 % carbon dioxide/ air mixture was circulated through the reaction mixture at the rate of 600 litre/ hour for 43 minutes During this period the mixture absorbed 20 litres of carbon dioxide The reaction mixture was stirred for 24 hours and the resulting highly basic calcium alkyl salicylates were obtained in the manner described in Example V The product had a basicity of 222 %. EXAMPLE VIII. The process of Example V was repeated using a 35 % solution in xylene of C 1 -C 18 mono and di-alkyl salicylic acids the solution having an

acid value of about 30 m g. KOH/g 1105 parts by weight of acid solution, 57 5 parts by weight of methanol and 87.5 parts by weight of calcium hydroxide ( 4 equivalents per equivalent of alkyl salicylic acids) were mixed together for 30 minutes A 20 % carbon dioxide/air mixture was then circulated through the reaction mixture for 20 minutes during which time 12 2 litres of carbon dioxide were absorbed The reaction mixture was then stirred for 24 hours and the highly basic calcium alkyl salicylates, which were obtained in the manner described in Example V, had a basicity of 185 %. The process of the present invention is also equally applicable to the preparation of other oil-soluble highly basic polyvalent metal salts of for example naphthenic acids and petroleum sulphonic acids, i e sulphonic acids or mixtures thereof which are derived directly from petroleum products, as is illustrated by the following Examples:- EXAMPLE IX. 3.3 kilograms of naphthenic acids having an acid value 170 mg /KOH per gram were dissolved in 7 6 gallons of xylene and were mixed with a slurry comprising 5 92 kilograms of calcium hydroxide and 7 kilograms of methanol in the reaction vessel used in Example 1 After mixing with continuous high speed stirring for 1 hour at 600 C, the system was flushed free from air and about 40 cubic feet of carbon dioxide was bubbled through the reaction mixture over a period of 4 hours The temperature during the carbon dioxide treatment was 35-40 ' C. The resulting reaction product was then filtered at room temperature through a filter pre-coated with "Clarcel" (the name "Clarcel" is a Registered Trade Mark) filter aid to remove suspended solids and the clear filtrate was then added to a light hydroCO carbon oil base and the methanol and xylene were removed by distillation, together with the water formed during the reaction, to give a solution o F highly basic calcium naphEXAMPLE XI. A mineral oil solution of highly basic calcium petroleum sulphonates was prepared from the acid oil obtained by 90 sulphonating a solvent refined lubricating oil having a viscosity of about 65 seconds Redwood 1 at 140 ' F and a viscosity index of about 95, the acid oil having an acid value of 21 5 m g /KOH 95 per gram and a sulphonic acids content of 12.5 % by weight. The acid oil was neutralised with excess calcium hydroxide at 45 ' C, the calcium hydroxide being added in the form of a 100 slurry with 99 % methanol so as to yield a mixture containing 5 equivalents (based on the sulphonic acids content of the acid oil) of free calcium hydroxide and 10 %, by weight of the acid oil, of methanol Alto 105 gether 5 5 % of calcium hydroxide by weight of the acid oil was added. The resulting mixture was then stirred vigorously ( 3000 r p m) at

