DE1068411B - Stabilized soap - Google Patents

Description

C 1OM 169 / OOB 18

GERMAN

PATENT OFFICE

internat354 ~ € lld

O 4816 IVa / 23 e

REGISTRATION DAY: 14th AP S TL 195 6

NOTICE JDER REGISTRATION AND ISSUE OF THE ADSLE LETTERING:

NOVEMBER 5, 1959

The invention relates to soaps which are stabilized with regard to the formation of odor and color.

Soaps are known to have a tendency to discolor and become rancid upon storage or use. These changes were attributed to various causes, e.g. the fact that the soaps were out Fats and oils are produced which themselves have a tendency to go rancid. It is also believed that minor amounts of metallic impurities, especially very Ide amounts of iron and copper, the formation accelerate oxidation products that produce an undesirable odor or color Have consequence. These changes can occur in different forms of soap, e.g. in soap bars, soap powders, granulated soap and soap pearls obtained by spray drying.

Liquid soaps, usually potassium soaps, are more difficult to stabilize than sodium soaps in this regard. Many of the proposed stabilizers are for the manufacture of persistent potassium soaps or of. Mixtures containing substantial amounts of potassium soaps are generally unsatisfactory suitable.

The above-mentioned problems have been sought to solve mainly by preventing these undesirable ones Changes in soap compositions, various antioxidants or others Stabilizing agent added. Many of the proposed stabilizers partially solve the problem, e.g. by preventing the formation of odors, but not influencing or even influencing the color fastness still adversely affect.

The problem of soap stabilization has recently been caused by the incorporation of phenolic bactericides Substances in soaps made more difficult. It is true that phenolic antioxidants are used for soap stabilization suggested, however, many of them are ineffective, and some phenolic compounds even accelerate that adverse changes. A phenolic bactericidal compound commonly used in soaps is this 2,2'-Dioxy-3,5,6,3 ', 5', 6'-hexachlorodiphenyl methane (hexachlorophene). Smaller amounts of it / e.g. 0.5%, seem in soaps to accelerate the discoloration. This effect can be masked by the fact that the composition incorporated a yellow dye, so that that which occurs during storage or use Yellowing does not appear so. This is the case with the incorporation of such phenolic bactericidal substances The problem encountered in white toilet soap has not yet been resolved. The provision of new and improved Stabilizers for soap that are effective in the presence of phenolic bactericidal substances consequently significant.

It has now been found that soaps, whether they are phe-stabilized soap

Applicant:

Olin Mathieson Chemical Corporation,
Baltimore, Md. (V. St. A.)

Representative: Dr. W. Beil, lawyer,
Frankfurt / M.-Höchst, Antoniterstr. 36

Claimed priority:
V. St. v. America April 14th and June 2nd, 1955

Victor Charles Fusco, Baltimore, Md.,
and Richard Calvert Harshman, Kenmore, NY

(V. St. A.),
have been named as inventors

Nolic bactericidal substances, whether or not they contain them, can be stabilized if they are given smaller amounts of Azines, hydrazines or hydrazinium salts of organic acids incorporated. According to the invention there is a composition which is a soap of an aliphatic monocarboxylic acid having 12 to 18 carbon atoms and as a stabilizing agent for the soap, an azine, a hydrazine or a hydrazinium salt organic acid in an amount of 0.05 to 1 percent by weight based on the weight of the soap. the Hydrazides and the hydrazinium salts of organic acids are particularly effective in soap compositions which contain phenolic bactericidal substances.

Azines which are suitable for the use according to the invention can be converted in a known manner of hydrazine with aldehydes and ketones. It can be aliphatic, aromatic, act alicyclic or heterocyclic aldehydes and ketones. The ketones can be more than one of these types or groups included. Mixtures of two or more azines can be used; but they can can also be used together with other known, compatible stabilizers.

