4256 4260.output

* GB784663 (A)

Description: GB784663 (A) ? 1957-10-16

Improvements in or relating to single-sideband radio transmission systems

Description of GB784663 (A)

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PATENT SPECIFICATION 784,663 Date of Application and filing Complete Specification: Oct 21, 1955 No 30158/55. Application made in Netherlands on Oct 25, 1954. Complete Specification Published: Oct16, 1957. Index at acceptance:-Class 40 ( 5), L( 15 C 3:27 C). Internationai Classification:-HO 3 c. COMPLETE SPECIFICATION Improvements in or relating to Single-sideband Radio Transmission Systems We, PHILIPS ELECTRICAL INDUSTRIES LIMITED, of Spencer House, South Place, Finsbury, London, E C 2, 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: - The invention relates to single-sideband radio transmission systems comprising a transmitter and a receiver for the transmission of speech

signals, in which the transmitter and the receiver are provided with a band compresser and a band expander respectively Such single-sideband systems may be used advantageously in carrier-wave telephone systems, in order to increase the capacity of speech transmission. The present invention has for its object to provide a comparatively simple single-sideband system of the aforesaid kind, which provides an economy of the band-width required for the transmission and good transmission quality, more particularly with respect to the intelligibility and the identification of the voices. In accordance with the invention, the single-sideband signal is fed to an envelope detector in order to obtain a signal envelope and also through a band compresser, to an amplitude modulator controlled by the signal envelope obtained from the envelope detector, the output signal of the amplitude modulator being transmitted to the receiver, which, in order to re-obtain the initial single-sideband signal, is provided with a band expander. In order to further improve the transmission quality, the speech signal, in one form of the invention is converted into single-sideband signals representing different formant ranges, at least one of the lower formant ranges being transmitted by means which are themselves in accordance with the invention. In order that the invention may readily be carried into effect, four embodiments will now be described in detail with reference to the accompanying drawings in which:Figs 1 and 2 show a transmitter and a receiver respectively for use in a single-side 50 band radio transmission system; Figs 3 and 4 show a variant of the singlesideband transmitter and receiver shown in Figs 1 and 2, and Figs 5 and 6 show one embodiment of a 55 transmitter and a receiver respectively, in which the speech signal is converted into single-sideband signals representing different formant ranges; and Figs 7 and 8 show a transmitter and re 60 ceiver having improvements on the transmitter and the receiver shown in Figs 5 and 6. The transmitter and the receiver shown in Fig 1 form part of a carrier-wave telephone system suitable for the transmission of speech 65 signals by means of single-sideband modulation. In the transmitter shown in Fig 1, the signals obtained from a microphone 1 are supplied through a filter 2 passing the speech 7 ( signals of 300 to 3200 c/s, subsequently to amplification in an amplifier 3, to a single. sideband modulator 4, having an oscillator operating at 60 kc/s, connected thereto, and a single-sideband filter 6, which passes 75 the upper sideband ( 60 3 to 632 kc/s) The single-sideband signal thus obtained is fed to a band compressor 7 which is connected by way of a filter 8 and a group modulator 9 with an oscillator 10 and an output

filter 11 80 to a transmission cable 12. The single-sideband signal in the band compresser 7 is supplied in order to obtain a signal envelope, to an envelope detector 13, and also by way of a band compresser 15 to 85 an amplitude modulator 16, which is governed by the signal envelope obtained from the envelope detector 13 In practice it has been found to be favourable to provide a limiter 14 before the band compresser 90 784,663 The band compresser 15 is constructed in the form of a frequency-division circuit, as a counting circuit arrangement comprising a counting tube, provided with a suitable output filter to suppress unwanted distortion products If the division factor is 10, a singlesideband signal is obtained from the singlesideband signal of 60 3 to 63 2 kc/s, the said signal lying in the frequency band from 6 03 to 6 32 kc/s, the bandwidth of which ( 0 29 kc/s) is reduced in this manner with respect to the bandwidth of the initial single-sideband signal ( 2 9 kc/s) by a factor 10. In the amplitude modulator 16, the singlesideband signal from 6 03 to 6 32 kc/s, of approximately constant amplitude, is modulated in amplitude by the output signal of the envelope detector 13, which is constituted by an amplitude detector 17 and a next-following low-pass filter 18 having a cut-off frequency of 300 c/s and supplied through the group modulator 9 to the transmission cable 12. Compared with the initial single-sideband signal, a material economy in bandwidth is thus obtained, whilst the speech signal thus transmitted by band compression can be reproduced at the receiver end with a fairly good quality. In order to improve the transmission quality with respect to the property of the limiter 14 to pass those speech components of the components supplied thereto which have a larger amplitude better than the other components, it has been found to be favourable to supply the speech signals from the microphone I by way of a pre-emphasis network 19 to the single-sideband modulator 4 The pre-emphasis network 19 then provides an amplitude equalization of tha transmitted signals, so that in the limited single-sideband signal, the higher speech frequency components of the speech frequency band of for example 2000 to 3200 c/s are also fairly well represented. Instead of using the frequency division arrangement shown in this embodiment, use may be made of other frequency division arrangements Thus, use may, for example, be made of a counting circuit comprising a plurality of pulse generators exciting one another in succession, each of these pulse generators producing a division by a factor 2, that is a so-called binary counting circuit. For the frequency division, use may furthermore be made advantageously of an oscillator tuned approximately to the desired subharmonic of the carrier-frequency of the single-sideband signal and synchronized by

the single-sideband signal, as described in the Proceedings of the I R E of December 1944, pages 730 to 737. Fig 2 shows the receiver co-operating with thile transmitter shown in Fig 1. The incoming signals from a transmission cable 12 are supplied, subsequently to highfrequency amplification in an amplifier 20, by way of a group demodulator 21, comprising an oscillator 22, connected thereto, and an output filter 23, to a band expander 70 24, feeding an output filter 25 and converting the single-sideband signal transmitted by band compression into the initial frequency band The single-sideband signal thus obtained is demodulated in a single-sideband de 75 modulator 26, comprising a local oscillator 27 and a filter 28, passing only the speechfrequency band from 0 3 to 3 2 kc/s and supplied through a de-emphasis network 29 and a low-frequency amplifier 30 to a reproduc 80 ing device 31. In order to re-obtain the initial single-sidesignal, the incoming single-sideband signal is supplied in the expander 24 on the one hand to an envelope detector 32 which is consti 85 tuted by an amplitude detector 33 and a lowpass filter 34, having a cut-off frequency of for example 300 cls, and on the other hand via a limiter 35 and a band expander 36 to an amplitude modulator 37, which is govern 90 ed by the signal envelope obtained from the envelope detector 32. The band expander 36 is constituted by a frequency multiplication circuit, comprising a suitable output filter to suppress unwanted 95 distortion products To this end, use may be made of frequency multiplication circuits of the kind used with frequency-modulation transmission as described for example, in United Kingdom Patent Specifications Nos 100 663,619 and 652,717 If, in the embodiment shown, the frequency band of the single-sideband signal obtained from the limiter 35 is 6.03 to 6 32 kc/s, a single-sideband signal is obtained in the initial frequency band from 105 60.3 to 63 2 kc/s After frequency multiplication by a factor 10 in a frequency multiplier 36 and amplitude modulation with the signal envelope in the amplitude modulator 36, this signal yields approximately the initial single 110 sideband signal The intelligibility of the transmitted conversation is, in this case, satisfactory. In the system shown, transit time differences between the envelope channel and the 115 band-compression or the band-expansion channel may produce a reduction of the transmission quality If these transit time differences are a source of interference, one of these channels may be provided with a 120 network equalizing the transit time differences. A particularly simple band expansion arrangement is obtained by using a Class C amplifying stage, which is controlled by the 125