40-42 ' C for 1 hour during which time carbon dioxide 110 was bubbled through the mixture, about 1.8 % of carbon dioxide, by weight of the acid oil, ( 75 % equivalent based on the free calcium hydroxide) being absorbed The reaction product yielded on filtration a 115. 12.5 % mineral oil solution of basic calcium petroleum sulphonates which was of good colour and had a viscosity of 94 centistokes at 100 ' F and a basicity of 200 %. EXAMPLE XII 120 The process of Example V was repeated using 100 parts by weight of the acid solution, 250 parts by weight of acetone, and 144 parts of calcium hydroxide ( 4 equivalents per equivalent of alkyl salicylic acids) 125 786,167 9 y An 80 % carbon dioxide/air mixture was circulated through the reaction mixture at the rate of 60 litres per hour for 75 minutes. During this period 22 4 litres of carbon dioxide were absorbed The unreacted solids were removed by centrifuging, and the liquid was distilled to remove acetone, water and some xylene The remaining solution was filtered, a quantity of spindle oil was added and the remaining xylene was removed leaving a concentrated spindle oil solution of highly basic calcium alkyl salicylates having a basicity of 151 %. EXAMPLE XIII. A highly basic additive for lubricating oils was prepared in the form of a mixture of basic calcium salts of alkyl salicylic acids and petroleum sulphonic acids The starting materials comprised:(a) 47 % basic calcium petroleum sulphonates obtained by sulphonating a lubricating oil fraction having a viscosity of about 400 SUS at 100 ' F and converting the resulting sulphonic acids into the calcium salts via the sodium salts: the 470 ' basic calcium salts had a calcium content of 2.52 % by weight, a sulphonate content of 0.86 m eq/gram and an oil content of about 50 % and (b) 60 % -basic calcium alkyl salicylates (C 14-C,, mono, and di-allkyl salicylates) having a calcium content of 2 26 % by weight, a salicylate content of 0 705 m eq/ gram and an oil content of about 60 %. 200 parts by weight of the 47 % basic calcium sulphonates and 200 parts by weight of the 60 % basic calcium alkyl salicylates were dissolved in 400 parts by weight of xylene A slurry comprising 150 parts by weight of lime (calcium hydroxide content 97 %) in 80 parts by weight of methanol was then added to the xylene solution and the resulting mixture heated to 60 C with stirring. Carbon dioxide was then bubbled through the mixture which was maintained at 60 C. with constant stirring until the mixture had absorbed 36 3 parts by volume of carbon dioxide The temperature of the reaction mixture was then raised and the methanol and reaction water distilled off,

together with some of the xylene, until the bottom temperature was 1350 C The residue, which still contained xylene, was centrifuged to remove excess lime and any solid calcium carbonate formed during the reaction and 100 parts by weight of mineral oil added and the resulting mixture was distilled under vacuum to give 628 5 Darts by weight of a mineral oil concentrate of the mixed highly basic calcium sulphonates and alkyl salicylates, having a basicity of 1160 %, a calcium content of 5 48 m eq/gram, a sulphonate + salicylate content of O 435 m eq/ gram and a ratio of calcium to total acids of 12 6. ( 3.5


* GB786168 (A)

Description: GB786168 (A) ? 1957-11-13

Photographic emulsions

Description of GB786168 (A) Translate this text into Tooltip



PATENT SPECIFICATION Inventor: GEORGE DE WINTER ANDERSON Date of filing Complete Specification: Oct 26, 1955. Application Date: Nov 4, 1954.

No 31909/54. -1 - Complete Specification Published: Nov13, 1957. Index at acceptance:-Classes 2 ( 3), C 2 (A 2: A 14: R 16); 2 ( 4), DIQ; and 98 ( 2), C 3 International Classification:-CO 7 c C 09 b G 03 c. COMPLETE SPECIFICATION Photographic Emulsions We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, of Imperial Chemical House, Millbank, London, S W 1, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - This invention relates to photographic emulsions and more particularly to photographic emulsions containing a sensitiser and a supersensitiser. It is known ithat the sensitising effect of a single sensitiser in a photographic emulsion does not increase continuously as the quantity of the sensitiser is increased but that the effect passes through a maximum and then decreases. It is also lknown that with certain cyanine dyestuff sensitisers an enhanced sensitising effect can be obtained by adding a supersensitiser in addition Ito the sensitiser These supersensitisers do not however give beneficial results with all classes of sensitising dyestuffs, the effect of a particular supersensitiser being usually restricted to a relatively small class of sensitisers, and no supersensitising effect has hitherto been described for emulsions sensitised with certain sensitising dyestuffs, as hereinafter defined. With certain sensitising dyestuffs, as hereinafter defined, the sensitising effect on a photographic emulsion increases normally with increasing concentration of the dyestuff up to a maximum, but if the concentration of dyestuff is further increased the sensitising effect rapidly decreases owing to the pronounced desensitising effect of the excess dyestuff We have now found that certain dicyano compounds exert a supersensitising effect on these sensitising dyestuffs, especially by inhibiting this desensitising effect of excess sensitiser. According to our invention we provide a gelatino-silver halide emulsion containing a sensitising dyestuff of the formula: wherein m is O or 1, R is an alkyl or allyl radical and X represents the atoms required to complete a 5 or 6-membered heterocyclic ring which may form part of a condensed ring system, and a dicyano compound of the 50 formula: Cs = CH (CH = CH), NH Ar wherein N is 0, 1 or 2 and Ar is an aryl radical, such that the combination of the sensitising dyestuff and the dicyano compound gives a supersensitising effect. The alkyl or allyl radical in the sensitising dyestuff may be for example one containing from one to five carbon atoms such as methyl,