The azines can therefore be those derived from aliphatic aldehydes of the RCHO type are in which R is an alkyl radical having 2 to 12 carbon atoms; z. B. of acetaldehyde, propionaldehyde, Butyraldehyde, isobutyraldehyde, valeraldehyde, Isovaleraldehyde, capronaldehyde, enanthaldehyde, cyprylaldehyde, pelargonaldehyde, capricaldehyde and laurylaldehyde. The azines can also be aromatic

909 647/400

Be derived from aldehydes, ζ. Β. of benzaldehyde, p-thiylaldehyde, p-isopropylbenzaldehyde, o-chlorobenzaldehyde, ο - nitrobenzaldehyde, m - nitrobenzaldehyde, p-nitrobenzaldehyde, sah'cylaldehyd, anisaldehyde, vanillin, Veratrumaldehyde, Piperonal, Phenylacetaldehyde and Cinnamaldehyde. Azines, those of furfural and tetrahydrofurfural can also be used with success.

The azines can also be aliphatic from a large number Be derived from ketones, especially from dialkyl ketones. These ketones include acetone, methyl ethyl ketone, Methyl n-propyl ketone, methyl isopropyl ketone, Diethyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, Pinacolin, methyl-n-amyl ketone, ethyl-n-butyl ketone, Di-n-propyl ketone, di-isopropyl ketone, methyln-hexyl ketone, 6-methyl-2-heptanone, di-isobutyl ketone, methyl-n-nonyl ketone and stearone. The azines can also of alicyclic or aromatic ketones, such as cyclopentanone, cyclohexanone, acetophenone, benzophenone and methyl benzyl ketone.

Suitable hydrazides which can be used according to the invention are the hydrazides of aliphatic monocarboxylic acids with 1 to 18 carbon atoms, such as formic acid hydrazide, acetic acid hydrazide, propionic acid hydrazide, butyric acid hydrazide, Valeric acid hydrazide, caproic acid hydrazide, lauric acid hydrazide, myristic acid hydrazide, palmitic acid hydrazide, Stearic acid hydrazide and elaidic acid hydrazide. The hydrazides of dibasic acids such as the of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid and fumaric acid-derived hydrazides can also be used. The dihydrazide of carbonic acid, Carbohydrazide, is also very effective. Hydrazides derived from substituted hydrazines are e.g. B. the beta-oxyäthylhydrazid of stearic acid, the di- (beta-oxyäthyl) hydrazide of stearic acid and the unsymmetrical dimethylhydrazide of oleic acid can be used. Mixtures of hydrazides organic acids, hydrazides of mixed fatty acids and mixtures of hydrazides with known compatible ones Soap stabilizers can be used.

Suitable hydrazinium salts which can be used according to the invention include the hydrazinium salts of aliphatic monocarboxylic acids having 1 to 18 carbon atoms, e.g. B. the vinegar, propion, butter, valerian, Caproic, lauric, myristic, palmitic, stearic and elaidic acids. The hydrazinium salts of polybasic acids, such as monohydrazinium oxalate, dihydrazinium oxalate, monohydrazinium succinate, monohydrazinium adipate, dihydrazinium adipate, Monohydrazinium fumarate, monohydrazinium tartrate, dihydrazinium tartrate, dihydrazinium citrate, Monohydrazinium citrate and hydrazinium naphthenate can be used. Also the hydrazinium salts monobasic aromatic acids such as hydrazinium benzoate and the di-, tri- and tetrahydrazonium pyromellitates are usable. Furthermore, hydrazinium salts derived from substituted hydrazines can be used are, such as beta-oxyethymydrazinium stearate, di- (betaoxyethyl) hydrazinium stearate, unsymmetrical dimethylhydrazinium kerylbenzenesulfonate and phenylhydrazinium oleate, as well as hydrazinium kerylbenzenesulfonate can be used. Mixtures of hydrazinium salts organic acids, hydrazinium salts of mixed fatty acids or mixtures of the hydrazinium salts with known ones compatible soap stabilizers can be used.

The stabilizers should not be added to the soap compositions in one stage, the decomposition, Causes leaching or partial decomposition of the stabilizer. They will be the soap compositions expediently added at any suitable stage after saponification. For example, they can use pure soap can be added in the manufacture of molding soap. It is common in the manufacture of pearled soap It is advantageous to add the stabilizer to the mixer prior to processing, optionally with perfumes and dyes to add. The stabilizing agent can also be added during the crutching process.

ίο be given. The stabilizers can with Advantageously, they can be added in the form of aqueous suspensions if the stabilizers are water-soluble, or they can be added as dry solids, preferably finely divided. That after the addition of the Mixing using stabilizers is sufficient to homogenize the soap composition.

