FR2523606A1 - CONCENTRATED SOFTENING COMPOSITIONS FOR FABRICS BASED ON QUATERNARY IMIDAZOLINE DERIVATIVES - Google Patents

Abstract

THE INVENTION RELATES TO CONCENTRATED AND STABLE FABRIC SOFTENER COMPOSITIONS COMPRISING A MIXTURE OF A QUATERNARY AMMONIUM COMPOUND OF THE IMIDAZOLINIUM TYPE WITH A DICATIONIC COMPOUND OF QUATERNAL AMMONIUM OR A LONG CHAIN DIALKYL RADICALALKYL OR SHORT CHAIN DIALKYL RADICALALKYL. THESE COMPOSITIONS SHOW STABLE VISCOSITY CHARACTERS AT LOW AND HIGH AMBIENT TEMPERATURES.

Description

The present invention relates to softener compositions for

  fabrics, intended for use in

  the rinsing cycle of a laundering process, and in par-

  Particularly concentrated aqueous softener compositions for fabrics which exhibit characteristics of viscosity stable at ambient temperatures, both low and high, that is to say that the viscosity of these compositions does not increase.

not to the point of forming a gel.

  The compositions containing ammonium salts quater-

  naire having at least one long chain hydrocarbyl group are commonly used to soften fabrics

  when used in the flushing cycle of an operation

  laundry; see for example, United States patents

  United States of America No 3 349 033, No 3 644 203, N '3 946 115,

  N O 3 997 453, N O 4 073 735 and N '4 119 545.

  For most aqueous softener compositions

  sants containing cationic ammonium compounds quater-

  As active ingredients, the concentration of these

  cationic poses has generally been limited to the range of about

  3 to 6% by weight (see US Pat. Nos. 3,904,533 and NO 3,920,565) This low concentration is generally required by the fact that cationic compounds form gels in aqueous systems. concentrations

  greater than about 8% and although the use of electro

  trolytes to reduce the viscosity of these compositions is known (see in particular the patent of the United States of America No 4,199,545), these electrolytes are far from satisfactory

from several points of view.

  On the one hand, from an economic point of view, the use of such electrolytes contributes to the price of the product and this is generally undesirable From a functional point of view, electrolytes often do not behave as desired, in particular at of concentrations of neighboring cationic compounds of approximately 12 to 15% And finally, although the contain electrolytes may alleviate most of the gelation problem, their use is far from being

  satisfactory to obtain a strongly con-

  centered on cationic compounds, which does not gel or whose viscosity does not change within the usual range of time

  peratures encountered in its handling, for example

  approximately -18 to approximately 60 C) The patent of the United States of America

  risk 3 681 241 describes a concentrated softening emulsion

  tissue material which consists essentially of 3.5 to 6.5 parts by weight of a compound represented for example by distearyldimethylammonium chloride, 3.5 to 6.5 parts by weight of an alkyl alkyl sulfate amido-imidazolinium and

  O to 3 parts by weight of an amido-imidazolyl sulphate

  fatty nium, different but similar, the latter being assumed

  providing low temperature stability to the composition.

  The total active compounds envisaged are in the

range of about 8 to 13%.

  U.S. Patent No. 4,155,855

  describes concentrated liquid fabric softeners for soft fabrics

  holding (1) a substantive agent for fabrics which can be a polyamine, an alkylpyridinium salt, or a mixture of both and (2) a fabric softener in which the polyamines have the formula: R Ri RN +

R é Ril '- (CH) -

R R 1

  & 1 in which R is a C 10 to 24 alkyl or alkenyl group u R O (C 12) n; R 1 can be hydrogen, hydroxy-alkoxy, C 1 -C 3 alkyl, etc; N has a

  value from 2 to 6 and m has a value from 1 to -5 and A (-) represents

  feels one or more anions balancing the charge Among

  fabric softeners, there may be mentioned

  kyl-imidazolinium generally analogous to imida salts

  zolinium used in the compositions of this in-

  vention The composition contains 25% to about 55% of a

  active system of substantive agent for tissues and a compound

  health softener for fabrics the first representative 25

  about 85% and the second 15 about 75% of the compound

  According to preferred aspects, the substantive component for tissues represents 50 to 85%, and preferably 65% to

  80%, and the softener 15 to 50%, and preferably 20 to 35%.