frequency-compressed single-sideband signal. In this case, a suitable output filter permits of obtaining approximately the initial singlesideband signal. Figs 3 and 4 show a variant of the single 130 784,663 sideband system described above. Fig 3 shows the transmitter and Fig 4 shows the receiver, corresponding elements are designated by the same reference numerS als. The transmitter shown in Fig 3 differs from the transmitter shown in Fig 1 in the construction of the band compressor 7. In this system the compression is obtained by supplying the single-sideband signal taken from the limiter 14 to the frequency discriminator 38, which is coupled with a frequency modulator 40, connected to an oscillator 39, in this example a reactance tube This band compressor 38, 39, 40 is constructed so that a frequency variation of the limited singlesideband signal by way of the frequency discriminator and the frequency modulator 40 produces a correspondingly smaller variation of the oscillator frequency In this case a frequency variation of the limited singlesideband is reduced to a ten times smaller variation of the oscillator frequency, i e, the band compresser factor is 10. Fig 4 shows the corresponding single-sideband receiver, comprising a band expander constituted by a frequency discriminator 41 and a subsequent frequency modulator 42, which is coupled with a local oscillator 43. This band expander 41-43 thus corresponds in construction to the band compressor 38-40 used in the transmitter However, this band expander 41-43 is proportioned so that a frequency variation of the limited singlesideband signal produces a correspondingly larger variation of the oscillator frequency. In the example shown, the band expansion factor is chosen to be 10 in order to re-obtain the initial single-sideband signal. In the arrangement shown, small differences between the band compression factor and the band expansion factor appear to be permissible, which is of particular importance for a simple construction of the band compressor and the band expander. After the foregoing, it will be obvious that the transmitter shown in Fig 1 may be used in conjunction with a receiver shown in Fig. 4 or else the transmitter shown in Fig 3 may be combined with the receiver shown in Fig. 2. A further improvement in transmission quality may be obtained by converting the speech signal into single-sideband signals representing different formant ranges, at least one of the lower formant ranges

being transmitted by means of the single-sdeband system as described above. Such a single-sideband system is shown in Figs 5 and 6; Fig 5 shows the transmitter and Fig 6 shows the receiver. In the transmitter shown in Fig 5, the lowfrequency amplifier is connected to a band compresser 44, comprising three parallelconnected channels 45, 46, 47 with input filters 48, 49, 50, passing respectively formant ranges from 300 to 800 c/s, 800 to 2000 c/s and 2000 to 3200 c/s Each of these parallel-connected channels comprises the cascade combination of a single-sideband 70 modulator 51, 52, 53, a single-sideband filter 54, 55, 56, a limiter 57, 58, 59, a frequency division stage 60, 61, 62 and an output filter 63, 64, 65, which are connected in parallel with the group modulator 9 The channel 45, 75 associated with the lowest formant range, from 300 to 800 c/s, comprises furthermore a modulator stage 66, connected to the frequency division stage 60 controlled by the output voltage of the envelope detector, con 80 stituted by an amplitude detector 67 and a subsequent low-pass filter 68, having a cutoff frequency of for example 300 c/s. To the modulators 51, 52, 53 are connected oscillators 69, 70 respectively, having a fre 85 quency of 57 kc/s and 60 kc/s to obtain the amplitude modulation of the speech frequencies lying in the various formant ranges: the single-sideband filters 54, 55, 56 allow the upper sidebands in frequency bands from 90 57.3 to 57 8 kc/s, 60 8 to 62 kc/s and 62 to 63.2 kc/s respectively to pass These singlesideband signals are divided after limitation, in the frequency division devices 60, 61, 62 by a factor 10 and, after division, they pro 95 duce single-sideband signals in the frequency bands from 5 73 to 5 78 kc/s, 6 08 to 6 2 kc/s and 6 2 to 6 32 kc/s respectively The frequency space introduced between the single-sideband signal from 5 73 to 5 78 kc/s 100 and the single-sideband signal from 6 08 to 6.2 kc/s (i e, 0 3 kc/s) is used for the transmission of the amplitude modulation of the single-sideband signal from 5 73 to 5 78 kc/s. In the example shown, the output filter 63 105 of the channel 45 has a minimum pass-band from 5 73 to 6 08 kc/s. The output voltages of the channels 45, 46, 47 (only the signal envelope of the channel 45 is transmitted) are transmitted via the 110 group modulator 9 and the output cable 12 to the receiver shown in Fig 6. In the receiver shown in Fig 6, the output voltage of the group demodulator 21, in order to re-obtain the initial single-sideband 115 signal, is supplied to a band-expander 71, comprising three parallel-connected channels 72, 73, 74, which correspond to the band compresser channels 45, 46, 47 respectively in the transmitter 120 Each of these channels 72, 73, 74 comprises the cascade connection of

the frequency-transformer stage 75, 76, 77, a filter 78, 79, 80, a limiter 81, 82, 83, a frequency multiplier 84, 85, 86, an output filter 87, 88, 125 89, and the channel 72, associated with the lowest formant ranges, comprises also an amplitude modulator 90, which is controlled by the output voltage of an envelope detector 91, connected to the filter 78, and the sub 130 784,663 sequent low-pass filter 92, having a cut-off frequency of 300 c/s. To the frequency transformer stages 75, 76, 77 are connected oscillators 93 and 94 respectively, producing frequencies such that the single-sideband signal of the lowest formant range with respect to the single-sideband signals representing the further formant ranges is shifted into its initial position. In the example shown, the single-sideband signal from 6 03 to 6 08 kc/s, which is amplitude-modulated by the signal envelope, is produced at the output of the filter 78, having a pass-band of 6 03 to 6 08 kc/s, whilst the filters 79 and 80 pass the single-sideband signals of constant amplitude lying in the adjacent frequency bands from 6 08 to 6 2 kc/s and 6 2 to 6 32 kc/s These single-sideband signals yield, after frequency multiplication by a factor of 10 in the frequency multipliers 84, 85, 86, the single-sideband signals in the initial formant ranges from 60 3 to 60 8 kc/s, 60 8 to 62 kc/s and 62 to 63 2 kc/s. The single-sideband signal from 60 3 to 60 8 kc/s, after amplitude modulation with the signal envelope in the amplitude modulator 90, is supplied, together with the singlesideband signals from 60 8 to 62 kc/s and 62 to 63 2 kc/s, to the single-sideband demodulator 26, from the output circuit of which the transmitted speech signal is obtained. In order to avoid interference signals during the speech intervals in the transmission channels for the higher formant ranges, it may be advantageous to provide a threshold device in these channels. In this arrangement, the speech signal is characterized by the three components in the various formant ranges, which determine together the speech signal with a satisfactory accuracy By using the system described above, an improvement in the transmission quality is obtained. The dynamic power of the speech components, transmitted with constant amplitude, in the formant ranges from 800 to 2000 c/s and 2000 to 3200 c/s may be introduced at the receiver end, in a simple manner, by including an amplitude modulator 95 and 96 in each of the channels between the frequency multiplier 85 and 86 respectively and the output filter 88 and 89 respectively, this modulator being controlled by the output voltage of the envelope detector 91 and 92 respectively of the channel 72 The dynamic power of the speech components in the formant ranges from 800 to 2000 c/s and 2000 to 3200 c/s appears to follow

that of the lowest formant range. If desired, instead of using the envelope of the speech component of the formant range from 300 to 800 c/s, use may be made of that of the formant range from 800 to 2000 c/s. A further improvement in the transmission quality may be obtained by using the system shown in Figs 7 and 8 This improvement consists in that the speech components of the various formant ranges are united in the correct intensity ratio 70 In the transmitter shown in Fig 7 the output voltages of the frequency multipliers 61, 62 in the band compression channels 46, 47, associated with the higher formant ranges are supplied to amplitude modulators 97, 98 75 which are controlled by the output voltage of an amplitude detector 99 and 100 respectively, connected to the output circuit of the single-sideband filter 55 and 56 respectively and to a subsequent low-pass filter 101 and 80 102 respectively, having a low cut-off frequency of 40 c/s The level of the output signals of the channels 46, 47 is then determined by the level of the speech components supplied to the channels 46, 47 85 In order to reproduce the speech components of the various formant ranges in the correct intensity ratio at the receiver end (see Fig 8) each of the input filters 79, 80 of the channels 73 and 74 respectively is connected 90 to an envelope detector, constituted by an amplitude detector 103 and 104 respectively and a low-pass filter 105 and 106 respectively, having a cut-off frequency of 40 c/s, the output voltage of which controls a govern 95 ing valve 107 and 108 respectively connected after the amplitude modulator 95 and 96 respectively in order to control the level. In order to avoid a reaction of the level of the channel 72 on the signal levels of the 100 channels 72 and 74 the signals from the envelope detector 91 in the channel 72 are supplied to the amplitude modulators 95 and 96 respectively via an automatic volume-control amplifier 109 the automatic volume con 105 trol-voltage being obtained by rectification of the signals supplied to the channel 72. For level control, the governing tube 107 or 108 may, be connected between the amplifier 109 and the amplitude modulator 95 or 110 96 respectively The dynamic power control and the level control in the channels 73 and 74 substantially do not influence one another. since they are operative in different frequency ranges 115 By using this single-sideband system a very satisfactory speech quality is obtained. In order to improve the economy in bandwidth, in the single-sideband system the band compression factor may be raised and/or 120 the frequency band of the envelope signal may be reduced For example band compression factors from 40 to 50 may be used and an economy of the band of the envelope to 100 c/s or even 40 c 1 S is possible 125