The soap product can then be dried and converted into cakes, bars, pearls and others as desired Shapes are molded. In the manufacture of liquid soap compositions, the stabilizing agents be dissolved immediately in the soap solutions; or, if prepared appropriately, they can be aqueous Solutions of these stabilizers are added to the liquid soaps.

The stabilizers are available in various types of soaps including laundry soaps, facial soaps and soaps, which is subsequently incorporated into cosmetic compositions such as toothpaste, face creams and body creams become effective.

The invention is illustrated by the following specific examples:

example 1

A mixture of dried neat soap material (essentially the sodium soap of tallow fatty acids) was prepared by mixing 0.5 parts by weight of benzalazine with 99.5 parts by weight of soap at about room temperature. The mixture was pressed into pieces of 20 g each under a pressure of 140.6 kg / cm ^{2. Four of these pieces were kept in an oven at HO 0} C for 7 days, together with four pieces that had been produced by the same method but without benzalazine. At the end of this period, the light reflected from the surface of the pieces was measured with a Hunter reflectometer. If the light reflection from the surface of the soap bars is assumed to be 100% immediately after production, then the test pieces which do not contain benzalazine show an average reflection of 56.0 ⁰ J ₀ after heating for seven days, while the 0.5 ° / ₀ pieces containing benzalazine have an average light reflection of 81.0 ° / ₀ . These data show that the addition of benzalazine significantly reduces the discoloration.

Example 2

A mixture of benzalazine and soap (essentially the sodium soap of tallow fatty acids) was prepared in the manner described in Example 1 using only 0.05 percent by weight benzalazine, based on the soap. After heating at 110 ° C for seven days, the average reflectance of the four bars of soap without additive was 30.5% of the reflectance of the bars before treatment. The four pieces, which contained 0.05 ° / ₀ Benzalazin, exhibited an average reflectance of 52.3 ° / _0th

Example 3

Three different azines were treated with purified and dried white Bradforde soap flakes (in the

mainly the sodium soap of tallow fatty acids) were mixed to form compositions containing 0.05 percent by weight of the azine. Each mixture was pressed into four pieces of 20 g each at a pressure of 140.6 kg / cm ^2. The pieces were aged in an oven at 100 to 110 ° C for 7 days. After aging, the reflectance of light from the surface of each bar was measured using a Hunter reflectometer and compared to that of an untreated soap bar that contained no additive. The results, which each represent the average of four tests, are listed in the table below:

Additive, 0.05%

Blank value, not treated

Bund value, treated

Dimethylketazine

Salicylaldehydazine

Cinnamaldehyde azine

Reflection in Vo

100.0
23.5
48.0
37.2
39.1

Example 4

Mixtures of soap with acetic acid hydrazide and sebacic acid dihydrazide were made by that 0.5 parts by weight of the hydrazide with 99.5 parts by weight of dried pure soap material (essentially the sodium salt of tallow fatty acids) mixed thoroughly at room temperature. The mixture was under Applying a pressure of 140.6 kg pressed into pieces of 20 g each. Four pieces of each hydrazide mixture and four pieces made from the same soap material but without the hydrazide, were kept in an oven at 110 ° C for 7 days. After this period of time, the light reflection stopped the surface of the pieces measured with a Hunter reflectometer. When you look at the reflection of the soap surface assumes 100% immediately after manufacture, the following results were obtained:

Stabilizers,
Weight percent

None

None

Acetic hydrazide, 0.5
Sebacic acid dihydrazide, 0.5

treatment

not heated
heated
heated

heated

Light reflection, ° / ₀

100.0
55.5
64.3

75.1

The data show that the aging test caused significant discoloration on the soap without any additive became. However, the addition of acetic acid hydrazide or sebacic acid dihydrazide prevents the discoloration largely.

Example 5

Acetic hydrazide and carbohydrazide were tested by following the procedure of Example 4 for their effects as stabilizers checked. The following results were obtained.

Stabilizers,
Weight percent treatment Light-
reflection, ° / o None
None
Acetic hydrazide,
0.05
Carbohydrazide, 0.5 ... not heated
heated
heated
heated 100.0
30.5
43.5
49.5

Even at a concentration of 0.05% by weight, acetic hydrazide showed a remarkable one Decrease in discoloration. Carbohydrazide was also at a concentration of 0.5 weight percent very effective.