  In all cases, the lowest concentration of

  posing noun for tissue in relation to the sum of

  this one and the softener is given (in terms of for-

  percent) as 25%, but based on the ratios of the two agents (6: 1 to 1: 4); this percentage could

  conceivably be as low as 20%.

  The present invention provides concentrated aqueous softener compositions stable at low and high temperatures based on softening compounds of the imidazolinium type and a secondary amount of a dicationic or conventional quaternary ammonium compound which, in

  is not a softener The present invention provides

  also lays down a process for producing compounds

  fabric softener for highly concentrated fabrics.

  The compositions of the present invention are stable aqueous compositions which contain a high concentration of the cationic fabric softener which

  is a mixture of two different types of am-

  quaternary monium as described below.

  The aqueous compositions of the present invention

  contain at least about 8% and up to about 25% of a-

  cationic softener, and preferably approximately 9 to 15% of this softener, this cationic softener comprising a mixture of a softener of the imidazolinium type generally of formula (A) CE 2 l HI l H r NRC R- I- -t- x in which:

  R 1 is a C 8 to C 30 aliphatic radical and of pre-

  refers to a C 14 -C 18 alkyl or alkenyl radical; R 2 and R 3 may independently have the definition of R 1 or, preferably, they represent a lower alkyl or substituted C 1 to C 4 alkyl group, for example haloalkyl, hydroxyalkyl, acylaminoalkyl, etc. ; X is a water-soluble anion such as chloride, bromide, iodide, fluoride, sulfate, methosulfate, nitrite, nitrate, phosphate, and carboxylate (for example acetate, adipate, phthalate, benzoate, oleate, etc); The preferred compounds corresponding to the formula (AA) CH 2

r N C 2 -

/ \

C R

R. o He

N C R

) 5

Rli

H 2 C -

  N + X k I in which R is as defined in formula (A); R 2 may have any definition of R 1 or preferably represents a lower alkyl or substituted C 1 -C 4 alkyl group, such as haloalkyl, hydroxyalkyl, etc; R 4 may be hydrogen or a C 1 -C 4 alkyl or substituted alkyl group; R 5 can have any definition of R 1 and R 2, preferably a C 8 -C 30 aliphatic radical and more preferably C 14 -C 18 alkyl or alkenyl; and X is as defined in formula (A)

  and a dicationic quaternary ammonium compound of

general mule (B)

R 1 R 1

R _-N, C 1 I;) nN + R 1 X-

r R N Ic I) d ', x

R 1 -Ri.

  in which the group R is chosen from radicals ali-

  C 1 O to C 30 phatics, preferably alkyl or alkenyl; or R 0- (CH 2) n o R has the same meaning as above, that is to say C 1 O to C 30 aliphatic radicals, and

  preferably alkyl or alkenyl; the symbols R 1 can represent

  smell hydrogen; C 1 -C 4 alkyl or hydroxyalkoxy groups; N is an integer from 2 to 6 and m is an integer from 1 to 5; and X has the definition given in formula (A), the preferred compounds being those in which R is C 12 to C 18 and R 1 is a lower alkyl group, in particular methyl; or a conventional quaternary ammonium compound of general formula (C) R I

R _ N y-

  R in which the R groups are chosen from C 1 to C 30 aliphatic radicals, preferably alkyl or alkenyl, aryl (for example phenyl, tolyl, cumyl, etc.); aralkyl

  (for example benzyl, phenethyl, etc.); and their substitutes

  halogeno, amide, hydroxy and carboxy killers; provided that at least one symbol R is C 14 to C 30, preferably C 14 to C 18, and the others are lower alkyl groups, and more preferably at least two of the symbols R are C 14 to C 18 and that the others are C 1 to C 4 lower alkyl groups (and in particular methyl or ethyl) and Y is an anion as defined for X in formula (A). The concentration of the imidazolinium compound (A) may

  be between 8 and 20% by weight relative to the composition

  total and that of the dicationic compound (B) or the

  classic se (C) can be between about 0.5 to 5% by weight of the total composition, the ratio of A to B (or C) being between about 40: 1 and about 3: 1, preferably between 40 : 1

  and 5: 1, and better still for (B) between 15: 1 and 7: 1.

