4371 4375.output

* GB784778 (A)
Description: GB784778 (A) ? 1957-10-16
Improvements in and relating to three-heat electric switches
Description of GB784778 (A)
PATENT SPE Ci FICATION
784 778 Date of Application and filing Complete
Specification: May 16 1956.
No 15265/56 Complete Specification Published: October 16, 1957
Index at acceptance:-Class 38 ( 5), BMP 2, 12 (B 3:B 6:Bll:E).
International Classification:-',101 n H 02 c COMPLETE SPECIFICATION
Improvements in and relating to Three-Heat Electric Switches We,
WARMEX LIMITED, a British Company, of 375, Milton Road, Cambridge, and
ARTH Up R GOLDSTEIN, a British Subject, of the same address, 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 electric switches and particularly such
switches for electric blankets, of the type which have a miniature
tell-tale lamp located in the switch casing visually to indicate
through the transparent or translucent material thereof or a window
therein, when the current is switched on and the blanket in circuit.
Hitherto such switches which include tell-tale lamps, for electric
blankets, have only been constructed for use with and in the circuit
of electric blankets having a single heating wire or element which
allows for no variation of heat to be given to the blanket.
Electric blankets however are known having two heating wires or
elements, connected by a triple conductor to a so-called " three-heat"
switch, which also has terminals for connection to the usual double
conductor to the mains.
In addition to the position or positions into which the parts of this
three-heat switch are set when the blanket is out of circuit, it can
be set into three other positions in which the blanket is in circuit
In one of these, both heating wires or elements of the blanket,
connected in series, are in circuit; in another, one wire or element

alone is in circuit; whilst in the third position the two wires or
elements connected in parallel are in circuit Consequently, three
variations of heat can be given to the blanket at the choice of the
user.
Multi-position electric switches of the kind comprising a rotary
member carrying a lPrice 3 s 6 d l plurality of axially-spaced
contacts cooperating with a plurality of series of angularly spaced
fixed contacts provided within a housing and arranged in different
transverse planes, are known for controlling the 50 connections of
heating resistance means employed with electric heating apparatus,
such as electric stoves, electric heaters, and like electric heating
appliances and apparatus, and which include a " pilot light," pilot 55
light circuit, and switch means for controlling said circuit, wholly
within the switch casing, and wherein the pilot light is energised
only during the actual circuit closure on each and all of the several
heats, the pilot light being 60 visible through an opening in the
switch guarded by a transparent cover.
According to the present invention, a three-heat switch for an
electric blanket having two heating wires or elements, in 65 cludes in
its construction a tell-tale lamp the light from which is visible when
the blanket is switched on through the material of the switch casing
or a window therein, the said lamp being connected to two exist 70 ing
contacts of the switch provided for the said triple conductor and
mains supply, which are at different potentials when the switch is in
any one of the " on " positions.
Preferably, the tell-tale lamp is a glow 75 lamp and is in series with
a resistance, and the lamp and resistance are arranged in parallel
with the terminals to which they are connected, that is, in effect
they are in parallel across one or both of the heating 80 wires or
elements.
In a preferred arrangement one connection to the lamp is always to a
terminal in the switch connected to one lead of the mains, whilst the
other connection to the 85 lamp is always to the terminal in the
switch of the lead of the triple conductor which is connected to the
junction between the two heating elements of the blanket.
The invention is particularly suitable for 90 J a-Jc d 784,778 use
with the known type of three-heat electric switches for electric
blankets having a rotary member carrying a plurality of
circumferentially spaced and grouped contacts, co-operating with fixed
contacts having terminal connections to the leads for the supply and
to the blanket.
In certain constructions and especially to adapt the present invention
to such existing three-heat switches for electric blankets, the lamp
and its associated resistance can be carried by a shaped member of

insulating material having contacts on one surface connected to the
lamp and resistance circuit, which is fitted between the switch cover
and body so that, when the parts are assembled, the contacts connect
up with the requisite terminals, contacts and connections in the
switch body to hold the lamp in position for its glow to be seen
through the transparent or translucent switch cover or a window
therein.
In order that the invention may be better understood, it will now be
described with reference to the accompanying drawings which are given
by way of example only and in which:Fig 1 is a front elevation of one
form of three-heat switch for an electric blanket constructed
according to the invention.
Fig 2 is a top plan of Fig 1.
Fig 3 is a similar view to Fig 2 but with the cover removed and parts
broken away.
Fig 4 is a top plan of a component of the switch according to the
invention, to be fitted on the switch body shown in Fig 3, before the
cover is attached in position.
Fig 5 is a plan of the cover, with the component shown in Fig 4 in
position, taken from below.
Figs 6 and 7 are sectional elevations, to a somewhat larger scale, of
details shown in Fig 3.
Fig 8 is an electrical diagram of the switch shown in Fig 3 and the
blanket heating wires or resistances, in one "switched-off" position.
Figs 9, 10 and 11 are similar views of the switch in the three
"switched-on" positions, and Fig 12 a similar view of the switch in
the other "switched-off " position.
The drawings show a three-heat switch for electric blankets, of known
type, with certain additions and modifications to constitute a switch
according to the present invention.
In the drawings, 13 is the body of the switch formed from insulating
material and go consisting of an outer casing 14 with an integral
upstanding annular platform or ridge 15, surrounded by a groove 16
opening into the axial half sockets 17 and having a central
cylindrical cavity 18 in which is mounted a central spindle 19 on
which turns a cylindrical rotor or drum 34 of insulating material by
means of the handle 20 which projects to the exterior where it has an
operating thumb-piece 21 This handle is shown broken away in Fig 3 but
it has five 70 definite positions of setting, viz VIII, IX, X, XI and
XII, spaced 30 ' apart and which correspond to the diagrams Figs 8 to
12 to be hereafter described.
The ridge 15 has mounted therein termi 75 nals 22 and 23 in Fig 3
spaced at 120 ' apart, 22 being 600 on one side of the horizontal axis
and 23 being 600 on the other side These are the terminals for the

supply or main leads 24 and 25 which pass 80 as a duplex cable into
the socket at this end and then into the groove 16.
The ridge 15 also carries terminals 26, 27 and 28, the first 26 spaced
at 30 ' from the terminal 22 and being spaced at 60 from 85 27, which
is spaced 600 from 28; thus, the terminals 27 and 28 are located at
300 on each side of the horizontal axis The terminals 26, 27 and 28
are for the leads to constitute the triple conductor to the blanket,
90 and 66 is hereafter termed the " common " lead, 67 the " outer "
lead and 68 the "'central " lead The terminals 22, 23, 26, 27 and 28
have contact tongues 29, 30, 31, 32 and 33, respectively, connected
thereto which 95 project down into the cavity 18 of the casing which
forms part of the body of the switch.
The rotor 34 carries on its cylindrical face two groups of strip
contacts One group of four-35, 36, 37 and 38-are spaced at 300 100
apart and connected at the end by an integral portion 39 (Fig 8) The
other group of five -40, 41, 42, 43 and 44-have 40, 41 and 42 at 30 '
spacing, 42 and 43 at 60 ' apart, and 43 and 44 at 30 ' spacing; these
are con 105 nected at the end by an integral portion 45 (Fig 8) The
two groups at their ends are spaced at 30 ' apart.
The mounting and arrangement is as shown in Fig 3, where the switch is
in one 110 extreme out-of-circuit position represented by the handle
position VIII and is such that when the handle is moved in a
counterclockwise direction to the position IX the contact 35 connects
with the terminal 26 115 and the contact 40 with the terminal 23,
whilst the other contacts connect with other terminals to be more
fully explained hereafter.
As thus far particularly described the 120 switch is as hitherto
constructed and it is completed by a cover having complementary half
sockets for the duplex cable and triple conductor, which cover is
secured in position by screws 46 engaging threaded bores 125 47 in the
ridge 15.
In the case of the particular switch according to the present
invention being described, the cover 48 is either of transparent
material and is lined on its flat inner 130 784,778 surface with a
sheet 49 of opaque material with a rectangular slot 50 to leave a
transparent window 51 to the interior, or it can be moulded in a
translucent plastic, leaving for a window a thinned-out portion of the
plastic Further, this cover on the interior has such volume and shape
that it can accommodate the component shown in Fig.
4 between itself and the switch body when the cover is screwed into
position.
This component comprises a somewhat crescent-shaped carrier 52 of
insulating material, the end portions of which are thinned and
apertured at 53 to coincide with j 5 the threaded bores 47 The central

