DE1617218B2 - Toilet detergent bar - Google Patents

Description

35

The invention relates to improved toilet detergent bars.

While it was expected that non-soap synthetic detergents might be milder to the skin than soaps because of their high alkalinity, this expectation has not been met in practice. Indeed it has been believed for many years that, with very few exceptions, non-soap detergents, which unfortunately have proven too costly except for special purposes, considerably less mild for the skin than are soaps.

It is an object of the invention to provide non-alkaline toilet bars which are substantially milder to the skin than any toilet soap. Toilet soaps here are to be understood as meaning those which are composed in the usual way of soap from a mixture of fats, so that the undesirable effects on the skin of nut oils, which _{contain substantial proportions of C 10} -C ₁₄ fatty acids, largely, if not can be completely softened by mixing the soaps made from nut oils with oils and fats, which mainly consist of combined C _{1 ( .C 20} fatty acids, such mixtures being completely state of the art.

It is a further object of the invention to provide such milder non-alkaline toilet pieces, which have all the desired properties of a good toilet soap, namely a smooth handle, high foaming power, even in cold water, economical in use, little tendency to muddy will not crack, retain color and smell during consumption, combined with the ability of some syndets not to form deposits in hard water. It was found that a toilet piece with the aforementioned properties is made from an alkene sulfonate can be.

The alkene sulfonates suitable for use in the invention can be obtained by well known series of reactions by the action of SO ₃ or similar sulfonating agents on alpha-olefins. The particularly preferred alkene sulfonates are those which result from the reaction of alpha-olefins of C ₁₂ -C ₂₄ carbon chain lengths with a strong sulfonating agent, in particular sulfur trioxide, in an inert gas, for example air, and wherein the liquid olefin and the SO ₃ / air streams are brought together in a reactor which is designed to allow a short contact time, e.g. B. less than 10 minutes and preferably less than 1 minute, and which is provided with means to dissipate the heat of reaction. A reaction product is obtained which, by acid hydrolysis followed by neutralization, or by alkali hydrolysis, gives salts of sulfonic acids. These sulfonic acids are complex mixtures of alkane hydroxysulfonic acids and alkene sulfonic acids with a proportion of sulfonic acids of low equivalent weight; these latter are appropriately referred to as "disulfonic acids" without implying that they are entirely true disulfonic acids. In addition to true disulphonic acids (which are partly formed from a smaller proportion of diolefins in the starting olefin mixture), they can contain some short-chain monosulphonic acids which are formed as a result of acid cleavage of the olefin chain.

The immediate reaction product should be a mixture of alk-2: 3-en-1-sulfonic acid and alkanebeta-sultone. The latter, however, isomerizes rapidly to the gamma and delta sultone, which on alkaline hydrolysis give alkane-3-hydroxy-1-sulfonic acid salts and alkane-4-hydroxy-1-sulfonic acid salts ( . The amount of residual beta sultone is such that less than about 2% alkene-2-hydroxy-isulphonic acid salts are present in the mixture. The proportions of alkene sulphonates are about 2: 1 to the total hydroxy-alkane sulphonate. The "disulphonate" factor can be up to a proportion, that is about 25% of the total product, but by suitable choice of the quality of the olefin starting material and the reaction conditions it can be kept substantially lower Products in which the disulfonate content is reduced to as low a value as possible Thus, the term "alkene sulfonates" as used herein is intended to mean all of the above-mentioned reaction products.

It has been found that the _{alkene sulfonates as defined above prepared from C lo} -C ₂₄ alpha-olefins (which can be obtained from a cracking paraffin distillate or synthesized from hydrocarbons which contain fewer carbon atoms, e.g., ethylene by Ziegler catalysts, or similar catalysts, or by dehydration of primary alcohols obtained by hydrogenation of esters of naturally occurring ones

Fatty acids, for example animal and vegetable oils and fats, or in any known manner Way), especially those which contain only small proportions of the alkyl 2-hydroxy-l-sulfonates, e.g. B. on the order of less than 2% alkene sulfonate, particularly suitable for manufacture of toilet pieces of the type according to the invention. Toilet pieces cannot be made from alkanesulfonates either Carbon chain lengths are made which are known to be mild to the skin because of these sulfonates are too insoluble. The alkene sulfonates, however, have carbon chain lengths which are mild to the skin are sufficiently soluble for making a bar for washing the human body.

The invention therefore relates to a toilet detergent bar based on a synthetic detergent, characterized in that the synthetic detergent is a water-soluble alkali or magnesium salt of an alkene sulfonic acid, which is obtained from the reaction of an alpha-olefin of 12-24 carbon atoms, preferably 12-24 carbon atoms SO ₃ / air and hydrolysis of the sulfonation product, wherein at least a portion of that product is alkane-3-hydroxy-1-sulfonic acid salt and alkane-4-hydroxy-1-sulfonic acid salt. This corresponds to an average molecular weight corresponding to approximately C ₁₆ -C ₂₀ . "Alkali" means lithium, sodium, potassium and ammonium.