  Examples of softeners of the imidazolinium type include the following within the framework of formula (A) above:

  2-heptadecyl-1-methyl-1-oleylamido-ethosulfate

  thyl-imidazolinium, '2-Heptadecyl-1-methyl-1- (2stearoylamido) ethyl-imidazolinium sulfate, 2-heptadecyl-1-methyl-1- (2-stearoylamido) ethyl-imidazolinium chloride,

  2-copra-1- (2-hydroxyethyl) -1-benzyl- chloride

imidazolinium,

  2-copra-1- (hydroxyethyl) -1 (4-chlorobu-) chloride

tyl) -imidazolinium,

  2-copra-1- (2-hydroxyethyl) -l-octadecec chloride

nyl imidazolinium,

  2-tail oil chloride-it C-2-hydrox Yeth Yl) -1-benzyl-

fatty imidazolinium,

  2-tall oil-1-C-2-hydroxy-thyl chloride) -1 (4-chia-

robutyl) -imidazolinium fatty,

  2 "heptadecenyl chloride 1" 2-hydrox yethyl) -l-

(4-chlorobutyl) -im: idazolinium,

  2-heptadecenyl-1 2-hydroxyethyl chloride) -l-

ben zyl-imida zolinium,

  2-Heptadecyl-1- (, hydroxyethyl) ethyl sulfate -1-

octadecyl-imidazolinium.

  Examples of dicationic compounds of Formula (B) include the following N- (tallow derivative) -N, N, N 1, N 1-tetra methyl1,3-propanediamnmonium dimethosulfate

  N- dimethosulfate (derivative of tallow) -N, N 1, N 1-trimethyl-

thyl-1, 3-propanediamnmonium

  N-Oleyl-N, N, N Nt, N 1-pentamethyl-1,3- dimethosulfate

propanediammonium

  N dimethosulfate (derived from tallow) -N, N, N ', N 1, N 1-pen-

tamethyl-1,3-propanediamnmonium

  N-stearyl-N, N, N 'N 11 N -pentamethyl dimethosulfate

1-3-propane di ammonium

  N-stearyloxypropyl-N, N 11 N 1 tris diacetate (3-hydroxy-

  propyl) -1, 3-propane-diammonium Examples of cationic compounds of formula (c) include the following distearyl-dimethylammonium chloride disuif chloride-dimethyl ammonium dihexadecyldimethyl ammonium chloride distearyl dimethyl ammonium bromide (disuif bromide hydrogenated) dimethyl ammonium distearyl di (isopropyl) ammonium chloride

  distearyl dimethyl ammonium methosulfate.

ô 523 G 6 O

  In addition to the cationic components of this

  invention, it is also possible to incorporate into the compositions

  many other conventional materials or optional components which do not adversely affect the stability and / or functional characteristics of

  the present invention Thus, for example, one can incorporate

  secondary quantities of various surfactants and in particular certain surfactant phosphoric esters which

  can have the advantageous effect of combating electricity

  static city of washed items These additional components

  classic silences also include perfumes,

  dyes, pigments, germicides, brightening agents

  optical age, anti-corrosion agents (sodium silicate), etc. When used, each of them can constitute

  example 1% by weight of the compositions of the invention.

  It may also be advantageous to strengthen and / or

  to modify the viscosity characteristics of the compound

  tion of the present invention by the addition of an electrolyte

  such as calcium chloride, sodium nitrate, form-

  sodium mate, etc., in proportions of between

  about 0.05 and about 5% by weight

  other components (e.g. 0.5 to 10%) other components may

  also be incorporated, for example lower alkanols

  laughing, for example ethyl and isopropyl alcohol as well as conventional opacifiers, in particular of the types

  resin emulsion which are well known in the art.

  The following examples illustrate the invention without limiting it. The parts are expressed by weight unless otherwise indicated. 9-

EXAMPLE 1

  The following composition is prepared:% by weight Deionized water 73.05

1-methyl-1-tallow methosulfate

  amidoethyl-2-tallow-imidazolinium 15.00

  N- dimethosulfate (tallow derivative) -

  N, N, N 1, N 1, Nl-pentamethyl-1,3-propane 2.00 diammonium Dye and perfume, 100% supplement This composition has a viscosity of approximately 24 Omi Pa s immediately after preparation, which increases up to just under 400 m Pa S after six weeks of aging at room temperature and to around 840 m Pa S after six weeks of aging at 43 CA these values, the

  viscosity of the product is quite within the acceptable range

  ble viscosities which varies from about 100 to about 1000

  m Pa s, and preferably from about 200 to about 800 m Pa s.