portion is thickened and on its upper side is recessed at 54 to
accommodate a miniature glow lamp 55 which on the assembly is so
positioned that it comes beneath the transparent window 51 so that
when alight this fact is readily visible.
At one end the recess 54 opens into another recess 56 for a resistance
57 in series with the lamp 55 The ends of the lamp and resistance
circuit are connected to pins 58 and 59 passing through and held in
the thickened part of the carrier 52 and terminating in slightly
projecting contacts 60 and 61 on the flat underside of the carrier
(Fig.
5) When the parts are assembled, these contacts 60 and 61 come above
the terminal 22 and another free terminal 62 mounted on the ridge 15.
The terminal 22 is shown in Fig 6 and the head of the screw serves to
secure a spring contact 63 in position above the terminal, as shown
Similarly, as shown in Fig 7, the head of the screw of the terminal 62
serves to secure a spring contact 71 in position above the terminal
These spring contacts are slightly and forcibly depressed by the
contacts 60 and 61 when the parts are assembled and hold the lamp 55
and resistance 57 in the required circuit.
64 is a conducting wire which connects the terminals 62 and 28 In Fig
3 the wire is shown as a dotted line on the exterior of the switch
casing, for the sake of clearness.
Actually, it is disposed in the groove 16 so beneath the insulated
leads 66 and 68.
In the operation of the switch according to the invention, it is
pointed out that Fig.
8 and also Fig 3 show one position in which the blanket is out of
circuit and consequently the lamp 55 not lit This is due to the fact
that although the contact 60 (Fig 5) is in connection with the
terminal 22 and supply lead 24, yet the contact 61 (Fig 5) although
connected to the group of contacts 40 to 44, through the terminal 62,
wire 64 and terminal 28, is not "live" as the contact 40 is at 30
spacing from the terminal 23 for the other supply lead 25.
The other position in which the blanket is out of circuit is the
position of the parts when the handle is set into the position XII,
Fig 3 This is set out in Fig 12 where although the contact 60 is above
and connected to the terminal 22 and the contact 61 above and in
connection with the termi 70 nal 62, the supply lead 25 is isolated.
In the other three positions of the switch, that is, the " on "
positions, shown in Figs.
9, 10 and 11 and corresponding to the positions IX, X and XI of the
handle in Fig 75 3, the blanket is switched into the circuit, the
contact 60, as in Figs 8 and 12, remaining connected to the input lead
24.

In Fig 9 the connections to the blanket are via the common lead 66 and
the outer 80 lead 67 so that both of the heating wires or elements 69
(Fig 8) connected in series, are in the heating circuit The central
lead 68, however, is " live " due to its connection to the junction
between the two heating ele 85 ments 69 and 70, and consequently its
connection via the wire 64, terminal 62 and contact 61 completes the
circuit through the lamp, in parallel with part of the heater circuit
90 In Fig 10 the connected contacts 35 and 36 bridge the gap between
the terminals 22 and 26 and the connected contacts 41 and 43 the gap
between the terminals 28 and 23.
The common lead 66 and central lead 68 95 are thus the conveyors of
current to the heating wire or element 69 alone, and the lamp is lit
owing to its associated contacts and 61 being connected in parallel
with the live terminals 22 and 28 In this case it 100 should be
appreciated that the outer lead 67 to the blanket is cut out as its
terminal contact 32 comes in the gap between the two groups of moving
contacts of the rotor.
In Fig 11 the group of four contacts con 105 nect the common lead 66
and the outer lead 67 to the supply line 24 and the group of five
contacts the central lead 68 to the supply line 25 As a result, both
heating wires or elements 69 and 79 are in circuit arranged 110 in
parallel and the lamp 55 is alight by the same connections as set
forth for Fig 10.
Obviously, switches for electric blankets in accordance with the
invention can take many forms other than that particularly 115
described For instance, in place of the lamp and resistance being
mounted in a separate component, this structure could be integral with
the cover and in this case the recesses for the lamp and resistance
would be open 120 from below Care would also be necessary to arrange
that the closed top of the lamp recess was thin enough for the glow to
be seen from the exterior In this last-mentioned form, in place of a
contact such as 61 being 125 located above a terminal such as 62,
provided for the purpose, it could come above a terminal such as 28
for the outer lead 68, and the terminal 62 dispensed with The wire 64
would then be replaced by a wire 130 784,778 in the cover leading to
its associated contact 61.
In other variations the moving part of the switch could have a
rectilinear path and the other parts be modified accordingly.
The invention is not limited to the precise forms or details of
construction herein described, as these may be varied to 3 wit
particular requirements.
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* GB784779 (A)
Description: GB784779 (A) ? 1957-10-16
Dynamo-electric machine rotor spider
PATENT SPECIFICATION
Date of Application and filing Complete Specification: June 1, 1956.
Application made in Sweden on June 18, 1955 Complete Specification
Published: October 16, 1957
784,779 No 16944/56 Index at acceptance:-Classes 35, A 13 X; and 83 (
2), A 44.
International Classification:-B 23 p H 02 k.
COMPLETE SPECIFICATION
Dynamo-Electric Machine Rotor Spider We, ALLMANNA SY PNSKA ELEKTRISKA
AKTIEBOLAGET, a Swedish Company of Visteras, Sweden, 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 a l O dynamo-electric machine rotor
spider of thekind comprising a hub and arms extending from the hub for
carrying an annular armature core made from magnetic stampings.
According to the invention a dynamoelectric machine rotor spider is
characterised in that it consists of a number of thick rectangular
sheets each of which along one edge is welded to the side of its
adjacent sheet with the sheets arranged in such a way that the parts
of the sheets between the welded joints form a hub in the form of a
tube of polygonal section and the other parts of the sheets form arms
extending from said tube for carrying the armature The said tube of
polygonal section, the inscribed circle of which has a smaller
diameter than the shaft intended to carry the rotor spider, is turned

internally to fit the said shaft and is provided with a key groove,
and thus forms a hub The arms.
which preferably leave the hub tangentially, are turned at their ends
remote from the hub to fit inside the annular armature core of the
machine.
The spider according to the invention is very suitable for mounting
the rotor of a direct-coupled exciter for a large electric generator
Such generators are usually designed, and made in accordance with, the
wishes of the purchaser and are very seldom standardised The auxiliary
machinery, however, is very often constructed from standardised parts
Thus, for example, the exciter may be constructed from a standard
annular armature core made from stampings which is fixed to the
generator shaft by means of a spider adapted to fit the shaft in
question.
An advantage of the invention is that no 50 separate hub is necessary
as in the case of spiders used at present Due to this it is a simple
and inexpensive matter to construct a spider to fit inside a standard
annular armature core and onto a non-standard 55 generator shaft
Hitherto the cost of the separate hub has been a considerable part of
the total cost of the spider.
A spider according to the invention will now be described with
reference to the ac 60 companying drawing, in which Figure 1 is a end
elevational view of the spider and Figure 2 is a longitudinal section
along the line A-A of Figure 1 65 Referring to the drawing, 1
designates plane thick rectangular sheets and 2 the welded joints
joining the sheets together.
The parts 3 of the sheets 1 between the welded joints form the sides
of a tube or 70 hub of polygonal section which is turned internally to
fit a shaft 5, and is provided with a key-groove The hub is secured
against rotation relative to the shaft 5 by a key 6 The outer parts 4
of the sheets 1 75 form arms carrying an annular armature core (not
shown).
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* GB784780 (A)