The salts can be used alone or in combination so that the mixture can be pelletized, extruded and stamped in the manner customary for the manufacture of toilet pieces. Minor levels of other known additives can be included. Special additions of carbon chain regions of, for example, C ₁₄ -C ₁₆ can be used if the above conditions are met. Water up to about 20%, preferably from about 3 to about 10%, will be present, as will minor amounts of simple electrolytes such as sodium sulfate, which should be present in no greater than about 2%, and sodium chloride, which should be present up to about 10% can be present. Combinations of alkene sulfonates which are preferred are sodium and potassium alkene sulfonates; Sodium and / or potassium magnesium alkene sulfonates, of carbon chain length 12-24, in particular 12-16 or 15-18. Other combinations, such as ternary combinations, can be made.

It has been found that toilet pieces made from combinations of two alkene sulfonates are preferred contain them in a ratio of 1: 9 to 9: 1.

Combinations of alkene sulfonates derived from alpha olefins from fractions of a particular one Carbon length, can also be used with or without a common cation. The required Mixture of alkene sulfonates can be obtained by sulfonating a mixture of olefins desired distribution of carbon chain lengths or by mixing sulfonation products of olefins of one chain length. It was found that the ratio of longer chain fractions to shorter-chain fractions between 3: 1 and 1: 3. Mixtures of the shorter and the Longer-chain alkene sulfonates result in improved foam volume.

Superfatting agents may be present, such as. B. the higher molecular weight monocarboxylic acids of the aliphatic Line. Suitable acids are those with carbon chain lengths of 8-20, preferably 8-16.

The amount employed can be 5 to 40% by weight of the bar, preferably 5 to 20%.

Among the other ingredients known in the art that can be added are: Plasticizers and / or foam modifiers, e.g.

ίο higher aliphatic straight or branched chain Paraffins, fatty alcohols, phospholipids, fatty acid amides, or higher aliphatic-lower alkylelamides, Gums or slimes or synthetic polymeric substances to convey lubricity, or

* 5 binders, e.g. B. starch, lower starch alkyl ethers, lower starch alkoxy ethers, lower starch alkyl carboxy ethers or lower starch alkyl sulfonate ethers, lower cellulose alkyl ethers, lower cellulose alkoxy ethers, lower cellulose alkyl carboxy ethers, lower Cellulose alkyl sulfonate ether, locust bean gum, guar gum, slippery mucus, or Chondroitin sulfates, proteins, polypeptides or polyacrylamides, polyalkylene oxides, especially polyethylene oxides, z. B. Carbowaxes, polyoxene (RTM), very high molecular weight water-soluble polymers and Mixed polymers of vinyl alcohol, maleic acid, acrylic acid, itaconic acid, pyrrolidone, or allyl alcohol, wherein a portion of the polymerized monomer groups an ionizing carboxy, sulfate, sulfonate, Phosphate or phosphonate group carries, coloring substances, pigments, bactericides, fungicides, Protective agents, perfumes, sequestering agents, glucose or glycerin.

The invention will now be further exemplified

explained.

composition
40 foam
volume
at 20 ° C Kremwert
(Creaminess) example 1
96% sodium alkene sulfo-
nat of C ₁₅ -C ₂₀ chain
length,
4% water
Example 2
95% sodium alkene sulfo-
5 ° nat of C ₁₂ -C ₁₆ chain
length,
5% water
Example 3
55 97% sodium alkene sulfo-
nat of C _ls -C ₁₈ -chain-
length,
3% water
Example 4
⁶⁰ 94.6% sodium alkene sulfo-
nat of C ₁₄ -C ₁₈ chain
length,
5.4% water
6 ₅ B eis ρ ie I 5
97% potassium alkene sulfonate
of C ^ -Cjg-Ketten-
length, 3% water 275
530
225
425
340 1
7th
2
2
4th

composition foam
volume
at 20 ° C Kremwert
(Creaminess) Example 6
91.5% magnesium alkene
sulfonate of C ₁₅ -C ₁₈ -
Chain length,
2% lubricant,
7.5% water
Example 7
90% magnesium alkene sulphate
fonat of C ₁₅ -C ₁₈ -Ket-
length,
10% water 350
375 co co

More whole alkene sulfonate pieces were made, in which the alkene sulfonates were of different chain lengths or possessed different cations, as follows:

isäthionat, exist. Such synthetic pieces have a foam volume of 215 and a cream value from 2.