  In the absence of the dicationic compound in the composition and in the presence of 0.1% Na Cl, it is found that the viscosity is initially around 324 m Pa s, of 1700 m Pa S after aging for six weeks at the room temperature and

  2300 m Pa S after six weeks aging at 43 C.

EXAMPLE 2

  0.05 part of sodium formate is added to 80 parts of deionized water, then 15 parts of 1-methyl-1-stearyl-amidoethyl-2stearyl-imidazolinium methosulfate and 2.0 parts of the dicationic compound of Example 1 0.05 part of calcium chloride is then added. A very satisfactory product is obtained from the above components.

  as well as the operational sequence of mixing the

posing.

EXAMPLE 3 a-f

  Each of Examples i and 2 is repeated except that the dicationic compound (2.0% by weight) is replaced by the following compounds (a) Dicationic compound of Example i (b) Dicationic compound of l 'Example i

  (c) N-C dimethosulfate tallow derivative) -

  N, N, N 1, N 'tetramethyl-1,3-propane-

  d iaxnmonium (d) N-oleyl-N, N, N, N 11 N 11 N 1 pentamethyl1,3-propanediammonium dimethosulfate

  (e) N- dimethosulfate (tallow derivative) -

N ,, 1-trmty 1, 4-butanediammonium,

  (f N-stearyloxypropyl-N diacetate, N 1, N 1-

  tris (3-hydroxypropyl) -1, 3-propanediammonium% by weight 3.0 1.0 2.5 1.5 1.5 2.0 2.0

EXAMPLE 4 a-f

  Each of Examples 1, 2 and 3 a to 3 f is repeated except that the cationic softener of the imidazolinium type is replaced by the following compounds

  () 2-heptadé cyl-1-methyl- methosulfate

1-oleylamidoethyl-imidazolinium

  (b) 2-Heptadecyl-1-methyl methosulfate

1-Oleylamidoethyl imidazolinium

  (c> 2-Heptadecenyl-1 methyl methosulfate

1-oleylamidoethyl-imidazolinium

  (d) 2-Heptadecenyl-1- (2-hydroxy-) chloride

thyl) -l-benzyl-imidazoliniumi

  (e) 2-Heptadecenyl-1 (2-hydroxy-) chloride

thyl) -l-benzyl-imidazoliniumn

  (f) 2-Heptadecenyl-1 (2-hydroxy-) chloride

  thyl) -1-benzyl-imidazolin-ium% by weight 12.0 14.0 16.0 12.0, 0.5

EXAMPLE 5

  The following composition is prepared:% by weight Deionized water 78.90 Na Cl (10% aqueous solution) 1.50

  1-methyl-1-tallow-amidoethyl- methosulfate

  2-tallow-imidazolinium 12.0 Distearyl dimethyl ammonium chloride 1.5

  Color and fragrance, sufficient quantity for 100%.

  This composition has a viscosity of approximately 79 m Pa s

  immediately after preparation, this viscosity increases

  both at a little less than 400 m Pa S after six weeks of aging at 43 CA a viscosity of about 400 m Pa s, the product is entirely within the acceptable range of viscosities, which varies between about 100 and about 1000 m Pa S and preferably between about 200 and about 800

  m Pa s In the absence of the dimethyl-distearyl softener

  cationic, the composition, after aging, has a

  viscosity of approximately 1500 to 2000 m Pa s.

EXAMPLE 6

  Example 5 is repeated except that, in addition to sodium chloride (0.15%), calcium chloride (0.15%) and sodium formate (0.15%) are also added. and

sodium nitrate (0.15%).

EXAMPLE 7

  A composition similar to that of Example 5 is prepared, except that the softener is only

  consisting of 13.5% distearyl dimethyl ammo chloride

  nium This gives a very firm gel which is not

all marketable.

EXAMPLE 8

  To 80 parts of deionized water, 0.04 part of sodium formate, then 12 parts of 1-methyl-1-stearyl-amidoethyl2-stearyl-imidazolinium methosulfate and 1.5 parts of hydrogen chloride (hydrogenated tallow) are added. ) dimethylammonium. 0.04 part of calcium chloride is then added. A very satisfactory product is obtained from the above components as well as from the operational sequence of mixing.

components.