Description: GB784780 (A) ? 1957-10-16
Method of dissolving or dispersing metal naphthenates in liquid
hydrocarbons, especially lubricating oils
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amongst the following family members:
CH323327 (A) DE1006564 (B) FR1076375 (A) NL111902 (C)
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The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
PATENT 8 PECIFICAT 1
784,780 Date of Application and filing Complete Specification April
13, 1953.
/& ue No 10082/53.
Application made in Germany on April 12, 1952.
Application made in Germany on May 2, 1952.
Application made in Germany on May 16, 1952.
Complete Specification Published Oct 16, 1957.
Index at Acceptance:-Class 91, F 1.
International Classification: -CI O m.
Method of Dissolving or Dispersing Metal Naphthenates in Liquid
Hydrocarbons, especially Lubricating Oils We, RHEIN-CHEMIE
GESELLSCHAFT MIT BESCHRINKTER HAFTUNG, a body corporate organised
according to the laws of Germany, of Heidelberg, 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: It is known
to add oil-soluble soaps or salts of sulphonic acids to mineral oils
in order to bind sulphurous or sulphuric acid formed during the
combustion of fuels containing sulphur This is necessary because the
free acids lead to the formation of resinifying or coking products on
the pistons, piston rings and oil wiping rings The use of metal salts
of naphthenic acids, especially barium or aluminium naphthenate, has
been proposed for this purpose As is known, salts of naphthenic acid
are also used in admixture with organic solvents, especially liquid
hydrocarbons, for various purposes in chemical technology, for
example, in the fields of impregnation, pest control, and plastics
However, they are difficult to use owing to their physical properties.
They form gels with liquid hydrocarbons or are insoluble or sparingly
soluble in liquid hydrocarbons In consequence they considerably
increase the viscosity of the liquid hydrocarbons with which they are
mixed This increase in viscosity does not permit, for example, large
amounts of metal salts of naphthenic acids having polyvalent cations
to be incorporated with engine oil, so that in the case of high power
engines, which are driven with fuels containing considerable amounts
of sulphur, insufficient cations are present to bind sulphuric acid
formed and to prevent undesired attack on lubricating oil films and on
engine parts.
In order to enable the metal naphthenates, which in the pure state are
solid and in some case brittle substances, to mix easily with
solvents, especially liquid hydrocarbons and hydrocarbon oils, it has
been proposed to use solution promoters of various kinds, for example,
glycols, glycol esters of lower acids and glycol ether with alcohols
of low molecular weight.
The present invention is based on the observation that the solvent
action of solution promoters can be combined with other actions which
are favourable to the properties of the solutions produced therewith
and to the purposes for which the solutions are used.
An object of the invention is to provide for use in dissolving metal
salts of naphthenic acids in liquid hydrocarbons solution promoters
which lower the viscosity of hydrocarbon oils containing metal
naphthenates and at the same time exert a solvent or dispersing action
on resinfication products and other decomposition products of the oil.
A further object of the invention is to provide, in addition to the
solution promoter which is hereinafter referred to as " solvent A ", a
second substance, referred to as " solvent B ", which supplements the
action of solvent A.
The invention also includes special procedures for preparing mixtures
of metal naphthenates with liquid hydrocarbons or hydrocarbon oils
with the aid of solvent A and, if desired, also solvent B It has been

found that in many cases it is of advantage first to prepare a
solution or mixture of the metal naphthenate with the solvents A and
B, and then to mix the resulting solution or mixture with the liquid
hydrocarbon Solutions consisting of the metal naphthenate, a solvent A
and a solvent B have been found especially valuable as additives to
hydrocarbon lubricating oils, in particular engine oils Accordingly,
the invention also includes the preparation of metal
naphthenate-containing compositions having special properties and
their use as additives to hydrocarbon lubricating oils.
In accordance with the invention liquid solutions or liquid
dispersions of metal salts of _ 784,780 naphthenic acids, especially
barium naphthenate or aluminium naphthenate, in liquid hydrocarbons or
hydrocarbon oils, such as mineral oils, and especially lubricating
oils, are prepared with the aid of an etherified or esterified
polyaliylene glycol of the general formula XO-RP-O),-R-OY, in which R
represents an alkylene radical 2 or 3 carbon atoms, N represents a
whole number from 2 to 20 or higher, and especially from 2 to 7, X
represents a hydrocarbon or acyl radical containing more than 6 carbon
atoms, and advantageously more than G carbon atoms, and Y represents a
hydrogen atom or a hydrocarbon or acyl radical containing any desired
number of carbon atoms The etheriie-d or esterified polyalkylene
glycol of the above general formula constitutes the solvent A referred
to above.
As etherified polyalkcylene derivatives there come into consideration,
for example, the following:Dodecyl pentaethylene glycol, octadecenyl
hexaethylene glycol, lauryl pentapropylene glycol (the term " jauryl"
throughout the specification denotes the hydrocarbon radical of the
fatty alcohols obtained from coconut oil fatty acids), 2-ethylhexyl
pentaethylene glycol, nonyl heptaethylene glycol, phenylethyl
pentaethylene glycol, methyl-cyclohexyl octaethylene glycol,
para-actyl-phenyl tetrapropylene glycol, dodecyl cyclohexyl
hexapropylene glycol, hexylnaphthyl tetraethylene or tetrapropylene
glycol.
As polyalkylene glycols etherified on both sides there may be used,
for example, the following: Dodecy I or lauryl pentaethylene glycol
methyl ether, para-octylphenyl tetraethylene glycol isopropyl ether,
octadecenyl hexaefnylene glycol ethyl-hexyl ether, 2-ethylhexyl
heptaethylene glycol benzyl ether As alcohols for the etherification
there may also be used those which are obtainable by the reduction of
natural or synthetic fatty acids, by the hydrogenation of carbon
monoxide under atmospheric or superatmospheric pressure, by the
oxo-synthesis or by the oxidation of paraffin wax.
Among the polyallylene glycols esterified on one or both sides there
are suitable, inter aia, pentaethylene glycol rnonostearate,