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* GB784664 (A)

Description: GB784664 (A) ? 1957-10-16

Process for dyeing wool with metal complex dyestuffs

Description of GB784664 (A) Translate this text into Tooltip



PATENT SPECIFICATION 784,664 Date of Application and filing Complete Specification: Oct 26, 1955. No 30655/55. Application made in Germany on Oct 28, 1954. Comrhlits C,-; - ', Index Index The inventors of ths irnvention in te sense of being the ctual devisers within the Ieanrig o Sectio 16 of the Patents Act, 1949, are Walter Justus, Carl-Runpff-Strasse, 41, Leverl nsen-Bayeerkl Germa N y and lierbert Yi::pel Y, Roonstrasse 20, Le Verllwsen, Getra T, both of Geranf nationality' S THE PATENT OFFICE, 1 ith November, 1957 l'he present invention relates to the dyeing of wool; more particularly it concerns a process for dyeing wool with metal complex dyestuffs containing less than one atom of a complex-forming metal per molecule of a complex-forming dyestuff,

which may have a carboxyl group participating in the complex formation but no further acid, water-solubilising groups. In the dyeing of wool with the said metal complex dyestuffs satisfactory level dyeings may only be obtained without the application of auxiliaries if the wool is dyed from a neutral bath Since the neutral dyeing process may detrimentally affect the quality of the wool, it is preferable to apply the said metal complex dyestuffs in an acid bath, possibly at a p H 4-5; but this dyeing process requires levelling agents in order to produce level dyeings. It has now been found that surprisingly satisfactory effects can be obtained in dyeing wool with the aforesaid metal complex dyestuffs in the acid range, at a p H 4-5, by using levelling agents which are produced by the action of at least 30 mols of ethylene oxide on 1 mol of a compound containing a hydroxyl group or a primary or secondary amino group and having at least 3 carbon atoms Examples of compounds containing a hydroxyl group or a primary or secondary amino group are alcohols such as stearyl and oleyl alcohol, and amines such as cetylamine. It has further been found that these reaction products of ethylene oxide permit correction or brightening of uneven dyeings produced with the aforesaid metal complex dyestuffs by an after-treatment in an acid bath The subsequent levelling up of dyeings with the aforesaid dyestuffs makes the use of neutral or alkaline baths unnecessary. The advantageous effect of the levelling lPrice 3 s 6 d l DB 00130 if 1 ( 6) Iro 597 100 l 15 f 7 R mn me ixamples by the letters A, B, C, D, are further designated in the Table at the end of the Examples. EXAMPLE 1 60 12 Kilograms of all-wool gabardine piecegoods were dyed in a winch vat containing 400 litres of liquor, as follows: 240 Grams of the reaction product of 60 mols of ethylene oxide on 1 mol of oleyl 65 alcohol, 240 grams of 96 % sulphuric acid, 3000 grams of crystalline sodium sulphate, 60 grams of the dyestuff A, 36 grams of the dyestuff B and 45 grams of the dyestuff C were introduced into the liquor at 40 C, brought to 70 the boil within 45 minutes and boiled for two hours The p H value of the dyebath was 4 5 during the dyeing In this way the gabardine goods were dyed a level beige shade. EXAMPLE 2 75 Kilograms of all-wool worsted goods on reels were dyed in a dyeing machine containing 200 litres of liquor as follows: Grams of the reaction product of 55 mols of ethylene oxide on 1 mol stearyl 80 alcohol, 250 grams of 96 % sulphuric acid, 2000 grams of sodium sulphate, 50 grams of the dyestuff A and 10 grams of the dyestuff C were introduced into the liquor at 400 C, brought to the boil within 30 minutes, and 85 boiled for 20 minutes The steam was

then shut off, and at 85 C there were added to the dyebath 15 grams of the dyestuff A and 5 grams of the dyestuff C, whereupon the whole was brought again to the boil and boiled for a 90 further 20 minutes The p H value of the dyebath was 4 1 during the dyeing The reels of wool were dyed a level greenish grey shade. EXAMPLE 3. Kilograms of all-wool worsted goods on 95 reels were dyed in a dyeing machine containing 100 litres of liquor as follows: Grams of the reaction product of 50 thereof Z 8 -564 hl PATENT SPECIFICATION 784,664 Date of Application and filing Complete Specification: Oct 26, 1955. No 30655155. Application made in Germany on Oct 28, 1954. Complete Specification Published: Oct 16, 1957. Index at acceptance:-Class 15 ( 2), B 2 F. Index at acceptance:ication:-DO 6 p. COMPLETE SPECIFICATION Process for Dyeing Wool with Metal Complex Dyestuffs We, FARBENFABRIKEN BAYER ARTIENGESELLSCHAFT, a body corporate organised under the laws of Germany, of Leverkusen, Germany, 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: - The present invention relates to the dyeing of wool; more particularly it concerns a process for dyeing wool with metal complex dyestuffs containing less than one atom of a complex-forming metal per molecule of a complex-forming dyestuff, which may have a carboxyl group participating in the complex formation but no further acid, water-solubilising groups. In the dyeing of wool with the said metal complex dyestuffs satisfactory level dyeings may only be obtained without the application of auxiliaries if the wool is dyed from, a neutral bath Since the neutral dyeing process may detrimentally affect the quality of the wool, it is preferable to apply the said metal complex dyestuffs in an acid bath, possibly at a p H 4-5; but this dyeing process requires levelling agents in order to produce level dyeings. It has now been found that surprisingly satisfactory effects can be obtained in dyeing wool with the aforesaid metal complex dyestuffs in the acid range, at a p H 4-5, by using levelling agents which are produced by the action of at least 30 mols of ethylene oxide on 1 mol of a-compound containing a hydroxyl group or a primary or secondary amino group and having at least 3 carbon atoms Examples of compounds containing a hydroxyl group or a primary or secondary amino group are

alcohols such as stearyl and oleyl alcohol, and amines such as cetylamine. It has further been found that these reaction products of ethylene oxide permit correction or brightening of uneven dyeings produced with the aforesaid metal complex dyestuffs by an after-treatment in an acid bath The subsequent levelling up of dyeings with the aforesaid dyestuffs makes the use of neutral or alkaline baths unnecessary. The advantageous effect of the levelling lPrice 3 s 6 d 1 agents according to the invention may be con 50 siderably improved by the addition of watersoluble salts, such as for example sodium sulphate to the dyeing bath. Suitable ratios of dyestuffs, levelling agents and salt additives are given in the following 55 illustrative Examples The dyestuffs designated in the Examples by the letters A, B, C, D, are further designated in the Table at the end of the Examples. EXAMPLE 1 60 12 Kilograms of all-wool gabardine piecegoods were dyed in a winch vat containing 400 litres of liquor, as follows: 240 Grams of the reaction product of 60 mols of ethylene oxide on 1 mol of oleyl 65 alcohol, 240 grams of 96 % sulphuric acid, 3000 grams of crystalline sodium sulphate, 60 grams of the dyestuff A, 36 grams of the dyestuff B and 45 grams of the dyestuff C were introduced into the liquor at 40 C, brought to 70 the boil within 45 minutes and boiled for two hours The p H value of the dyebath was 4 5 during the dyeing In this way the gabardine goods were dyed a level beige shade. EXAMPLE 2 75 Kilograms of all-wool worsted goods on reels were dyed in a dyeing machine containing 200 litres of liquor as follows: Grams of the reaction product of 55 mois of ethylene oxide on 1 mol stearyl 80 alcohol, 250 grams of 96 % sulphuric acid, 2000 grams of sodium sulphate, 50 grams of the dyestuff A and 10 grams of the dyestuff C were introduced into the liquor at 400 C, brought to the boil within 30 minutes, and 85 boiled for 20 minutes The steam was then shut off, and at 85 WC there were added to the dyebath 15 grams of the dyestuff A and 5 grams of the dyestuff C, whereupon the whole was brought again to the boil and boiled for a 90 further 20 minutes The p H value of the dyebath was 4 1 during the dyeing The reels of wool were dyed a level greenish grey shade. EXAMPLE 3. Kilograms of all-wool worsted goods on 95 reels were dyed in a dyeing machine containing 100 litres of liquor as follows: Grams of the reaction product of 50 2 784,664 mols of ethylene oxide on 1 mol of cetylamine, grams of 85 Yo formic acid, 1000 grams of crystalline sodium sulphate, 15 grams of the dyestuff A, 75 grams of