Example 6

White soap flakes (essentially the sodium soap of tallow fatty acids) has been used as the soap material for further ίο experiments according to the procedure of example 4 used. The following reflections were obtained.

Stabilizers,
Weight percent treatment light
reflection,% None
None
Lauric acid
hydrazide, 0.05 not heated
heated
heated 100.0
23.5
34.4

Lauric acid hydrazide achieved remarkable stabilization at a concentration of 0.05 weight percent the soap regarding the formation of discoloration.

Example 7

Liquid potassium coconut oil soap was prepared by heating a mixture of 420 g of coconut oil, 300 g of 36 ° / _o aqueous sodium potassium hydroxide and 1867 g water was heated for 16 hours on a steam bath. Sufficient 2,2'-dioxy-3,5,6,3 ', 5', 6'-hexachlorodiphenylmethane (hexachlorophene) was dissolved in the solution so that it contained 0.5 percent by weight of hexachlorophene, based on the dry weight of the soap . 0.26 g of stearic acid hydrazide were added to 50 ecm of the soap solution containing hexachlorophene. The same amount of myristic acid hydrazide was added to the soap solution for a further 50 ecm. The two samples, along with another 50 cc sample containing hexachlorophene and a 50 cc sample not containing hexachlorophene, were heated in an oven at 100 to 120 ° C for 2 weeks. When heated, most of the water evaporated from the samples after a few hours. At the end of the heating period, the samples were cooled to 28 ° C. and diluted to 50 ecm with water. All insoluble material was nitrided off and the light transmission of the feed material was determined using a "Series blue filter No. 525" in a Fischer electrophotometer. The results shown in the table below were obtained:

50
Stabilizers Hexa
chloro
phen, ° / ₀ treatment light
by
nonchalance,
7o None
⁵⁵ None
Kernes
Stearic acid
hydrazide
Myristic acid
⁰ hydrazide none
none
0.5
0.5
0.5 not heated
heated
heated
heated
heated 100.0
60.0
44.0
52.0
54.0

The data show that the hexachlorophene affects the color fastness of the soap solution and that the two hydrazides significantly improve the color fastness.

Example 8

In the experiments below, the same was found

Potassium soap solution as in the previous example

applies and several hydrazides and commercially available sta-

solvent in each 50 ecm of this soap solution, which already contained 0.5 percent by weight of hexachlorophene, based on the dry weight of the soap, dissolved. Included solutions were obtained containing 0.5 percent by weight of the stabilizer, also based on dry weight the soap. A portion of each of these solutions was enclosed in a glass ampoule and Heated in an oven at 80 ° C for 2 weeks. After that were the vials cooled, opened and the transparency of the contents using a Fischer electrophotometer measured using an iSeries blue filter No. 525 «. The light transmission of the unheated Solution without addition was assumed to be 100%. The following results were obtained.

Stabilizing agents
0.5 percent by weight Hexa
chloro
phen,% treatment Ijcht-
by-
nonchalance
Vo None none not heated 100.0 None 0.5 heated 87.5 Lauric acid hydrazide 0.5 heated 90.0 Myristic acid hydrazide 0.5 heated 100.0 Sebacic acid dilhydrazide 0.5 heated 97.5 Commercially available Stabilization medium No. 1. ,. 0.5 heated 80.5 Commercially available Stabilization medium No. 2 0.5 heated 61.0

Formation of a Series blue filter No. 525 .. in a Fischer electrophotometer certainly. The results obtained are shown in the table below.

5
Stabilizers
in grams per 50 ecm
the soap solution Hexa
chloro
phen,
Weight
percent treatment Light-
by-
nonchalance,
O.
0 ¹⁰ None
None
None
Hydrazinium
glycollate, 0.26 ...
¹⁵ hydrazinium
naphthenate, 0.26 none
none
0.5
0.5
0.5 not heated
heated
heated
heated
heated 100.0
60.0
44.0
57.1
63.2

The test conditions are less strict than in the example 7, since the non-stabilized soap after trying a light transmittance of 87.5 ° / ₀ had the untreated soap solution without addition here. The hydrazides investigated, however, had a significant stabilizing effect with regard to the formation of discoloration. This is in contrast to the two commercially available stabilizers, which even seem to have an effect that accelerates the discoloration.