hexaethylene glycol monostearate, dodecyl-benzyl pentapropylene glycol
oleate, stearyl-pentaethylene glycol isopropyl ether,
bzizoylpentaethylene glycol oleate, benzoyl-1 lieptaethylene or
heptapropylene glycol cctyl ether or benzoyl-pentaethylene glycol
methyl ether.
in general there are advantageously used fatty alcohol polyglycol
ethers of the foregoing formula, in which N advantageously represents
4 Of advantage are those ethers or esters of the above formula in
which X represents a hydrocarbon or acyl radical containing 12 carbon
atoms.
The solutions of metal salts of naphthenic acids in liquid
hydrocarbons can be made in accordance with the invention in various
ways.
The metlhod used depends on the particular metal naphthenate,
polyglycol derivative and the hydrocarbon oil in which these
substances are to be incorporated It is of advantage to work at a
raised temperature, for example, at 90-150 C C For example, the
aforesaid components may be mrixed together, advantageously while
stirring at a raised temperature, or a solution, a gel or a suspension
of a metal naphthenate in a liquid hydrocarbon may be mixed with the
palyalkyiene glycol derivative Alternatively, the metal naphthenate
may be added, while stirring, to a solution of a polyalkyleine glycol
derivative in a liquid hydrocarbon Finally the two components may each
be sepa-rately dissolved in the liquid hydrocarbon and the solutions
subsequently muied together.
The proportion of the polyalkylene glycol derivative required may vary
within wide limits, for example, from 1 per cent by weight calculated
on the metal naplhthenate up to an equal weight or higher 1 ihe
proportion to be added depends on the nature of the metal naphthienate
used and also of the liquid hydrocarbon and on the viscosity of the
desired solution.
The following examples illustrate the invention, the parts and
percentages being by weight: EXAMPLE 1 100
The capacity of lauryl pentaethylene glycol ether for lowering the
viscosity of mixtures ot mineral oils with various metal salts of
naphthenic acid is strong This is shown by the table given blowv The
parts by weight of the 105 naphlthenates given below are stirred into
159 parts by weight of a mineral oil (specific gravity at 20 C = O
882, viscosity index= 89, carbon number according to Gonradson= 0.11,
constituents insoluble in benzene= 0) at 110 a temperature of 1 C
0-110 C until a homogeneous mixture is obtained, and the viscosities
of -the resulting slutieons are determined at O C or 50 C The same
solutions are mix-d with lauryl pentaethylene glycol ether 115 in the
proportions by weight given in the table and the viscosity of the

solutions is determined at 80 C or 50 C.
-784; 7 j 8 Parts by weight Parts by of lauryl penta Viscosity at of l
a C y penta-tke Naphthenate weight glycol ether C centistokes
Aluminium naphthenate l 80 27 59 ,, 1 0 4 80 19 80 Aluminium and
calcium naphthenate 5 + 5 80 49 99 ,,, ,, 5 + 5 4 80 30 00 Zinc
naphthenate 30 800 72 76 ,,, 30 4 80 37 04 Iron naphthenate 30 50 119
02 ,,, 30 4 500 108 20 Lead naphthenate 30 50 85 2 ,,> 30 4 50 78
EXAMPLE 2.
The addition of polyalkylene glycol derivatives lowers the viscosity
also in the case of naphthenate solutions which are themselves of low
viscosity A solution of 30 parts by weight of calcium naphthenate in
100 parts by weight of a hydrocarbon oil having a boiling range of
150-270 C and resembling Diesel oil has a viscosity of 3 02
centi-stokes at 80 C By the addition of 8 parts of methyl
heptaethylene glycol naphthenic acid ester to 100 parts of the
aforesaid solution the viscosity is lowered to 2 74 centi-stokes at 80
C.
EXAMPLE 3.
The viscosity of a mineral oil having a viscosity of 18 7 centi-stokes
at 80 C is increased to 29 5 centi-stokes at 80 C by dissolving
therein 10 per cent of potassium naphthenate The addition of 20 per
cent of decyl pentaethylene glycol ether to the solution lowers the
viscosity to 21 26 centi-stokes at 80 C.
The methyl ether of the aforesaid polyglycol ether or its benzoate has
a similar action.
EXAMPLB 4 parts of tetrahydronaphthalene and 20 parts of barium
naphthenate have an average viscosity of 15 5 centi-stokes at 80 C By
adding 10 parts of lauryl pentaethyleneglycol ether to 100 parts of
the aforesaid solution, the viscosity falls to 1 76 centi-stokes at 80
C.
EXAMPLE 5.
The neutral barium naphthenate prepared from distilled naphthenic
acids having an acid number of 180 is a brittle resin at ordinary
temperature, which changes into a rubberlike condition at about 100 C
and has a dropping point of over 230 C It is only very sparingly
soluble in mineral oils and the solution yields a stiff jelly after
cooling A fatty alcohol containing 6 8 per cent by weight of hydroxyl
and obtained by hydrogenating under a high pressure a fatty acid
obtained by the oxidation of paraffin wax, is oxyethylated in known
manner with 5 mols of ethylene oxide with the use of an alkali as a
catalyst, and there is obtained a polyglycol ether which is wax-like
at room temperature and has a dropping point of 38 C.
When 40 parts of the brittle barium naphthenate are mixed at about 100
C with 15 parts of the aforesaid polyglycol ether, while stirring

well, the rubber-like structure disappears, and after cooling there is
obtained a syrup which can be drawn out into filaments and which is
easily soluble without leaving any residue in liquid hydrocarbons.
In many cases it has been found advan.
tageous when incorporating a metal salt of a naphthenic acid in a
liquid hydrocarbon with the aid of a polyglycol derivative (solvent
A), also to use an ether (solvent B), which is free from polyglycol
groups and contains at least one radical having 6 or more carbon
atoms.
The ethers may be of the aliphatic, aromatic, or alicyclic series or
of a mixed character It has been found very advantageous to use high
boiling ethers which are liquid at room temperature These ethers
differ from solvent A in that they contain no polyalkylene glycol
groups.
It is surprising that ethers of this kind act as solution promoters
with respect to both the naphthenate and the esterified or etherified
polyalkylene glycol and mixtures thereof, and are moveover easily
soluble in organic solvents, especially in liquid hydrocarbons and
hydrocarbon oils.
Among these high boiling ethers there may be used, for example, the
following:Di-n-hexyl ether di-nr-octyl ether, di-nnonyl ether,
di-2-ethylhexyl ether, dodecyl ethers, for example, a dodecyl octyl
ether and especially dodecyl 2-ethyl-hexyl ether, dodecyl phenyl
ether, dodecyl cyclohexyl ether, octadecen-( 9)-yl-1-isobutyl ether,
octadecyl-Ptetrahydronaphthyl ether, nonyl-4-methylcyclohexyl ether,
4-octylphenyl-2-ethyl-hexyl ether,, tetrahydronaphthyl-methyl phenyl
ether and also benzyl ethers or alkyl substituted benzyl ethers of
aliphatic or alicyclic alcohols, for example, nonyl benzyl ether,
octadecenyl4-methyl-benzyl ether, dibenzyl ether,
tetrahydronaphthyl-methyl benzyl ether, and also tetrahydronaphthyl
methyl-2-ethylhexyl ether, 784,780 butanediol-( 1: 3)-monooctyl ether,
butane diol-( 1: 4)-dibenzyl ether and butane diol( 1:4)-isobutyl
dodecyl ether.
There can also be used with advantage the ethers of fatty alcohols
prepared by the reduction of fatty acids obtained by the oxidation of
paraffin wax or the alcohols of forerunnings or oxo or
naphthene-alcohols, for example, paraffin wax fatty alkyl cyclohexyl
ether, dodecyl fatty alkyl (forerunnings) ether, the alcohols of the
forerunnings being a mixture of alcohols obtained by hydrogenating
fatty acids from the oxidation of paraffin wax under a high pressure
and then distilling the alcohols, the latter being obtained as
forerunnings and contain a chain length of 6-9 carbon atoms From
naphthenic acids, such as are obtained in the raffination of mineral
oils, there can be made by reduction under high pressure or by the