the dyestuff B and 30 grams of the dyestuff D were introduced into the liquor at 40 C, brought to the boil within minutes and boiled for 40 minutes The p H value of the dyebath was 4 6 during the dyeing There was obtained a level claret shade. TABLE Designation Dyestuff Chromium complex of the monoazo dyestuff 1-amino-2A hydroxybenzene 5 methylsulphone -> 1-carbomethoxyamino7-hydroxynaphthalene, whereby one chromium atom is linked to two dyestuff molecules. Cobalt complex of the monoazo dyestuff 2-amino-phenol-4-sulB phometlylamide -> naphthol, whereby one cobalt atom is linked to two dyestuff molecules. Chromium complex of the monoazo dyestuff o-aminoC benzoic acid > 1 phenyl -3methyl-5-parazolone, whereby one chromium atom is linked to two dyestuff molecules. Chromium complex of the monoazo dyestuff 2-amino-1D hydroxybenzene-4 sulphamide > 1 ( 21,51 dichlorophenyl) -3methyl-5-pyrazolone, whereby one chromium atom is linked to two dyestuff molecules. The outstanding suitability of the proposed levelling agents for the aforesaid specified metal complex dyestuffs is the more surprising as the levelling agents obtainable by the action of about 6-20 mols of ethylene oxide on 1 mol of a compound containing a hydroxyl group or a primary or secondary amino group and having at least 3 carbon atoms, which otherwise have been very satisfactory in use, are objectionable with the dyestuff group employed according to the invention, since these levelling agents either do not level sufficiently or tend to precipitation. The levelling agents according to the invention are also clearly superior to levelling agents produced by condensation of naphthalene sulphonic acid with formaldehyde which have already been proposed for dyeing wool with the aforesaid specified metal complex dyestuffs, as in contrast to the condensation products they even secure level dyeings of piece goods at a p H value of 4-5.


* GB784665 (A)

Description: GB784665 (A) ? 1957-10-16

Improvements relating to metallisable trisazo dyestuffs, and their use

Description of GB784665 (A) Translate this text into Tooltip



PATENT SPECIFICATION 784,665 Date of Application and filing Complete Specification: Dec 2, 1955. No 34538/55. Application made in Switzerland on Dec 3, 1954. Complete Specification Published: Oct 16, 1957. Index at acceptance:-Class 2 ( 4), P 3 E, P 8 (A 1 C: A 2 A: B 3: D 1: D 2: E), P 9 A 4 (A: B). International Classification:-CO 9 b. COMPLETE SPECIFICATION Improvements relating to Metallisable Trisazo Dyestuffs, and their use We, J R GEIGY A -G, a body corporate organised according to the laws of Switzerland, of 215 Schwarzwaldallee, Basle, Switzerland, 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:- The present invention concerns metallisable trisazo dyestuffs which are distinguished by good affinity to cellulose fibres and by the very good wet and light fastness properties of the coppered cellulose dyeings It concerns also processes for the production of these new trisazo dyestuffs, processes for the fast dyeing of cellulose fibres using the new trisazo dyestuffs and also, as industrial product, the cellulose material fast dyed with the help of these dyestuffs. It has now been found that very valuable metallisable dyestuffs having affinity to cellulose fibres are obtained if 1 mol of a tetrazotised 4

41-diamino 3 31 dialkoxydiphenyl is coupled first with 1 mol of an o-hydroxybenzene carboxylic acid and then with 1 mol of a monoazo dyestuff of the general formula I HN=N-X H IN 2-X (I) ON 01 t in which formula X represents the radical of a diazotised aromatic-heterocyclic amino compound containing nitrogen which contains the azo group in the neighbouring position to a nitrogen atom in the ring or in the isocyclic ring in an adjacent position to a carbon atom linked with a nitrogen atom of the hetero ring and wherein R represents hydrogen, an alkyl, aralkyl or an aryl group Primary amines with a heterocyclic or isocyclic heterocyclic substituent of aromatic character are to be understood by the term aromatic-heterocyclic lPrice 3 s 6 d 1 amino compounds. Chiefly 441 diamino 3 31 dimethoxydiphenyl but also if desired 4 4 '-diamino-3 31diethoxy or -3 31-dicarboxymiethloxy-diphenyl can be used as tetrazo, components in the process according to the present application. o-Hydroxybenzene carboxylic acids, advantageously 2-hydroxybenzene-l-carboxylic acid, are used as the first coupling component. However, their reactive homologues and derivatives substituted in the ring can also be used, for example the 3 or 4-methyl-2hydroxybenzene 1 carboxylic acid, 3 6dimethyl-2-hydroxybenzene-1-carboxylic acid, 3-chloro-2-hydroxybenzene-1-carboxylic acid, 4-methoxy or 4-amino or 4-acetamino-2hydroxybenzene-1-carboxylic acid. The monoazo dyestuffs corresponding to the above formula I which can be coupled and which are used as azo components in the second step are obtained by acid coupling of a 2-primary or secondary amino-5-hydroxynaphthalene-7-sulphonic acid with a diazotised aromatic-heterocyclic amino compound containing nitrogen which contains the amino group in an adjacent position to a nitrogen atom in the ring Such aromatic-heterocyclic amino compounds containing nitrogen can contain the amino group at a carbon atom which itself is part of the hetero ring and is in a neighbouring position to a nitrogen atom in the ring In condensed isocyclic-heterocyclic compounds, they can contain the amino group in the isocyclic ring also, in this case in an adjacent position to a carbon atom linked with a nitrogen atom of the hetero ring Trisazo dyestuffs from monoazo compounds of this last named type are often distinguished by good drawing power onto cellulose and very good fastness to light of their coppered cellulose dyeings and are, therefore, preferred. Particularly valuable trisazo dyestuffs according to the present invention are derived from such monoazo dyestuffs of the above formula wherein X represents the radical of an aromatic-heterocyclic compound containing nitrogen which contains the azo group in an adjacent

position to such a nitrogen atom in the ring which forms part of an imino group or, as a result of tautomeric displacement, can form part of an imino group Such preferred monoazo dyestuffs of the above formula are obtained, for example from diazotised 5aminc-1 2 4-triazcles, 3-amino-pyrazoks, 4amino imidazoles, 3 amino indazoles, 5amino-1 2 3 4-tetrazoles, 7-amino-indoles, 7amino-indazoles, 7-amino-benzimidazoles, 7amino-benztriazoles, which may possibly be further substituted by the usual atoms and groups in aromatic substances, e g by halogen, alkyl, aralkyl, phenyl, carboxyl, nitro, acylamino, sulphonic acid amide, alkyl sulphone groups, by acid coupling with 2-primary or secondary amino 5 hydroxynaphthalene 7sulphonic acids, e g with 2-amino-, 2methylamino-, 2-ethylamino-, 2-/3-oxethylamino-, 2 3 aminoethylamino-, 2 phenylamino-, 2-( 41-methylphenyl)-amino-, 2-( 41methoxyphenyl)-amino-, 2-( 41-hydroxyphenyl)amino-, 2-( 41 hydroxy 31 carboxyphenyl)amino-5-hydroxynaphthalene-7-sulphonic acid. However, in the production of the monoazo dyestuffs usable according to the present invention corresponding to formula I, also diazo compounds of such aromatic-heterocyclic amines containing nitrogen can be used which contain the diazo group as adjacent substituent to a nitrogen atom in the ring which does not form part, nor can become, part of an imino group Examples are: diazotised 2-aminothiazoles, 2 aminobenzthiazoles, 2 aminooxazoles, 2-aminobenzoxazoles, 5-amino-1alkyl-, -aralkyl or -phenyl-1 2 3 -triaz Qles or -1.2 3 4-tetrazoles, 4-amino-1-alkyl-, -aralkylor -phenyl-benztriazoles, 4-amino-2-alkyl-, -aralkyl or -phenyl-benztriazoles, 4-aminopiazothioles, 4-aminobenzothiazoles, 4-aminobenzoxazoles, 8-aminoquinolines, 8-aminocinnolines, 8-amino-quinazolines, 8-aminoquinoxalines. It is of advantage to use 2-amino-5hydroxynaphthalene-7-sulphonic acid itself for the production of the monoazo dyestuffs which can be coupled and which correspond to the above formula. The coupling of the monoazo diazo compounds obtained under the usual conditions in the first step with the monoazo dyestuff of the general formula I, is performed in an alkaline medium, for example in the presence of sodium carbonate or of ammonia and if necessary of tertiary organic nitrogen bases such as pyridine and triethanolamine which accelerate the coupling. In the form of their water soluble alkali metal or ammonium salts, the new trisazo dyestuffs are dark powders which dissolve in water according to their composition with a more or less dull violet colour and in concentrated sulphuric acid with a blue-black colour They dye cellulose fibres from a liquor containing Glaubers' salts in violet-black shades Black dyeings which are fast to wet and light are