A piece approach with a typical series of pieces commonly included in toilet pieces Additions is the following:

Example 14

ίο parts by weight

Weight percent

C ₁₄ -C ₁₆ sodium alkene sulfonate 40

C ₁₈ -C ₂₀ sodium alkene sulfonate 30

C ₂₂ -C ₂₆ sodium alkene sulfonate 30

Lauryl isopropanolamide 3

Titanium dioxide 0.4

Slippery Agent 0.5

Perfume 0.8

Protective agent 0.2

Electrolytes 8

Water 8

Alkene sulfonate water
(Vo) foam
volume
at 20 ° C Krem-
value Example 8
C ₁₅ -C ₂₀ sodium salt 46.5%
C ₁₂ -C ₁₆ sodium salt 46.5%
Example 9
C ₁₈ -C ₂₀ sodium salt 65.1%
C ₁₂ -C ₁₆ sodium salt 27.9%
Example 10
C ₁₈ -C ₂₀ sodium salt 28.8%
C ₁₅ -C ₁₆ sodium salt 67.2% 7th
7th
4th 470
325
350 6th
1
7th

Use of alkene sulfonates of different: ..; '. Cations

Example 11
C ₁₂ -C ₂₀ sodium salt 46.5%
C ₁₅ -C ₂₀ magnesium salt 46.5%

Example 12
C ₁₄ -C ₁₈ sodium salt 27%
CC

7th 225 10 430 10 500

salt 63%

Example 13
C ₁₄ -C ₁₈ sodium salt 63%
C ₁₅ -C ₁₈ -Magnesium-

salt-27%

The properties of the pieces according to the invention prove to be favorable in comparison with such a common toilet soap, e.g. B. a soap made from 80% sebum and 20% nut oil fat. Such common pieces give a foam volume of 167 at 20 ° C and a cream value of 2 after the same tests and measured by the same person as in the previous results. In equally, they are superior to the commercially available, successful toilet pieces which are im essentially of a synthetic detergent, namely one based on sodium In a 1% solution in distilled water, the pH is 6.0-7.5.

In these examples, the foam volume was determined by the following test method:
The examiner's hands are covered with thin medical gloves. Water of 24 ° hardness (ie 240 ppm of CaC / ₃ ) at 20 ° C is allowed to run up to a height of about 7.5 cm in circular pure plastic bowls about 25 cm in diameter at the base and about 35 cm in diameter at the top . This corresponds to about 5 liters of water. The gloved hands and pieces are wetted by dipping, and the piece is rubbed 15 times in the hands in a standardized manner. The foam on the hands is created by rubbing the hands back and forth back and forth in a standardized manner 20 times in each direction (two alternating periods of 10 rubs each time) and the foam is transferred to a calibrated vessel.

The total volume accumulated from three such manipulations is measured as the foam volume.

Repetitions can be done with good accuracy by an experienced person. Even though If repetitions between different people produce poor results, each examiner places one Series of pieces in the same order and recorded the same relative difference as the other examiners do it. The results recorded here were created by a single skilled person obtain.

The term "Kremwert" is easily understood by those skilled in the art, but it is extremely difficult to define. It describes a subjective impression from the qualitative estimate of the species (usually from usual size) the bubble sizes, the "whiteness" of the foam, and especially, the suppleness or thickness, assessed by tactile feel. The cream value was rated, represented by a scale through the words:

very bad, bad, fairly bad, moderate, moderately good, good, very good, excellent, with the following corresponding numerical values: 0, 1, 2, 3, 4, 5, 6, 7.

In the preceding examples, the fractions drawn should be taken so that they include both even plus odd chains only, on average about the same average molecular weight, and approximately the same range in numbers of carbon atoms in the chains full. It should be noted that olefins, formed catalytically from ethylene, mixtures of carbon chains of the same number, as are those which, by dehydration of fatty alcohols, the latter obtained by hydrogenation of natural oils and fats, while being obtained mixtures obtained from cracked paraffins both odd and even carbon chains exhibit.

The toilet pieces according to the invention are mild for the skin and give foam in soft or hard form Water, even in the cold, which is rich, extraordinarily constant, and creamy in structure. The wear is comparable to the rate of wear in spite of copious foaming of a bar of soap.

409 525/378

Claims (5)

Patent claims: 1. Toilet detergent bar based on synthetic detergent, characterized in that the synthetic detergent is a water-soluble alkali or magnesium salt of an alkene sulfonic acid, which is obtained from the reaction of an alpha-olefin of 12-24 carbon atoms, preferably 14-20 carbon atoms, with SO ₃ / air and Hydrolysis of the sulfonation product originates in which at least a portion of that product is alkane-3-hydroxy-1-sulfonic acid salt and alkane-4-hydroxy-1-sulfonic acid salt. 2. Detergent bar according to claim 1, consisting essentially of sodium alkene (C ₁₂ -C ₁₆ ) sulfonate. 3. Detergent bar according to claim 1, consisting essentially of a mixture of Sodium salts of alkene sulfonates with carbon chains of 15-20 and 12-16. 4. detergent bar according to claim 1, consisting essentially of a mixture of Sodium salts of alkene sulfonates with carbon chains of 18-20 and 12-16. 5. Detergent bar according to claim 1, consisting essentially of a mixture of 63% sodium salt of C ₁₄ -C ₁₈ alkylene sulfonate and 27% magnesium salt of C ₁₅ -C ₁₈ alkylene sulfonate.