method of Bouveault-Blanc the corresponding naphthenic alcohols, which
can easily be converted into ethers which can be used with advantage
in the method of the invention As examples thzre may be mentioned,
dinaphthenyl ether and also naphthenyl benzyl ether or
naphthenyl-2-ethylhexyl ether.
Instead of a single ether there may be used a mixture of two or more
ethers or a solution of a single ether or a mixture of' thers in a
liquid hydrocarbon or hydrocarbon oil.
By the use of ethers of the kind described above (solvent B) in
accordance with the invention there is obtained an improvement or
acceleration in the solubility of metal salts of naphthenic acids in
liquid hydrocarbons ot hydrocarbon oils in the presence of solvent A.
Whereas, for example, a mixture of a metal naphthenate with a poly
alkylene glycol derivative is a wax-like mass at room temperature,
there is obtained a clear solution even after the addition of 20 per
cent of an ether or mixture of ethers to the mixture of metal
naphthenate and polyalkylene glycol derivative The resulting solution
can easily be diluted with liquid hydrocarbons.
The aforesaid ethers act not only as solution promoters, but they also
lower the viscosity of solutions or mixtures in which a polyalkylene
glycol derivative and a metal salt of a naphthenic acid are
incorporated in a liquid hydrocarbon Furthermore they also act as
solvents or dispersing agents for deposits of resins, lacquers or
asphalts, when a mixture of a metal naphthenate, solvent A and solvent
B is used as an addition to hydrocarbon engine oil.
The proportion of solevnt B to be added to the mixture of a metal
naphthenate and a polyalkylene glycol derivative may vary within wide
limits, for example, up to 200 per cent.
and higher The proportions are not dependent only on the nature and
quantity of the metal naphthenate or mixtures of metal naphthenates or
the polyalkylene glycol derivative added thereto, but also on the
improvement desired in the solubility or msicibility of the metal
naphthenates in liquid hydrocarbons or hydrocarbon oils and also on
the viscosity desired in the solutions.
Solutions of metal naphthenates in hydrocarbon oils in the presence of
an ether (solvent B) and a polyalkylene glycol derivative can be
prepared in various ways Thus, for example, the metal naphthenate may
first be dissolved with the aid of heat in the ether (solvent B) or in
the polyalkylene glycol derivative (solvent A) and the other of these
solvents added to the resulting solution, and the solution so obtained
diluted with the liquid hydrocarbon or hydrocarbons The metal
naphthenate may first be thoroughly mixed or stirred, preferably after
being melted, with the polyalkylene glycol derivative, and the ether
added to the resulting mixture and the whole mixture added to the

liquid hydrocarbon or hydrocarbons Furthermore, a solution of the
liquid hydrocarbon or hydrocarbons, ether and polyaikylene glycol
derivative may first be prepared, and the metal naphthenate then
dissolved in the solution.
Finally, the metal naphthenate and the polyalkylene glycol derivative
(solvent A) may each be dissolved separately in the ether, and the two
solutions may then be united The resulting mixture dissolves easily in
hydro.
carbon oils.
EXAMPLE 6
This example shows that by the addition of ethers used in the
inevntion clear solutions of 100 metal naphthenates in the
polyalkylene glycol derivatives are obtained.
Various metal naphthenates having the cations mentioned below are
melted with the polyalkylene glycol derivatives described 105 below in
the ratio 10: 1 at a temperature of 40-80 C After cooling, there are,
obtained wax-like substances These mixtures are mixed with the ethers
given below in the ratio 1: 1, and in this manner there is 110
obtained in each case a thinly liquid solution which can be easily
incorporated in hydrocarbon oils.
z 4 784,780 Polyalkylene glycol Cation derivative Ether Potassium
Naphthenic acid heptaethylene ethylhexyl benzyl glycol ester ether
Zinc (divalent) Dodecyl pentaethylene glycol lauryl N butyl methyl
ether ether Lead Benzyl pentaethylene glycol benzoate dioctyl ether
Iron (trivalent) Para-octylphenyl tetraethylene glycol ether dibenzyl
ether Aluminium/calcium Stearyl hexaethylene glycol tetradecyl
methylbenzoate cyclohexyl ether EXAMPLE 7
Neutral aluminium naphthenate is very sparingly soluble in liquid
hydrocarbons, for example, in a light petroleum fraction having a
boiling range of 150-270 C and a viscosity of 2 centistokes at 80 C or
in a higher boiling mineral oil boiling, for example, at 200-300 C and
having a viscosity of 20 centistokes at 80 C A solution of aluminium
napthenate in the higher boiling mineral oil produced by stirring for
a long time at a raised temperature, for example C, is a thick gel
which becomes nonhomogeneous upon cooling and from which a part of the
oil used separates out The viscosity of the freshly prepared solution
cannot be determined with accuracy, but it is approximately 6000
centistokes at 80 C.
Such a gel cannot be used for technical purposes, for which a solution
of aluminium naphthenate is desired An addition of 4 per cent of
lauryl pentaethyleneglycol ether lowers the viscosity of the aluminium
naphthenate solution in the oil from above 6000 to about 160
centistokes at 80 C.
It is even more advantageous first to dissolve the aluminium

napbthenate in an ether Viscosity of the mixture at 80 C.
+ 20 % of dodecyl ethyl-hexyl ether + 40 %,, ,,,,, , + 60 %,,,,,,,, +
80 %, 3,, , + 100 % ',,,,,, , The solutions so obtained are easily
miscible with hydrocarbon oils.
EXAMPLE 10
A solution of 50 per cent strength of barium naphthenate in a liquid
hydrocarbon, for 'example, of the type of spindle oil, could not be
prepared hitherto or could be prepared only with very great
difficulty, and could not be used for technical purposes It is
relatively easy to prepare a solution of the same (solvent B) By
dissolving 10 parts of aluminium naphthenate in 100 parts of
dodecyl2-ethyl-hexyl ether there is obtained a solution haivng a
viscosity of 1890 centi-stokes at C The viscosity is then lowered to
99 centi-stokes by the incorporation of 4 per cent of lauryl
pentaethyleneglycol ether The resulting solution is easily miscible in
all proportions with liquid hydrocarbons and thinly liquid solutions
are always obtained.
EXAMPLE 8
A solution of 50 per cent strength of calcium naphthenate in dodecyl
octyl ether has a viscosity of 18 60 centi-stokes at 80 C, which is
lowered by the addition of 10 per cent of dodecyl pentaethyleneglycol
ether of 11.4 centi-stokes The solution so obtained is easily miscible
with hydrocarbon oils.
EXAMPLE 9
The following table shows the effect on the viscosity of a mixture of
60 parts of barium naphthenate and 30 parts of lauryl
pentaethyleneglycol ether obtained by adding varying proportions of
lauryl ethyl-hexyl ether.
122 0 centi-stokes 38.1,, 18.5,, 12.5,,,, 9.2,, 7.2, concentration of
the naphthenate in lauryl ethyl-hexyl ether, and the solution has a
viscosity of 2335 centi-stokes at 80 C By the addition of the
polyethylene glycol derivatives named below the viscosity of the
solution is very considerably reduced This reduction in viscosity is
dependent on the degree of polymerisation of the polyalkylene glycol
derivatives used, as will be seen from the following results:% of
lauryl triethylene glycol ether= 11 80 centistokes at 80 C.
% of lauryl pentaethylene glycol ether= 11 94,,,,, %' of lauryl
heptaethylene glycol ether= 13 38 p,,, S 784,780 When the
viscosity-lowering substance lauryl hexaethyleneglycol ether is
further etherified with ethyl-hexanol to form lauryl
hexaethyleneglycol ethyl-hexyl ethere, the viscosity i is lowered
within the same limits and gives for an addition of 20 per cent a
viscosity of 13.64 centistokes.
The above solutions are easily miscible with hydrocarbon oils -EXAMPLE