obtained by treating the dyeings with agents giving off copper The coppering can be per 7 C formed in the dyebath or in a fresh bath. The usual inorganic or organic copper salts such as copper sulphate, copper chloride, copper acetate and, possibly also complex copper salts such as result from ammonia, 75 organic amines or from certain aliphatic hydroxy fatty acids in an alkaline medium, can be used for this purpose Sometimes, suitable trisazo dyestuffs according to the present invention can be treated in substance 80 with agents giving off metal. The following examples illustrate the invention without limiting it in any way Where not otherwise stated, parts are given as parts by weight and the temperatures are in degrees 85 Centigrade The relationship of parts by weight to parts by volume is as that of kilogrammes to litres. EXAMPLE 1. 24.4 Parts of 4 4 '-diamino-3 31-dimethoxy 90 diphenyl are tetrazotised in the usual way and coupled under ice cooling with 17 parts of 2hydroxy 3 methylbenzene-l-carboxylic acid and 30 parts of sodium carbonate in 150 parts of water to form the monoazo diazo com 95 pound. 8.4 Parts of 5-airin:-1 2 4-triazole in excess hydrochloric adid are diazotised with 6 9 parts of sodium nitrite A solution which is weakly acid to litmus paper of 23 9 parts of 2-amino 10 ( 5-hydroxynaphthalene-7-sulphonic acid and 5.3 parts of sodium carbonate in 200 parts of water is carefully added at 0-3 to this diazo solution To accelerate the coupling, so much sodium acetate can be added as will make the 105 coupling liquid turn congo red paper a clear blue colour The completely formed monoazo dyestuff is precipitated, with an alkaline reaction to litmus paper, with sodium chloride and filtered off It is dissolved in 800 parts 110 of water and, in the presence of excess sodium carbonate, coupled with the monoazo diazo compound described above at 0-5 ' The trisazo dyestuff of the formula: Hooc CocOCH OH O>N = N N t N HyZ Nii-N Ci 3 HQ 3 S< /N N =N i N-Ck is precipitated with sodium chloride, filtered off, freed from side products by washing with sodium chloride solution and dried It is a dark powder which dissolves in water with a dull violet and in concentrated sulphuric acid 12 ( with a blue-black colour Cellulose fibres are dyed dark violet, the coppered dyeings are 784,665 EXAMPLE 2. 24.4 Parts of 4 41-diamino-3 3 '-dimethoxydiphenyl in the necessary amount of hydrochloric acid are tetrazotised at 0-2 with 13.8 parts of sodium nitrite and coupled with 15.3 parts of 2-hydroxybenzene-1-carboxylic acid in the presence of 30 parts of

sodium carbonate to form the diazo monoazo dyestuff. This is poured slowly at 0-5 ' into an aqueous solution of the monoazo dyestuff obtained by mineral acid coupling of 12 8 parts of diazotised 5-amino-1 2 4-triazole-3-carboxylic acid with 23 9 parts of 2 amino 5 hydroxynaphthalene-7-sulphonic acid, which solution also contains 20 parts of sodium carbonate. As soon as the formation of the trisazo dyestuff of the formula: black and have excellent wet and light fastness properties. If in this example instead of 17 parts of 2-hydroxy-3-methylbenzene-1 l-carboxylic acid, S the same number of parts of 2-hydroxy-4methylbenzene-1-carboxylic acid, 15 3 parts of 2-hydroxybenzene-1-carboxylic acid, 19 2 parts of 2-hydroxy 3 chlorobenzene-1-carboxylic acid, 21 5 parts of 2-hydroxy-4-acetylamino-benzene-1-carboxylic acid or 18 4 parts of 2-hydroxy 3 6 dimethylbenzene-1-carboxylic acid are used and if 8 3 parts of 3aminopyrazole are used instead of 8 4 parts of 5-amino-1 2 4-triazole, and otherwise the same procedure is followed, then dyestuffs with similar properties are obtained. Hooc CHI O OCH OH HO Se N, NH N N =N-C II N C COOH is complete, it is salted out, filtered off, washed free of impurities and dried It is a dark powder which dissolves in water with a dull violet and in concentrated sulphuric acid with a blue-black colour It dyes cellulose, after later treatment with agents giving off copper, in black shades which have very good wet and light fastness properties. Dyestuffs with similar properties are obtained if the 5-amino-1 2 4-triazole-3carboxylic acid is replaced by 9 8 parts of 5amino-3-methyl-1 2 4-triazole, 9 9 parts of 5amino-3-imino-1 2 4-triazole, 17 5 parts of 2phenyl-3-imino-5-amino-1 2 4-triazole, 15 9 parts of 3-amino-5-phenylpyrazole or 9 7 parts of 4-amino-5-methyl imidazole. EXAMPLE 3. 24.4 Parts of tetrazotised 4 41-diamino3.31-dimethoxydiphenyl are coupled in the presence of 30 parts of sodium carbonate with 17 parts of 2-hydroxy-4-methylbenzene-1carboxylic acid to form the intermediate product. At the same time 14 8 parts of 1-methyl-4aminobenztriazole are dissolved in excess hydrochloric acid and an aqueous solution of 6.9 parts of sodium nitrite are added while stirring well at 0-2 After a few minutes, a weak acid to litmus paper solution of 23 9 parts of 2-amino-5-hydroxynaphthalene-7-sulphonic acid and 5 3 parts of sodium carbonate in 200 parts of water are added while cooling with ice to this diazo solution On completion of the coupling, the red monoazo dyestuff in a weakly alkaline solution is coupled at 0-5 with the diazo monoazo compound described above The trisazo dyestuff formed is

precipitated with sodium chloride, filtered off and dried The dark powder of the formula: oo 00 C CO OCH 3 OH H 09 N NN -NAP N = N-C< H -3 dissolves in water with a black-violet colour and in concentrated sulphuric acid with a blueblack colour Cellulose dyeings after being coppered are black and they have very good wet and light fastness properties. If in this example 19 2 parts of 4-aminobenztriazolyl-1-acetic acid, 15 1 parts of 4aminopiazothiole or 15 parts of 4-aminobenzthiazole, 22 4 parts of 4-amino-6-methoxybenzthiazole-2-carboxylic acid or 14 8 parts of 2-methyl-4-aminobenzoxazolone are used instead of 14 8 parts of 1-methyl-4-aminobenztriazole, and otherwise the same procedure is followed, then dyestuffs with similar shades and properties are obtained. EXAMPLE 4. 24.4 Parts of 4 4 '-diamino-3 3 '-dimethoxydiphenyl are tetrazotised in the usual way and coupled in the usual way in the presence of parts of sodium carbonate at 0-3 with 17 parts of 2-hydroxy-3-methylbenzene-1carboxylic acid On completion of the coupling, the red-brown diazo monoazo dyestuff is added to a solution of an orange coloured monoazo dyestuff which contains excess sodium carbonate and 10 % by volume of pyridine, the orange coloured monoazo dyestuff being 784,665 obtained by the mineral acid coupling of 8 5 parts of diazotised 5-amino-1 2 3 4-tetrazole with 23 9 parts of 2-amino-5-hydroxynaphthalene-7-sulphonic acid The dyestuff which on the next day is isolated with sodium chloride, filtered off, thoroughly washed and dried, is a dark powder of the formula: HOOC C QO c H, HO N =N-b-d-N= N CH, H Ov NH N N 11 N N-N It dissolves in water with a dark violet and in concentrated sulphuric acid with a blue-black colour The cellulose dyeings attained therewith after being treated with copper salts are black and have excellent wet and light fastness properties. If in this example the 2-hydroxy-3-methylbenzene-1-carboxylic acid is replaced by the same number of parts of 2-hydroxy-4-methylbenzene-l-carboxylic acid, 15 3 parts of 2hydroxybenzene-1-carboxylic acid, 18 6 parts of 2-hydroxy-4-methoxybenzene-l-carboxylic acid, 21 5 parts of 2-hydroxy-4-acetylaminobenzene-1-carboxylic acid, or 18 4 parts of 2hydroxy-3 6-dimnethylbenzene-1-carboxylic acid and the 24 4 parts of 4 41-diamino-3 31dimethoxydiphenyl is replaced by 27 2 parts of 4.41-diamino-3 3 '-diethoxydiphenyl and otherwise the same procedure is followed, then dyestuffs with similar properties are obtained. EXAMPLE 5. 24 4 Parts of 4 41-diamino-3 3 '-dimethoxydiphenyl are tetrazotised in the usual way and coupled with 15 3 parts of