Example 9

A liquid potassium coconut oil soap was prepared by adding a mixture of 420 g of coconut oil, 300 g of 36 ° / _o aqueous potassium hydroxide and 1867 g'Wasser was heated 16 hours on a steam bath. So much 2,2'-dioxy-3,5,6,3 ', 5', 6'-hexachlorodiphenylethane (hexachlorophene) was dissolved in the liquid soap that a solution was obtained containing 0.5 percent by weight of hexachlorophene on the dry weight of the soap. 0.26 g of hydrazinium glycole were added to 50 ecm of the soap solution containing hexachlorophene. The same amount of hydrazinium naphthenate was added to another 50 ecm soap solution. The hydrazinium glycoUate and hydrazinium naphthenate were prepared by mixing 1 gram mole of anhydrous (95%) hydrazine with about one gram equivalent of the organic acid.

The two samples were taken along with a 50 cc sample and a 50 cc sample containing hexachlorophene heated in an oven at 100 to 200 ° C for 2 weeks without hexachlorophene. After heating it evaporated a few hours most of the water from the samples. At the end of the heating period, the Samples are cooled to 28 ° C and diluted to 50 ecm with water. Any insoluble material was filtered off and the translucency of the filtrates checked using this Data show that the hexachlorophene adversely affects the color stability of the soap solutions and that the two hydrazinium salts improve the color fastness significantly.

Example 10

The same potassium soap solution was used in the following experiment. Hydrazinium GlycoUat and Hydrazinium naphthenate and several commercially available stabilizers were separated into 50 ecm each those already containing 0.5 percent by weight of hexachlorophene, based on the dry weight of the soap Soap solution dissolved to form solutions that are 0.5 percent by weight, also based on dry weight the soap, the stabilizer. A portion of each solution was enclosed in a glass ampoule and heated in an oven at 80 ° C for 2 weeks. After this time, the ampoules were cooled down, opened and using the percent light transmittance of the contents with a Fischer electrophotometer of a »Series blue filter No. 525«. Those listed in the table below were given Get results:

Stabilizers.
45 percent by weight Hexa
chloro
phen,
Weight treatment Light-
by-
looseness,
0 < percent , 0 None 0.5 not heated 100.0 None 0.5 heated 87.5 ⁵⁰ hydrazinium glycoUat, 0.5 0.5 heated 96.5 Hydrazinium naphthenate, 0.5 0.5 heated 100.0 Commercially available ⁵⁵ stabilization medium No. 1, 0.5 0.5 heated 80.0 Commercially available Stabilization medium No. 2, 0.5 0.5 heated 61.0

These data show that the experimental conditions were less stringent than in Example 9, where the water was allowed to evaporate and later replaced. The light transmittance of the sample without a stabilizing agent was 87.5 ° / ₀ of the non-heated sample; both containing 0.5 ° / ₀ hexachlorophene. The presence of the hydrazinium salts resulted in a substantial improvement in the color stability of the soap compositions. The two commercially available stabilizers were ineffective and even reduced the color fastness of the samples.

Example 11

Soap blends containing several hydrazinium salts were prepared by thoroughly mixing 0.5 parts by weight of the salt with 99.5 parts of pure soap material (essentially the sodium soap of tallow fatty acids) at room temperature. The mixture was pressed into bars of 20 g each at a pressure of 140.6 kg / cm ^2. Four bars of each mixture and four bars made from the same soap material but without the addition of hydrazinium salt were kept in an oven at 100-104 ° C for 2 weeks. At the end of this time, the light reflected from the surface of the bars was measured with a Hunter reflectometer. If the reflection of the soap bars immediately after their production is _{assumed to be 100 ° / 0} , the following average results are obtained.