ethyl, allyl, iso or normal propyl, butyl or amyl radicals and the heterocyclic ring may be for example a quinoline, pyridine, benzoxazole, thiazole, thiazoline, benzthiazole, benzselenazole, indolenine or benzimidazole ring These rings may carry nuclear substituents The sensitising dyestuffs used in the emulsion of our invention may be made by condensing a quaternary salt of a heterocyclic nitrogen ring compound carrying a methyl group on a carbon atom, in the or y position with respect to the nuclear nitrogen atom, for example quinaldine ethiodide, with diphenylformamidine in the presence of acetic anhydride and treating the condensation product with malonic dinitrile in ethanol solution in the presence of triethylamine or in pyridine solution in the presence of piperidine. In our co-pending Application 31910/54 (Serial No 786,169) there are described and claimed new photographic sensitisers of the formula: R A C N -C 11 'C CH-CH=C CNN R R (CH = H-CH C wherein R stands for an alkyl radical, and A 786,168 2 786,168 and B stand for hydrogen atoms or for ithe atoms necessary to complete a benzene ring which is fused to the heterocyclic ring, which are obtained by heating malonic dinitrile with a quaternary salt of the formula:R A-C-N 1 CHC =C H -NH C 6 H 5 B C-N-,e R X or an N-acyl derivative thereof, wherein R, A and B have the meanings stated and X stands for halogen, sulphonic acid or sulphuric ester in the presence of an organic amine. The dicyano compounds used in the process of our invention may be made by condensing malonic dinitrile with a compound of the formula C 6 H 5 N= CHI-(CH=CH),2-NH Ar where N and Ar have the meaning given above for example diphenylformamidine, y-anilinoacralaniline or glutaconic aldehyde dianil. The sensitising dyestuff and the dicyano compound may be added to the gelatino-silver halide emulsion before coating on a substrate or if desired either or both of these compounds may be introduced into the emulsion after coating by treating the coated material with a solution of the compound or compounds. The particular dicyano compound which gives the best result with a particular sensitising dyestuff and the best proportions of the two compounds to give any desired effect can readily be found by simple experimental trials but an especially valuable combination is that obtained by adding N-( 2: 2-dicyanovinyl)aniline to the sensitising dyestuff 4-( 1-ethyl1: 2 dihydroquinolylidene 2) 2 cyano2-butenontitrile This sensitising dyestuff is a valuable green sensitiser but the sensitising effect rises rapidly to a maximum with increasing concentration of dyestuff and then decreases rapidly with a further increase in concentration of dyestuff Accorlingly some difficulty is experienced in obtaining consistent and reproducible sensitising effects with this dyestuff under manufacturing conditions