2-hydroxybenzene1-carboxylic acid and 30 parts of sodium carbonate to form the diazo monoazo dyestuff. At the same time 13 4 parts of 7-aminobenztriazole are dissolved in excess hydrochloric acid and 6 9 parts of sodium nitrite dissolved in a little water are quickly added while stirring very quickly at 0-2 o A weakly acid to litmus paper solution of 23 9 parts of 2amino-5-hydroxynaphthalene-7-sulphonic acid and 5 3 parts of sodium carbonate in 200 parts of water is gradually added The coupling proce:ds without difficulty; it can be accelerated by the careful dropwise addition of an aqueous sodium acetate solution until the reaction is weakly mineral acid The monoazo dyestuff which, in an alkaline to litmus paper medium, has been precipitated with sodium chloride and isolated by filtration, is dissolved in 600 parts of water and 150 parts by volume of pyridine and is then coupled in the presence of excess sodium carbonate at 0-5 with the brown-red suspension of the above monoazo diazo compound The trisazo dyestuff of the formula: HOOC CHQ 03 Ho-b-N= N-6 N N N I Ho 3 N N HN N \N/l forms quickly and, after the usual isolation and purification, is a dark powder which dissolves in water with a dark violet and in concentrated sulphuric acid with a blue-black colour The full black cellulose dyeings obtained after treatment with copper, have excellent wet and light fastness properties. If, instead of 7-aminobenztriazole, 14 8 parts of 5-methyl-7-aminobenztriazole are used, then a dyestuff with similar good properties is obtained. EXAMPLE 6. The monoazo diazo compound obtained according to example 2 from 24 4 parts of tetrazotised 4 41-diamino 3 31-dimethoxydiphenyl and 15 3 parts of 2-hydroxybenzene1-carboxylic acid is poured while stirring well at 0-5 into a solution which is alkaline to litmus paper of the red monoazo dyestuff obtained by acid coupling of 14 4 parts of diazotised 8-aminoquinoline with 23 9 parts of 2-amino-5 hydroxynaphthalene 7-sulphonic acid On completion of the coupling, the trisazo dyestuff of the formula: NO H 2 HO-6 'k 4 $ 2 N = N, is precipitated with sodium chloride, drawn off under suction and dried The dark powder dissolves in water with a dark violet and in concentrated sulphuric acid with a blue-black colour When after coppered it dyes cellulose fibres in black shades which have very good fastness to wet and light. If in this example, the 8-aminoquinoline is replaced by 15 9 parts of 4-methyl-8-aminocinnoline, 14 5 parts of 8-aminoquinazoline, 14.5 parts of 8-aminoquinoxaline, 22 5 parts of 8-aminoquinoxaline-6-sulphonic acid or 15.9 parts of

6-methyl-8-aminoquinoxaline and otherwise the same procedure as described above is followed, then dyestuffs are obtained with similar properties. EXAMPLE 7. The monoazo diazo compound according to example 2 from 24 4 parts of tetrazotised 4 41diamino-3 31-dimethoxydiphenyl and 15 3 parts of 2-hydroxybenzene-1-carboxylic acid is poured under ice cooling into the aqueous solution of the red monoazo dyestuff obtained by coupling in an acid medium 17 8 parts of diazotised 7-aminobenztriazole-5-carboxylic 784,665 salts, the dyeings are black and have very good wet and light fastness properties. If in this example instead of 2-aminothiazole, 11 4 parts of 2-amino-4-methylthiazole, 17.6 parts of 2-amino-4-phenylthiazole, 14 4 parts of 2-aminothiazole-4-carboxylic acid, 18.6 parts of 2-amino-4-methylthiazole-5carboxylic acid ethyl ester, 8 4 parts of 2amino-oxazole, 9 9 parts of 5-amino-1-methyl1.2 3 4-tetrazole, 16 1 parts of 5-amino-1phenyl-1 2 3 4-tetrazole, 17 5 parts of 5-amino1-benzyl-1 2 3 4-tetrazole or 16 parts of 5amino-1-phenyl-1 2 3-triazole are used and otherwise the same procedure as described above is followed, then dyestuffs with similar properties are obtained. EXAMPLE 9. 24.4 Parts of 4 41-diamino-3 31-dimethoxydiphenyl in hydrochloric acid solution are tetrazotised at 0-2 with 13 8 parts of sodium nitrite and the tetrazo compound obtained is coupled with 15 3 parts of 2-hydroxybenzene1-carboxylic acid in the presence of 30 parts of sodium carbonate Also 13 4 parts of 7-aminobenztriazole are diazotised by dissolving in excess hydrochloric acid and quickly adding 6.9 parts of sodium nitrite dissolved in a little water at 0-2 A solution which is weakly acid to litmus paper of 31 5 parts of 2-phenylamino-5-hydroxynaphthalene-7-sulphonic acid and 5 3 parts of sodium carbonate in 300 parts of water is added to this diazo solution under ice cooling On completion of the coupling, the monoazo dyestuff is isolated in the form of the sodium salt, this is dissolved in 600 parts of water and 150 parts by volume of pyridine and coupled in the presence of 20 parts of sodium carbonate with the diazo monoazo compound described above On completion of the final coupling, the trisazo dyestuff of the formula: acid with 23 9 parts of 2-amino-5-hydroxynaphthalene-7-sulphonic acid, the solution also containing 20 parts of sodium carbonate As soon as the coupling to form the trisazo dyestuff is complete, this is precipitated with sodium chloride, filtered off and dried The dyestuff is a dark powder It corresponds to the formula: Hoop CHO OCH 3 N 4 "Nz COON "o N Nand dissolves in water with a dark

violet and in concentrated sulphuric acid with a blueblack colour The after-coppered dyeings of cellulose fibres are deep black and have excellent wet and light fastness properties. If in this example the 2-hydroxybenzene-1carboxylic acid is replaced by 17 parts of 2hydroxy-3 or -4-methylbenzene-1-carboxylic acid, 19 2 parts of 2-hydroxy-3-chlorobenzene1-carboxylic acid, 21 5 parts of 2-hydroxy-4acetylaminobenzene-l-carboxylic acid, 18 6 parts of 2-hydroxy-4-methoxybenzene-1carboxylic acid or 18 4 parts of 2-hydroxy-3 6dimethylbenzene-l-carboxylic acid and the 7aminobenztriazole-5-carboxylic acid is replaced by 21 4 parts of 7-aminobenztriazole-5sulphonic acid or by 21 2 parts of 7-aminobenztriazole-5-methyl sulphone and otherwise the same procedure is followed, then dyestuffs with similar properties are obtained. EXAMPLE 8. The brown-red diazo monoazo dyestuff produced from 24 4 parts of tetrazotised 4 41diamino-3 31-dimethoxydiphenyl and 15 3 parts of 2-hydroxybenzene-1-carboxylic acid in the presence of 30 parts of sodium carbonate is poured into a solution of the blueish-red monoazo dyestuff obtained by the acid coupling of 10 parts of diazotised 2-aminothiazole with 23.9 parts of 2-amino-5-hydroxynaphthalene7-sulphonic acid This solution also contains an excess of sodium carbonate As soon as the coupling is complete, the dyestuff is precipitated with a little sodium chloride, filtered off under suction and, if necessary re-dissolved and dried The trisazo dyestuff of the formula: 0 IH Ho OC OCH O r Ot N N Wi H N= N TJ 5-N U)Nz N-CH S-CH is a dark powder which dissolves in water with a dull violet and in concentrated sulphuric acid with a blue-black colour Natural and regenerated cellulose fibres are dyed in dark violet shades After treatment with copper Hooc CH 30 OCH O Ho b NN 2-i N N HO N = 3 r 4 HO NNN m is precipitated with a little sodium chloride, filtered off under suction and dried It is 95 obtained as a dark powder which dissolves in water with a dull violet and in concentrated sulphuric acid with a blue-black colour After coppered cellulose dyeings are reddish-black and have good wet and light fastness 100 properties. Further dyestuffs with similar properties are obtained if instead of 31 5 parts of 2-phenylamino-5-hydroxynaphthalene-7-sulphonic acid, 25.3 parts of 2-methylamino-5-hydroxy 105 naphthalene-7-sulphonic acid, 26 7 parts of 2ethylamino-5 hydroxynaphthalene-7-sulphonic acid, 28 2 parts of 2 /3-aminoethylamino-5784,665 hydroxynaphthalene-7-sulphonic acid, 28 3 parts of 2 13-oxethylamino-5-hydroxynaphthalene-7-sulphonic acid, 30 9 parts of 2-i-amylamino-5-hydroxynaphthalene-7-sulphonic acid, 32 1 parts of 2-cyclohexylamino-5-hydroxynaphthalene-7-sulphonic acid, 32 9 parts of