  EXAMPLE 9 af Each of Examples 5, 6 and 8 is repeated, except that in place of distearyl dimethyl ammonium chloride (1.5% by weight), the following ingredients are used:% by weight (a) sulfur chloride) dimethyl ammonium 2 (a) sulfur chloride) -dimethyl ammonium 2 (c) di methosulfate (hydrogenated tallow) b) di (tallow) dimthylammonium chloride 1.5 (c) di methosulfate (hydrogenated tallow) dimethyl ammonium 1.5 (e) di methosulfate (hydrogenated tallow) dimethyl ammonium 2.5 (e) di methosulfate (hydrogenated tallow) dimethyl 1 ammonium um 3.5 (f) di-oleyl acetate -diethylammonium 1.5 EXAMPLES 10 af Each of Examples 5, 6 and 9 a to 9 f is repeated except that in place of the imidazolinium compound (12% by weight) of these examples, we uses the following compounds:% by weight

  (a) 2-heptadecyl-1-methyl- methosulfate

  1-oleylamidoethyl-imidazolinium 12.0

  (b) 2-heptadecyl-1-methyl- methosulfate

  1-oleylamidoethyl-imidazolinium 14.0

  (c) 2-heptadecyl-1-methyl- methosulfate

  1-oleylamidoethyl-imidazolinium 16.0

  (d) 2-'heptadecenyl chloride 1- (2-hydro-

xyethyl) -1-benzyl-imidazolinium

  (e) 2-heptaidecenyl chloride 1, - (2-hydro-

  xyethyl) -1-benzyl-imidazolinium (f) 2-heptad chloride Cenenyl-1 - (, 2hydro'- xy 4thyl) -1-benzyl-imidazoliniumn by weight 12.0, 0.5

Claims (9)

R E V E N D I C A T I ONS   1 Concentrated, aqueous, stable fabric softener composition, characterized in that it contains approximately (A) 8 to 20% by weight of a softener of the imidazolinium type, (B) 0.5 to 5% by weight of ( i) a compound of formula: IP R 1 R Ii C) -RR 1 i -L V R 1 X-   | i -_i Ir R 1 in which R is an aliphatic radical in CO to C 30;   the symbols R 1 represent, independently of one another, hydrogen or a C 1 to C 4 alkyl or hydroxyalkoxy group; n is an integer from 2 to 6; m is an integer from 1 to 5; and x is a water solubilization anion or (ii) a compound of formula: RMNRR + X in which the groups R are C 1 to C 30 aliphatic radicals, at least one being a C 1 alkyl group 14 to C 30, the weight ratio of (A) to (B) being between about 40: 1 and about 3: 1.   2 Composition according to claim 1, characterized   in that it contains up to about 5% by weight of electro-   lyte 3 Composition according to claim 1, characterized in that the imidazolinium type softener is a salt of   1-heptadecyl-1-methyl- (2-stearoyl-amidoethyl) imidazolinium.   4 Composition according to claim 3, characterized in that the dicationic compound is dimethosulfate   N- (tallow derivative) N, N, N 1, N 1, Nl-pentamethyl-1,3-propanediam-   monium. 5 Composition according to Claim 4, characterized in that the amount of compound A is approximately 15% and that of compound B is about 2%.   6 Composition according to claim 1, characterized   in that A and B are the only fabric softeners for pre- feel in the composition.   7 Composition according to Claim 1, characterized in that the imidazolinium type softener (A) corresponds to the formula H 2 C Ci H 2 R 11 R \\ E / \ C R 2 R R 1 $ Z 536 06   in which; R 1 is a C 8 to C 30 aliphatic radical and preferably a C 14 alkyl or alkenyl radical to C 18;   R 2 and R 3 may independently have any meaning of R 1 or preferably a lower alkyl or substituted C 1 -C 4 alkyl group; and X is a water solubilization anion such as chloride, bromide, iodide, fluoride, sulfate,   methosulfate, nitrite, nitrate, phosphate and carbo- xylate.   8 Composition according to claim 3, character-   in that the cationic softener (B) is chloride distearyl dimethyl ammonium.   9 Composition according to claim 8, characterized   in that the ratio of (A) to (B) is from about 15: 1 to 5: 1.   Composition according to Claim 9, characterized in that the quantity of compound (A) is approximately 12% and that of (B) is about 1.5%.   11 Composition according to Claim 9, characterized in that the total concentration of softener is approximately 15% by weight.   12 A method of preparing a composition according to claim 2, characterized in that it consists first of all in preparing an aqueous solution of at least part of the electrolyte, then in successively adding the softening components (A) and (B), then the rest of the electrolyte of   so as to obtain a stable composition.