In combination with the dicyano compound mentioned, the sensitising effect remains at the maximum for a wide range of concentrations of dyestuff and a consistent and reproducible sensitising effect can readily be obtained. The invention is illustrated but not limited by the following Examples in which the parts are by weight:EXAMPLE 1 To 100 parts of a silver chlorobromide emulsion containing 88 % of gelatine, 17 % of silver chloride and 0 55 % of silver bromide there are added 6 parts of a 0 05 %,', solution of 4-( 1-ethyl-1: 2-dihydroquinolylidene-2-)-2cyano-2-butenonitrile in methanol and 10 parts of a 0 05 % solution of N-( 2:2-dicyanovinyl)aniline in methanol The mixture is stirred for 20 minutes at 40 C. The relative speed of the emulsion compared with that of a comparable emulsion made up without the addition of the methanolic solution of N-( 2:2-dicyanovinyl)aniline is determined by coating the two emulsions on glass plates, exposing the plates to yellow light behind a step-wedge, developing and fixing The relative speeds are as follows: Emulsion without N-( 2:2-dicyanovinyl)aniline 100 Emulsion with N-( 2: 2-dicyanovinyl)aniline 320 The N-( 2: 2-dicyanovinyl)-aniline used in this Example may be made as follows: 6.6 parts of malonic dinitrile and 21 6 parts of diphenylformamidine are heated together to C during 15 minutes and the mixture is maintained at this temperature for a further -15 minutes The reaction product is ground up with 60 parts of benzene, filtered off and washed on the filter with 60 parts of benzene. The light brown powder so obtained is crystallised from 1,000 parts of ethanol and obtained in the form of colourless needles, melting point 246-247 C. EXAMPLE 2 To 100 parts of the silver chlorobromide emulsion used in Example 1 there are added 8 parts of a 0 05 l% solution of 4-( 1-methyl-1: 2dihydroquinolylidene 2) 2 cyano 2 90 butenonitrile in methanol and 10 parts of a 0.05 %,o solution of N-( 4:4-dicyanobuta-1:3dienyl-l)aniline in methanol The mixture is stirred for 20 minutes at 40 WC and coated on a film base 95 The N-( 4: 4-dicyano-buta-1: 3-dienyl-1)aniline used in this Example may be prepared as follows: A mixture of 2 2 parts of malonic dinitrile, 8.63 parts of y,-anilinoacralaniline hydro 100 chloride and 80 parts of methanol is stirred and heated to its boiling point under a reflux condenser 3 7 parts of triethylamine are added and the mixture is then stirred and boiled under a reflux condenser for 10 minutes The 105 reaction product is filtered off and washed with parts of methanol The small orange coloured crystals so obtained are boiled with benzene,

filtered off and then crystallised rapidly from 450 parts of glacial acetic acid 110 The orange needle-shaped crystals so obtained melt at 141-145 "C. EXAMPLE 3 To 100 parts of a silver iodobromide emulsion containing 8 % '0 of gelatine, 4 8 l% of silver 115 bromide and 0 31 % of silver iodide there are added 6 parts of a 0 05 %,'0 solution of 4-( 1ethyl 6 ethoxy 1:2 dihydroquinolylidene-2)-2-cyano-2-butenonitrile in methanol and 10 parts of a 0 05 % solution of N-( 6: 6 120 dicyanohexa 1: 3: 5: trienyl 1) aniline in methanol The mixture is stirred for 20 minutes at 400 C and coated on a film base. The N-( 6: 6-dicyano-hexa-1: 3: 5-trienyl1)-aniline used in the Example may be pre 125 pared as follows: 786,168 786,168 8.3 parts of glutaconic aldehyde dianilide are dissolved in 80 parts of methanol and the solution is added to a stirred solution of 2 2 parts of malonic dinitrile 'in 4 parts of methanol The mixture is boiled under a reflux condenser for 10 minutes, cooled and filtered and the residue on the filter is washed with 40 parts of methanol and 35 parts of dry ether. The product is boiled with 80 parts of benzene and filtered hot, and ithe residue again boiled with 80 parts 'of benzene and filtered hot The residue is crystallised from methanol and obtained in the form of purple crystals, melting at 174-176 C The product decomposes on prolonged boiling with methanol.


5756 5760.output

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