2benzylamino 5 hydroxynaphthalene 7 sulphonic acid, 37 5 parts of 2-( 41-hydroxy-31carboxyphenylamino) 5-hydroxynaphthalene7-sulphonic acid, 34 5 parts of 2-( 4 '-methoxyphenylamino) 5 hydroxynaphthalene 7 sulphonic acid or 29 7 parts of the glycine of 2-amino-5-hydroxynaphthalene 7-sulphonic acid are used. EXAMPLE 10. 24.4 Parts of 4 41-diamino-3 3 '-dimethoxydiphenyl are tetrazotised in hydrochloric acid solution with 13 8 parts of sodium nitrite and the tetrazo compound obtained is coupled in the presence of 30 parts of sodium carbonate with 17 parts of 2-hydroxy-3-methylbenzene1-carboxylic acid The red-brown suspension of the diazo monoazo compound is poured at 0-5 ' into the sodium carbonate alkaline solution of the red monoazo dyestuff obtained by mineral acid coupling of 13 3 parts of diazetised 7-amino-indazole with 23 9 parts of 2amino-5-hydroxynaphthalene-7-sulphonic acid. As soon as the coupling to form the trisazo dyestuff of the formula: Hooc CH O OCH OH HO >D N N N -N CH 3 /i LNU H 03) z HE C Hi is complete, the dyestuff is precipitated by the addition of a little sodium chloride, filtered off, washed and dried It is a dark powder which dissolves in water with a dull violet and in concentrated sulphuric acid with a blueblack colour The cellulose dyeings which, on being after coppered are black, have excellent wet and light fastness properties. If in this example, 14 7 parts of 5-methyl7-amino-indazole, 14 7 parts of 6-methyl-7amino-indazole, 21 3 parts of 7-aminoindazole4-sulphonic acid, 13 2 parts of 7-amino-indole, 17.6 parts of 7-amino-indole-2-carboxylic acid, 19 parts of 3-methyl-7-amino-indole-2carboxylic acid or 17 3 parts of 2-ethyl-3methyl-7-amino-indole are used instead of 13 3 parts of 7-amino-indazole, and otherwise the same procedure is followed, then dyestuffs with similar properties are obtained. EXAMPLE 11. The diazo monoazo compound produced according to example 2 from 24 4 parts of tetrazotised 4 41-diamino-3 31-dimethoxydiphenyl and 15 3 parts of 2-hydroxybenzene-1carboxylic acid is poured at 0-5 into a solution, containing sodium carbonate, of the monoazo dyestuff obtained by acid coupling of 13.3 parts of diazotised 7-aminobenzimidazole with 23 9 parts of 2-amino-5-hydroxy 60 naphthalene-7-sulphonic acid in 600 parts of water and 150 parts by volume of pyridine. After the coupling, which occurs quickly, the trisazo dyestuff of the formula: HOO CH O (CH OH N =:N -' HN N is precipitated with sodium chloride, filtered off and dried The dark powder dissolves in water with

black-violet and in concentrated sulphuric acid with a blue-black colour On after treating the dark violet direct dyeings 70 with copper salts, they become black and have very good wet and light fastness properties. Further dyestuffs with similar properties are obtained if, instead of 13 3 parts of 7-aminobenzimidazole, 14 7 parts of 2-methyl-7 75 aminobenzimidazole or 16 1 parts of 2 5dimethyl-7-aminobenzimidazole or 19 1 parts of 2 methyl 7 aminobenzimidazole 5 carboxylic acid Or 22 7 parts of 2-methyl-7aminobenzimidazole-5-sulphonic acid or 28 9 80 parts of 2-phenyl-7-aminobenzimidazole-5sulphonic acid are used. EXAMPLE 12. 24.4 Parts of 4 4 l-diamino-3 31-dimethoxydiphenyl are tetrazotised in the usual way and 85 coupled with 15 3 parts of 2-hydroxybenzene1-carboxylic acid and 30 parts of sodium carbonate to form the intermediate product. Also, 13 4 parts of diazotised 7-aminobenztriazole are coupled in a clearly acid 90 medium with 29 7 parts of the glycine of 2amino-5-hydroxynaphthalene-7-sulphonic acid. The red monoazo dyestuff obtained is coupled in the form of an alkali metal salt in a solution containing excess sodium carbonate with 95 the monoazo diazo compound described above. The coupling is performed while cooling well. The trisazo dyestuff obtained of the formula: HOOC CH O CH ON NH=N N \ HN N is precipitated from the violet-black solution 10 C with sodium chloride, filtered under suction and dried The dark powder dissolves in water with a dull violet and in concentrated sulphuric acid with a blue-black colour When after coppered, cellulose fibres are dyed in reddish 105 black shades which have good wet and light fastness properties. 784,665 isocyclic ring in an adjacent position to a carbon atom linked with a nitrogen atom of the hetero ring. 2 A metallisable trisazo dyestuff having 60 the general formula NO CHO O OCH OH n -N N 6 N N H 00 C O N=N-B wherein A represents a benzene radical containing the hydroxyl and carboxyl group in the o-position to each other 65 B represents a phenyl radical containing in o-position to the azo linkage, an imino group which forms part of a fused 5-membered hetero ring. 3 Process for the production of metallisable 70 trisazo dyestuffs characterised by reacting 1 mol of a tetrazotised 4 41-diamino-3 31diallkoxydiphenyl first with 1 mol of an ohydroxybenzene carboxylic acid and then with 1 mol of a monoazo dyestuff of the general 75 formula: N=N-X V$lNH R OH in which X represents the radical of a diazotised aromatic-heterocyclic amino compound as hereinbefore defined

containing 80 nitrogen, which monoazo dyestuff contains the azo group in an adjacent position to a nitrogen atom in the ring, or in the isocyclic ring in an adjacent position to a carbon atom linked with a nitrogen atom of the hetero ring, and 85 whereinR represents a hydrogen atom, an alkyl, aralkyl or an aryl group. 4 Manufacture of metallisable trisazo dyestuffs substantially as described with reference 90 to any of the foregoing examples 1 to 12. Metallisable trisazo dyestuffs whenever prepared or produced by a process of manufacture particularly described. 6 A metallisable trisazo dyestuff as 95 identified in any of the foregoing examples 1 to 12 including a dyestuff resulting from an alternative reactant specified. 7 Coppered dyeings on cellulose fibres whenever produced with a trisazo dyestuff 100 within the general formula given in claim 1. 8 A process of dyeing cotton and of coppering the dyed goods substantially as hereinbefore described with reference to example 13. For the Applicants: HENRY IMRIE & CO, Chartered Patent Agents, 329, High Holborn, London, W C 1. If, instead of 13 4 parts of 7-aminobenztriazole, 17 8 parts of 7-aminobenztriazole-5carboxylic acid, 21 4 parts of 7-aminobenztriazole-5-sulphonic acid or 21 2 parts of 7aminobenztriazole-5-methyl sulphone are used and the glycine of 2-amino-5-hydroxynaphthalene-7-sulphonic acid is replaced by 28 3 parts of 2 fi-hydroxyethylamino-5-hydroxynaphthalene-7-sulphonic acid, 25 3 parts of 2methylamino 5 hydroxynaphthalene 7 sulphonic acid, 26 7 parts of 2-ethylamino-5hydroxynaphthalene-7-sulphonic acid, 28 1 parts of 2-i-propylamino-5-hydroxynaphthalene-7-sulphonic acid, 31 5 parts of 2-phenylamino-5-hydroxynaphthalene-7-sulphonic acid, 32.1 parts of 2-cyclohexylamino-5-hydroxynaphthalene-7-sulphonic acid, 32 9 parts of 2benzylamino 5 hydroxynaphthalene 7 sulphonic acid, 37 5 parts of 2-( 4 '-hydroxy-31carboxyphenylamino) 5-hydroxynaphthalene7-sulphonic acid or 33 1 parts of 2-( 41hydroxyphenylamino)-5 hydroxynaphthalene7-sulphonic acid and otherwise the same procedure is followed, then analogous dyestuffs with similar properties are obtained. EXAMPLE 13. 2 Parts of the dyestuff obtained according to example 2 are dissolved in a dyebath containing 3000 parts of water and 2 parts of sodium carbonate 100 Parts of cotton are introduced at 40-50 , the bath is heated within 30 minutes to 90-95 , 30 parts of sodium sulphate are added and dyeing is performed for 45 minutes at this temperature. After this time, the dyed goods are rinsed cold and after treated in a fresh bath with 2 parts of crystallised copper sulphate in 2000 parts

of water and 2 parts of 30 % acetic acid for 30 minutes at 70 The goods are rinsed and dried in the usual way The black cotton dyeing has excellent fastness properties.