11
This example illustrates the capacity of various polyalklylene glycol
derivatives for lowering the viscosity of a solution of 50 per cent
strength of barium naphthenate in lauryl ethyl-hexyl ether The initial
solution has a viscosity of 3255 centistokes at 80 C The following 2
olyalkylene glycol derivatives when used in a proportion amounting to
20 per cent yield solutions having the following viscosities:Benzyl
pentaethylene glycol ether 10 4 centistokes at 80 C.
Octyl-phenol octaethylene glycol ether 15 5,,, ,, Stearic acid
heptaethylene glycol ester 140,,,, ,, The solutions so obtained are
easily miscible with hydrocarbon oils.
The joint use of polyglycol derivatives (solvent A) and high boiling
ethers (solvent B) in addition to metal naphtlhenates has been found
to be especially effective in improving hydrocarbon engine lubricating
oils In applying the invention for this purpose it is especially
advantageous first to prepare a mixture of the metal naphthenate with
the polyglycol ether or ester (solvent A) and the high boiling ether
(solvent B), and to add the resulting mixture to the hydrocarbon oil,
advantageously with the aid of heat These additions are suitable for
all kinds of internal combust''on engines Even under severe conditions
they retain their cleansing action on the engine.
The new additions to hydrocarbon engine lubricating oils also act well
in the case of cold engines, that is to say, at low oil temperatures
of, for example, 40-50 C.
The proportions in which the additionsa should be incorporated in
hydrocarbon engine lubricating oils depends on various factors.
These include the quality of the hydrocarbon engine lubricating oil,
the period for which the engine is run without changing the oil, and
the sulphur content of the fuel.
The content of the added substances in the oil should be greater the
poorer the quality of the engine oil,; the longer the period for which
the engine is to be run without chang-' ing the oil, and the higher
the sulphur content of the fuel.
In general the proportion of the mixture of metal naphthenate, solvent
A and solvent B added to the engine oil is advantageously within the
range of 1 to 15 per cent on the weight of the oil Hlowever, smaller
or higher proportions may be added.
The substances, or mixtures or solutions ot substances, to be added to
the engine oil, may be incorporated in the oil simukltaneously or in
any desired order of succession.
A good homogeneous distribution of the added substances, namely a
mixture of a metal naphthenate with solvent A and solvent B, in
hydrocarbon engine lubricating oils is obtained by incorporating these
mixtures at temperatures of-about 40-60 C or higher.

For example, even temperatures up to 150 C may be used In many cases a
homogeneous mixture is obtained even at lower temperatures.
To the new additions for engine oils or to the mineral oil solutions
made there-with there may also be added agents improving the pour
point or viscosity and also age-protecting agents or oxidation
inhibitors, for exampe, alkyl substituted phenols or cresolhn,
compounds which contain divalent sulphur and also secondary aromatic
amines, phenthiazines, phosphoric acid esters or thiophosphoric acid
esters, or salts of thiophenols.
The favourable action of these new additions for engine oils is
illustrated by the following examples:EXAMPLE 12
The following mixture is prepared:parts of lauryl ethyl-hexyl ether,
parts of a pentaethyleneglycol ether of a fatty alcohol, which has
been obtained by hyd 95 rogenating under high pressure a fatty acid
obtained by the oxidation of paraffin wax, and which has a hydroxyl
number of 6 6, 49 parts of barium naphthmnate, parts of
para-ethyllexyl-phenol 100 parts of the above mixture were added to
parts of a paraffin base oil having the following characteristics:
Specific graivty at 30 ' C = O 885 Ignition point = 225 C 105
Viscosity at 500 C = 65 8 centi-stokes.
The above oil blend was tested as engine oil in a diesel engine under
the following severe conditions of test:Oil temperature 160 C 110
Duration of test 120 hours working under full lead.
There was used a Middle East diesel fuel which had a sulphur content
of 1 per cent.
At the end of the test all piston rings were 115 freely movable, the
oil wiping rings had no deposits of sludge or coke thereon and both
the outsides and insides of the pistons had a preponderantly metallic
appearance.
W 7 hen the used oil was tested for its lubri 120 cating property in
an Almen-Wieland machine it gave /l-values (coe ficient of friction)
rang: -g 784,780 ing between 0 2 and 0 1 at a load capacity of 28
plates ( 1400 kgs).
EXAMPLE 13 rhe following mixture was tested:
65 parts of lauryl ethyl-hexyl ether, parts of
lauryl-pentaethyleneglycol ether, 36 parts of barium naphthenate,
parts of ethylhexyl-phenol A paraffin base oil as described in Example
13 was mixed with 10 parts of the above mixture and the mixture was
tested as an engine oil in the engine of a travelling motor vehicle.
The distance travelled was 6000 kilometres without changing the oil
and merely making up the oil consumed.
At the end of the test journey the piston rings and the oil wiping
rings were freely movable and no deposits of coke or sludge had formed
in the grooves carrying the rings The walls of the pistons and the

interiors thereof had an entirely lustrous metallic appearance.
Tests on the lubricating property of the used oil in the
Almen-Wieldand machine gave Ax-values between O 1 and 0 2 at a plate
number of 20 '( 1000 kg).
EXAMPLE 14
The following mixture in the form of a 10 per cent addition to upper
cylinder lubricating oil was tested in a 2-stroke diesel engine:-parts
of barium naphthenate, parts of calcium naphthenate, parts of
naphthenic alcohol hexaethyleneglycol ether, parts of dioctyl ether,
parts of di-tertiary-butyl-paracresol.
As the upper cylinder lubricating oil there was used a paraffin base
oil such as is described in Example 13.
After a test period of 10 hours at 4500 revolutions per minute and a
water temperature of 95 C, the piston rings were freely movable, and
the pistons had a metallic appearance both inside and outside.
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* 5.8.23.4; 93p
* GB784781 (A)
Description: GB784781 (A) ? 1957-10-16
Manufacture of water-insoluble azo-dyestuffs

784781 Date of Application and filing Complete Specification: Dec 3,
1953.
' i' No 33695153.
Ski /1 Application made in Germany on Dec 3, 1952.
Complete Specification Published: Oct 16, 1957.
Index at acceptance:-Classes 2 ( 4), P 1 (A 4 B: F 4), P 2 G 2 A, P 2
H( 3: 9:10:12:13), P( 2 J: 4 K), P 9 A 3 C 1, P 9 A 4 (B: C); and 15 (
2), B 2 (A 2: C 1 D 2 C).
International Classification:-C 09 b D 06 p.
Manufacture of Water-Insoluble Azo-Dyestuffs We, FARBWERKE HOECHST
AKTIENGESELLSCHAFT vormals Meister Lucius & Br Uning, a body corporate
recognised under German law, of Frankfurt(M)-Hdchst, 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: According to
this invention new, valuable, water-insoluble azo-dyestuffs are made
by coupling in substance or on the fibre a diazocompound of an
amino-azo-compound of the following general formula:
0 4 al/yl //_ v i,,=,v-e A-eo-,w-R t Co 0 A//kyl #2 z 1< dop in which
R represents an aromatic, hydroaromatic, araliphatic or heterocyclic
radical and R, represents a methyl or phenyl group, with an arylide of
acetoacetic acid or terephthaloyl-bis-acetic acid, the dyestuff
components being free from groups imparting solubility in water to the
finished dyestuifs, such as sulphonic acid or carboxylic acid groups
The azo-dyestuffs so obtained correspond to, the following general
formula:
in which N represents one of the numbers 1 or 2, R represents an
aromatic, hydroaromatic, araliphatic or heterocyclic radical, R,
represents a methyl or phenyl group, and R 2 represents the radical of
an arylide of acetoacetic acid or terephthaloyl-bis-acetic acid the
dyestuff components being free from groups imparting solubility in
water to the finished dyestuffs, such as sulphonic acid and carboxylic
acid groups.
The new dyestuffs yield mainly clear red tints, and are of particular
importance for use in print style for the following reason The 40
diazo-components of the present invention can produce on the so-called
yellow naphthols of commerce (which term defines coupling components
which either contain acylacetyl-aminogroups or are derived from
pyrazolone), clear 45 yellowish-red to bluish red tints which have
hitherto been unlmown in practice on the basis of an arylide of a
/-ketocarboxylic acid, as compared with yellow tints produced by the