Stabilizers treatment Light-
reflection, "/ ₀ None
None
Hydrazinium
naphthenate
Hydrazinium
distearate
Hydrazinium benzoate.
Hydrazinium
propionate not heated
heated
heated
heated
heated
heated 100.0
72.8
79.4
80.6
74.0
76.0

The hydrazinium distearate was prepared by melting stearic acid and every 2 moles of stearic acid 1 gramol of anhydrous hydrazine was added and the mixture was then allowed to cool. The hydrazinium benzoate was prepared by adding equal moles of anhydrous hydrazine and benzoic acid separated into Methanol were dissolved, mixed and some of the methanol was distilled off; the residue was cooled and the hydrazinium benzoate crystallized out, filtered off and dried. The hydrazinium propionate was through Mix equimolar amounts of anhydrous hydrazine and propionic acid at room temperature.

All of these hydrazinium salts showed an improvement in the color fastness of this soap. The hydrazinium distearate and the hydrazinium naphthenate were particularly effective.

The procedures of the specific examples given can be modified in various ways, so that other improved soaps and soap-containing compositions falling within the scope of the invention may be obtained will. The invention is general to the improvement of soaps and soap-containing compositions suitable in the sense generally intended in technology. In the specific examples it acted The soaps used are sodium soaps made from tallow fatty acids or a potassium coconut oil soap. At Instead of the specifically used soaps, other soaps can also be used; the invention includes the improvement of soaps and soap-containing compositions in which the cationic part, for example from ammonia, an amine, an alkali metal, or an alkaline earth metal, such as sodium, potassium, lithium, Calcium or barium as well as magnesium, aluminum, zinc and cadmium. The anionic part the soap is derived from one or more aliphatic monocarboxylic acids having 12 to 18 carbon atoms, such as Lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid. For the use according to the invention Suitable soaps can also be made in a known manner from a large number of naturally occurring materials or their derivatives, such as tallow, palm oil, hydrogenated fish oils, (marine oil), ζ. Β. Whale oil, coconut oil, bee kernel oil, Rosin, tall oil, lard, olive oil, cottonseed oil, peanut oil, soybean oil and linseed oil will.

Furthermore, numerous other phenolic bactericidal substances can be used in place of that used in the examples

ίο hexachlorophenols are used; belong to them Hexylresorcinol, cresol, thymol, chlorothymol and guaiacol.

The soaps stabilized according to the invention are suitable for use in the production of thickened soaps Petroleum oils, the lithium, sodium, calcium, aluminum or other metal soaps of various acids including e.g. B. contain the acids derived from tall oil, tallow, castor oil or waste fatty acids.

Claims (11)

Patent claims: 1. Stabilized against odor and discoloration Soap based on aliphatic monocarboxylic acids with 12 to 18 carbon atoms, characterized in that that they, based on the weight of the soap, 0.05 to 1 percent by weight of an azine, one contains non-aromatic hydrazide or a hydrazinium salt of an organic acid. 2. Soap according to claim 1, characterized in that that it contains a sodium or potassium soap. 3. Soap according to claim 1 or 2, characterized in that it is benzalazine as a stabilizing agent, Contains salicylaldehydazine or cinnamic aldehyde. 4. Soap according to claim 1 or 2, characterized in that it is dimethylketazine as a stabilizing agent contains. 5. Soap according to claim 1 or 2, characterized in that it is acetic acid hydrazide as a stabilizing agent, Contains lauric acid hydrazide, stearic acid hydrazide or myristic acid hydrazide. 6. Soap according to claim 1 or 2, characterized in that it is sebacic acid dihydrazide as a stabilizing agent contains. 7. Soap according to claim 1 or 2, characterized in that it is used as a stabilizing agent carbohydrazide contains. 8. Soap according to claim 1 or 2, characterized in that it is hydrazinium glycollate as a stabilizing agent or contains hydrazinium propionate. 9. Soap according to claim 1 or 2, characterized in that it is hydrazinium distearate as a stabilizing agent contains. 10. Soap according to claim 1 or 2, characterized in that that it contains hydrazinium naphthenate or hydrazinium benzoate as a stabilizing agent. 11. Soap according to any one of claims 5 to 10, characterized in that it is an effective amount of a phenolic bactericidal substance, e.g. B. 2,2'-Dioxy-3,5,6,3 ', 5', 6'-hexachlorodiphenylmethane contains. Considered publications: U.S. Patent Nos. 2,062,675, 2,679,481,
587 581; German Patent Nos. 923 487, 929 806;
British Patent No. 570232. Legacy Patents Considered:
German Patent No. 1 028 731.