* GB784666 (A)

Description: GB784666 (A) ? 1957-10-16

Improvements in safety pins


PATENT SPECIFICATION Date of Application and filing Complete Specification: Dec 5, 1955. 784,666 No 34820/55. Complete Specification Published: Oct 16, 1957. Index at acceptance:-Class 43, R 1 International Classification:-A 44 b. COMPLETE SPECIFICATION Improvements in Safety Pins I, ROBERT DE KYVON, of I rue Regnault, Tangier, Morocco, of French Nationality, do hereby declare the invention, for which I pray that a patent may be granted to me, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to ordinary safety pins comprising a locking device designed to prevent inadvertent opening by the movable aim of the pin. According to the invention, the locking device is made up of a locking member, pivotally mounted on the end of the conventional head of the safety pin and is capable of being turned back on to this head to mask a conventional slot provided in said head for enabling the pin to be

opened and closed. In one embodiment of the invention the locking member has a tab engaged in an opening provided in the head, this tab being bent inwardly after passing through the opening to provide hinge means for the locking member. According to another embodiment, the locking member carries on its free end a tab adapted to be forced between the two arms of the safety pin. One particular form of safety pin according to the invention is shown, by way of illustrative example, in the accompanying drawings in which:Fig 1 is a perspective partial view of the safety pin including its locking member; Fig 2 is a front view of this pin in locked position; Fig 3 is a view showing the other face of the pin of Fig 2; Fig 4 is a partial view of the pin without the locking member; Fig 5 is a perspective view showing in detail the locking member; Fig 6 is a sectional view of the unlocked pin; Fig 7 is a sectional view of the locked pin. lPrice 3/63 The conventional safety pin shown in the accompanying drawings is made up of a wire shaped so as to form two arms 1 and 2 and a head 3 This head has a slot 4 to permit opening and closing the pin 50 A locking member such as shown in Fig 5 prevents inadvertent opening of the pin. This locking member is made up of a plate rotatably mounted on the head 3 which can be pivoted to a position over the latter to 55 mask the conventional slot 4 by means of which the pin is enabled to be opened and closed This plate 6 carries a tab 7, engaged in an opening 8 provided at the end of the head 3 This tab is curved, as shown in 60 Figs 5, 6 and 7, to provide a hinge when engaged in the opening 8 At the opposite end of the plate 6 another tab 9 is curved inwardly in a U-shape and is designed so as to form two notches 10 and 11 delimiting the tab 65 relatively to the plate 6 In locked position, the tab 9 is forced between the arms 1 and 2 which press yieldingly on both sides of the tab. Furthermore, the free end of this tab 9 may be bent inwardly to form a flange 12 which 70 engages behind the head 3 of the pin with the result of further securing the locking member in closed position, whereby is constructed in a very simple way, a pin having a safety catch 75

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* GB784667 (A)

Description: GB784667 (A) ? 1957-10-16

Improvements in or relating to clockwork motors


PATENT SPECIFICATION Inventor: STANLEY FREDERICK WATKINS 78 Date of application and filing Complete Specification: Dec 16, 1955 No 36184155. Complete Specification Published: Oct 16, 1957. Index at acceptance:-Class 10, F 2 A. International Classificatioin:-F 02 j. COMPLETE SPECIFICATION Improvements in or relating to Clockwork Motors We, STAMFORD METALLICS LIMITED, of 9 and 10 Royal Victor Place, Old Ford Road, London, E 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 relates to clockwork motors as used for example for driving mechanical toys and models, and more particularly to motors of the kind provided with a spring winding mechanism comprising a wheel or drum having operative connection with the winding spindle of the motor, and a string or cord which is wound at one end around said wheel or drum so that when a pull is exerted on the other end the drum is rotated and thereby winds the motor spring, the transmission between the drum and the winding spindle including a lost motion connection which, after a winding operation and when the pull string is released, permits the drum to return to its initial position under the action of a return spring and independently of the winding spindle. The object of the present invention is to provide an improved and simplified winding mechanism of this character. According to the invention the driving connection between the drum and

the winding spindle includes a seres of coaxial discs each provided with a lug or projection adapted to co-act with an abutment on the or an adjacent disc, the arrangement being such that with all the lugs engaging their co-acting abutments a positive drive is transmitted from the drum through the discs to the winding spindle, whilst the return movement of the drum independent of the winding spindle is permitted by limited relative rotation between each adjacent pair of discs. In the preferred construction where the discs are mounted on the winding spindle co-axial with the drum, each disc lug, except one, constitutes the co-acting abutment for the lug on the preceding disc, the first disc being lPrice 3 s 6 d l fast on the winding spindle and the remainder free to rotate thereon whilst the lug on the last disc engages an abutment on the drum. Reference will now be made to the 50 accompanying drawings which illustrate a preferred form of the invention and wherein: Fig 1 shows in side elevation the improved winding mechanism applied to the 55 clockwork driving motor of a model car and Fig 2 is a plan view to an enlarged scale of the mechanism shown in Fig 1. In the drawings, 1 indicates the supporting frame of a clockwork motor which may be 60 of any known type, that shown consisting of a winding spindle 2, a motor spring 3, a gear wheel 4 loose on said spindle, a clutch member 5 operable to transmit unidirectional drive from spindle 2 to gear wheel 4 and an 65 output shaft 6 which is driven from gear wheel 4 through a gear train 7 In Fig 1, the output shaft 6 is shown driving the rear wheels of the car through a conventional transmission 8 and it will be understood that 70 any other known form of transmission may be employed and the drive may alternatively be to the front wheels. For the purpose of the present invention, the winding spindle extends to one side of 75 the frame 1 and on it is mounted a wheel or drum 9 and a series of discs 10, 11, 12 and 13 coaxial therewith, the first disc 10 being fast on said spindle whilst the remaining discs and the drum are free to rotate upon 80 the spindle The discs are provided with peripheral lugs 10 a, 1 la, 12 a and 13 a respectively, the first three of said lugs being offset or bent over into the path of the lug on the adjacent disc The lug 13 a extends in the 85 plane of the plane of the disc 13 and is adapted to engage a stud or equivalent abutment 14 on the side face of the drum. Attached at one end to the drum and wound around the drum is a pull string 15, the other 90 end of said string extending through the dashboard of the vehicle and being provided Ls 3 with a finger knob 16 which may be formed to simulate a steering wheel The drum is also under control of a return spring 17 the inner end of which is attached

to a peg on the drum whilst the other end has a fixed attachment to the frame 1 The mechanism operates in the following manner: When the vehicle is at rest and the motor spring is unwound, the winding mechanism is in the condition shown in the drawings To wind the motor spring, the driving wheels, are held against rotation and by gripping the finger knob 16 pull is exerted on the string. Thus the drum is rotated anticlockwise (Fig. 1) and as the disc lugs are in abutment, rotation is transmitted directly to the spindle 2 so winding the spring 3 During this operation, the return spring 17 is tensioned and immediately the winding operation is completed the finger knob may be released whereupon the return spring rotating the drum in a clockwise direction, restores the drum and string to the starting position This reverse rotation of the drum is independent of the spindle 2 by reason of the fact that relative rotation of slightly less than one complete revolution is possible between each adjacent pair of discs and between the last disc and the drum With the use of four discs as shown a free reverse rotation of the drum of approximately three and a half revolutions is permitted but it will be understood that the number of discs used may be varied, depending upon the number of revolutions of the spindle 2 required to wind the motor spring fully. As the motor runs down, the spindle 2 transmits rotation successively to the discs until they are finally restored to the operative, i e spring unwound, position shown in the drawings.


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