use of known diazo-components on yellow 50 naphthols.
It is to be understood that no claim is made herein to the products of
reacting a diazocomponent of the present invention with a yellow
naphthol derived from pyrazolone 55 In a great number of cases, the
new dyestuffs possess good properties of wet fastness and good
fastness to light Therefore they constitute a valuable advance of the
class of icecolours 60 The aminoazo-compounds used as diazocomponents
can be obtained, for example, by coupling a diazotised 1-amino-2:
5-di-alkoxy4-nitrobenzene with an acylacetic acid anmide of the
following formula 65 R 1-CO-CH,-CO-NH-R, in which R represents an
aromatic, hydroaromatic, araliphatic or heterocyclic radical and R,
represents a methyl or phenyl group, and subsequently reducing the
nitro group to 70 the amino group.
The following Examples illustrate the inver;iion, the parts being by
weight, unless otherwise stated, and the relation between part by
weight and part by volume being the 75 same as that between the
kilogram and the litre:
EXAM Pi LE 1.
38.6 parts of -( 41-amino-21: 5-dimnethoxybenzen:-1 '-azo) acetoacetic
adi& 3-mthoxy 80 anilide of the following formula 1 cc 0 &A, Y/ 1 R,
784,781 oe HH 0 1 ce a C/I (obtainable by coupling diazotised
1-amino2:5-dimethoxy-4-nitro-benzene with acetoacetic
acid-3-methoxy-anilide and subsequently reducing the nitro group to
the amino group) are kneaded with 35 parts of hydrochloric acid of 35
per cent strength and 35 parts of water, the hydrochloride of the
amina compound being formed 1000 parts of water are then run in, while
stirring, and the mixture is diazotised at room temperature by adding
dropwise, in the course of about 10 minutes, 17 5 parts of a sodium
nitrite solution of 40 per cent strength The mixture is then stirred
further for a few minrutes The diazo-solution is clarified by
filtering with suction and the filtrate is run, while stirring, into a
suspension of acetoacetyl-aminobenzene, which is prepared as
follows:17 7 parts of acetoacetylaminobenzene are stirred with 250
parts of water, 15 parts of a sodium hydroxide solution of 38 B 6 and
5 parts of Turkey Red oil until dissolution is complete The anilide is
thnl precipitated again, while stirring, by adding dropwise an acetic
acid of 30 per cent strength, until a neutral reaction is attained.
The excess of mineral acid in the coupling mixture is then neutralised
by adding dropwise 230 parts of a sodium acetate solttion of per cent
strength The whole is stirred until the diazonium-salt can no longer
be detected The precipitate is then filtered with suction and washed
well with water A red pigment dyestuff of good fastness to light is
obtained.
EXAMPLE 2.

Cotton fabric is padded on the foulard with a solution containing per
litre 20 grams of 1acetoacetylamino 2:5 dimethoxy-4-chlorobenzene, 20
cc of a sodium hydroxide solution of 38 Be and 15 grams of Mononol
Brilliant Oil The fabric is dried and printed with a paste containing
in 1000 grams 50 grams of a dyeing salt consisting of the diazonium
chloride of -( 4-amnino-2: 5 '-dimethoxybenzene- 11-azo)-acetoacetic
acid anilide having a content of the base of 25 per cent, 480 grams cf
water, 450 grams of starch-tragacanth thickening and 20 grams of
acetic acid of 50 per cent strength After drying, the material is
passed through a boiling bath containing per litre 10 grams of
anhydrous sodium carbonate, rinsed and after-treated at the boil for
some minutes with a solution containing 3 grams of soap and 2 grams of
sodium carbonate per litre of liquor An intense scarlet red print of
very good fastness to light and good properties of wet fastness is
obtained.
A bluish red tint of the same good fastness properties is obtained
when the printing is applied to cotton fabric which has been padded
with a corresponding amount of 1acetoacetylamino-3-ethoxybenzene or of
acetoacetyl-arminobenzene.
The above printing process can also be applied to fabrics of other
kinds, for example staple fibres of regenerated cellulose or viscose.
EXAMPLE 3 70
Cotton yarn which has been well boiled and dried is treated for about
half an hour at a ratio of goods to liquor of 1:20 in a solution
containing per litre 1 gram of terephthaloylbis-acetic
acid-2-methoxy-4-chloro-5-methyl 75 anilide, 7 5 cc of a sodium
hydroxide solution of 38 Be and 10 cc of Turkey red oil After being
squeezed, the impregnated material is introduced into a developing
bath which has been prepared as follows: 1 5 parts of the 80
hydrochloride of -( 4 '-amino-21:
51-diethoxybenzene-l'-azo)-acetoacetic acid anilide are added, while
stirring, to a mixture of 150 parts of water and 1 5 parts of
hydrochloric acid of 20 per cent strength The mixture is 85
diazotised, by adding dropwise 1 3 parts of a sodium nitrite solution
of 20 per cent strength.
The excess of mineral acid is then neutralised by the addition of 5
parts of a sodium acetate solution of 10 per cent strength, 5 parts of
90 acetic acid of 30 per cent strength are then added and the solution
of the diazonium salt is made up to 1000 parts by volume.
The: dyeing is developed for 20-30 minutes, rinsed and after-treated
at the boil 95 for half an hour with a solution containing per litre 3
grams of soap and 2 grams of sodium carbonate A clear yellowish-red
dyeing of medium fastness to light and good properties of wet fastness
is obtained 100 When the same diazo-compound is coupled on cotton yam

which has been impregnated with a solution containing per litre 4
grams of 4:4 ' di(acetoacetylamino) 3: 31 dimethyldiphenyl, 3 cc of a
sodium hydroxide solution 105 of 38 Be and 10 cc of Turkey red oil, a
kluish-red dyeing is obtained.
By using other diazotised aminoazo-compounds of the above constitution
and other arylides of ( 8-keto-carboxylic acids in the usual 110
dyeing or printing processes, dyestuffs having similar good properties
of fastness are obtained.
In the following Table are given the tints obtained after subjecting
the material to an 115 after-treatment with a boiling solution of soap
ard sodium carbonate The samz tints are obtained when the dyestuffs
are produced in substance as opposed to on the fibre.
Diazo, Component:
K, 4 ' amino-21: 51dimethoxybenzene-l'-azo) -acetoacetic acid 1)
-anilide 4) 3 784,781 Coupling Component:
1-acetoacetylamino-4ethoxybenzene 1-acetoacetylamino2:
5-dimethylbenzene terephthaloyl-bis-acetic
acid-2-methoxyw-4chloro-5-methylanilide 4: 41-di-(acctoacetylamino)-3:
31-dimethyldiphenyl 11) 5 12) -4-methoxy-anilide
terephthaloyl-bis-acetic acid-2-methoxy-4chloro-5-methylanilide
1-acetoacetylamino2: 5-dimethoxy-4chlorobenzene 4:
41-di-(acetoacetylamino)-3: 3 ' -dimethyldiphenyl yellow-red
bluish-red brick-red bluish-red clear blue-red yellowish-red
yellow-red bluish-red 13) 14) 15) -2: 3-dimethyl-anilide -2:
5-dimethyl-anilide -2: 5-dimethyl-anilide 16) 3 17)
-3-trifluoromethylanilide dimethoxybenzene-1 'azo)-acetoacetic acid
18) -2-trfifuoromethyl4-chlaranilide 1-acetoacetylamino2:
5-dimnethoxy-4-chlorobenzene
tereplhthaloyl-bis-aceticacid-2-methoxy-4chloro-5-m-ethyl-anilide 4:
41-di(acetoacetylamino)-3: 31-dimethyldiphenyl 4: 4
'-di-(acetoacetylamino)-3: 3 '-dimethyldiphenyl Tint:
bluish-red scarlet bright red bluish-red 10) red yellowish-red orange
clear red yellow-red brick-red Diazo Component:
19) -cyclohexylamide 784,781 Coupling Component:
4: 4 '-di-(acetoacetylaminy)-3: 31-dimethyldiphenyl 20)
-naphthyl-2-amide,, 21) -6-methoxy-benz thiazole-2-amide 22)
-N-ethylcarbazolyl,, 3-amide 23) -benzimidazole-5,, amide o.-(
41-amino-2 ': 51dimethoxybenzene- 11-azo) -benzoylacetic acid 24)
-anilide,, -( 41-amino-21: 51diethoxy-benzene- 11-azo) -acetoacetic
acid 25) -3-methyl-anilide 26) -benzylamide,, 27) -2-methoxy-anilide
28) -4-chloranilide x.-( 41-amino-21: 51diethoxy-benzene-1 '-azo)
-benzoylacetic acid 29) -anilide terephthaloyl-bis-acetic
acid-2-methoxy-4chloro-5-methylanilide bright scarlet

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* 5.8.23.4; 93p
* GB784782 (A)
Description: GB784782 (A) ? 1957-10-16
Improvements in or relating to processes for the production of selenium
rectifiers
A high quality text as facsimile in your desired language may be available
amongst the following family members:
CH324326 (A) NL101501 (C) CH324873 (A)
CH324326 (A) NL101501 (C) CH324873 (A) less
7 $ 49782 Date of Application and filing Complete Specification:
February 10 1954.
t, t D Application made in Germany on February 10 1953 Complete
Specification Published: October 16, 1957
Index at acceptance:-Class 37, I((AE:2).
International Classification:-H Oll.

Improvements in or relating to Processes for the Production of
Selenium Rectifiers We, SIEMENS-SCHUCKERTWERKE AKTIENGESELLSCHAFT, of
Berlin and Erlangen.
Germany, a German 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 a process for the production of selenium
rectifiers Processes for the production of such rectifiers are known
in which an addition is made to the semi-conductor (composed of
selenium) for increasing the conductivity of the semiconductor, and
hence of the finished rectifier.
The addition for increasing the conductivity of the semi-conductor
consists of a halogen, or halogens, or halogen compound(s) and will
hereinafter be referred to as " the first addition " It is also known
to make an addition for promoting the formation of the barrier layer
In this specification the " barrier layer " is to be understood as
that which produces the blocking resistance in the rectifier Thus, an
addition which promotes the formation of the barrier layer is an
addition which increases the blocking resistance of the finished
rectifier, the blocking resistance of the rectifier being the
resistance offered to the current resulting from an inverse voltage
applied to the rectifier Known additions for promoting the formation
of the barrier layer are, for example, metals such as antimony,
bismuth, -35 tin, thallium, indium, gallium, cadmium, copper and lead,
or non metals such as arsenic or sulphur or alloys or compounds of
these substances The addition for promoting the barrier layer will
hereinafter be -40 referred to as " the second addition " In known
processes for the production of selenium rectifiers, the second
addition in the form of thallium is applied with the counter electrode
to the surface of the semiconductor, the thallium entering the semiI
Price 3 s 6 d J conductor by diffusion This has the drawback that it
is difficult to regulate the quantity and distribution of the diffused
addition in the semi-conductor.
According to the present invention there 50 is provided a process for
the production of a selenium rectifier, wherein the semiconductor body
is built up of a plurality of individually successively applied
selenium layers, each of which layers is provided with 55 the first
addition as herein defined, there being added to one layer in which
the barrier layer is formed in the finished rectifier (and, in the
case where the semi-conductor body is to consist of more than two
layers, 60 also to the successive layers adjacent to said layer, with
the exception of one or more of the last layers) the second addition
as herein defined, the quantity of the second addition, in the case

where the semi-conductor body 65 is to consist of more than two
layers, being made progressively greater in the layers approaching the
barrier layer.
As already stated, each of the layers contains the first addition for
increasing con 70 ductivity It will of course be appreciated that
different halogens or different mixtures thereof may be used in
various layers As the first addition there is preferably employed
chlorine, iodine, or bromine, 75 either in the elementary state or as
halogen compounds, for example selenium chloride, selenium bromide,
selenium tetrachloride or selenium tetrabromide The first addition,
which serves to increase conductivity, will 80 have its effect
modified by the presence of the second addition The latter, which
primarily serves to promote the formation of the barrier layer, will
also tend to reduce conductivity 85 For this reason therefore the
semiconductor body is built up of a plurality of individually applied
successive selenium layers, each of which may be prepared with a given
quantity of the first addition, there 90 No 3963/54 2 784,782 being
added to some of the layers neighbouring the barrier layer, the second
addition in such a quantity that as a result of the combined action of
the first addition and the second addition the final conductivity of
each layer provided with both additions is less than a layer having
only the first addition In this way the barrier effect of the
rectifier is enhanced.
J 0 Alternatively, the quantity of the first addition in the layer(s)
provided with both the first and second additions may be made larger
than that provided in the layers or layer having only the first
addition, so that the conductivity of the layers having both additions
is about the same as that of the layers having only the first addition
A rectifier having a relatively low forward resistance is thus
obtained.
The present process may be carried out with, for example, a metallic
carrier electrode which has been plated with another metal and which
has been suitably preheated or otherwise prepared to ensure good
adhesion of a subsequently applied selenium layer so that an electric
junction without a barrier layer is formed between the carrier
electrode and the semi-conductor body A first selenium layer
containing the first addition is applied to the carrier electrode, the
addition being, for example, chlorine, this layer being applied, for
example, by evaporation, painting, pressure, pouring or in another
known way A further selenium layer is then applied to the first
mentioned selenium layer in one of the known ways, the further
selenium layer containing the first addition again for example
chlorine, and the second addition for example thallium The second
selenium layer can be applied to the first selenium layer while the

first layer is still in the amorphous condition.
Alternatively, the first layer may, prior to the application of the
second layer, be subjected to a thermal pre-treatment by which it is
converted entirely or partially into the better conducting or into the
best conducting modification If desired, a final layer can be applied
The layer may consist in known manner of cadmium selenide, cadmium
sulphide or selenium dioxide The counter electrode consisting of the
usual known materials, for example bismuth, tin or cadmium in
elementary form or in the form of an alloy thereof, is then applied to
the semiconductor layer or the final layer, for example by spraying or
evaporation, if desired after the second layer has undergone thermal
treatment, and the rectifier in this W O state is then thermally
and/or electrically formed in the usual known manner until it reaches
the finished state.
For a better understanding of the invention and to show how the same
may be carried into effect, reference will now bo 65 made to the
accompanying drawing which shows diagrammatically a selenium
rectifier.
Referring now to the drawing, a rectifier is shown in which 1 is a
carrier electrode, 2 a and 2 b are two layers of the semi 70 conductor
body and 3 is the counter electrode of the rectifier The two layers 2
a and 2 b each consist of selenium with the first addition, the layer
2 b also having the second addition The counter electrode 3 is then 75
applied, this electrode being free from agents such as thallium which
promote the building up of the barrier layer Such an agent, which is
otherwise present in the counter electrode.
thus cannot produce any disadvantageous 80 undesirable effect on the
rectifier during operation which may result in ageing The usual
thermal and electrical treatments may be employed in the present
process in a manner which is well known 85
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