DE2215371A1 - laundry detergent - Google Patents

Description

PATENTAN WALT Ξ ·

) R. ING. A. VAN DER WERTH - D R. FRANZ LED E R E R

21 HAMBURG 90. 8 MUNICH 80

WILSTOBFER STR. 32 ■ TCL. (O4l.lt 77 0861 LUCILE-GRAHN-STR. 23 TEL. (Οβ I Il 47 29

Munich, March 29, 1972 C 47α

Unilever N.V., Museumpark 1, Rotterdam, the Netherlands

laundry detergent

The invention relates to detergents, in particular textile, Laundry detergent. .

Detergents, especially textile detergents, generally contain builders together with surfactants as main components (surface-active compounds). The conventional builders are customary inorganic substances, in particular condensed phosphates such as sodium tripolyphosphate. It. however, it has been suggested that the use of phosphate builders can contribute to the problem of overfertilization of water bodies. Other builders that have been suggested to use is like sodium nitrile triacetate (NTA) and synthetic polyelectrolytes, are either more expensive or less effective than that Phosphate builders, or they do not give satisfactory results for other reasons.

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It is known that sodium carbonate can act as a builder, by removing calcium from hard water in the form of precipitated calcium carbonate. However, this precipitation increases Some time to complete and during this time the non-precipitated calcium can with greasy dirt and the detergent The surfactants of the detergent interact, being a ^ compared to sodium tripolyphosphate as a builder containing detergents, poor detergency results. At the same time, the precipitated product easily accumulates Calcium carbonate on the washed fabrics, creating a Hardening of the textiles can be caused.

It has now been found that detergents which contain an alkali carbonate as a builder, by incorporation of mixed amine oxide and nonionic surfactants can be improved. These detergents tend to have reduced inorganic deposits on the washed textiles; the washed textiles have compared to conventional detergents Textiles washed on a carbonate basis have a softer feel.

The detergents according to the invention contain about 5 to 25 percent by weight mixed amine oxide and nonionic surfactants; and about 25 to 90 weight percent of an alkali carbonate builder.

Any water-soluble carbonates or mixtures thereof can be used as the alkali carbonate. The alkali carbonates, especially the sodium salt, are preferred for reasons of cost and effectiveness. The carbonate salt can be whole or partially neutralized, e.g., the carbonate salt

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be partially replaced by a sesquicarbonate. The amount of alkali carbonate in a detergent can vary widely Move frame but should be within the range of about 25 to 90 percent by weight. The practical quantity range depends on the conditions under which the detergent is to be used. For example, in a detergent, that is intended for use under typical North American washing conditions, i.e. with low product concentrations the amount of the alkali carbonate is preferably about 25 to 75 percent by weight, in particular about 45 to 70 percent by weight. Here, low levels of carbonate are within the appropriate range Range is more suitable if you work with higher product concentrations is working.

The amine oxide and nonionic surfactants are generally used within the range of about 1: 3 "to 3: 1 parts by weight, preferably about 2: 1 to 1: 2 parts by weight, and at a ratio of about 1: 1 for optimum detergency For economic reasons, however, it is generally desirable to use less amine oxide than the nonionic surfactant, ie to work within the range of about 1: 3 or 1: 1 parts by weight, since the amine oxide is generally considerably more expensive than the nonionic a marked improvement of the invention is a surfactant. For the achievement in accordance with the minimum Aminoxidmenge about 1 part to 10 parts of the nonionic surfactant. ^{the & e} "total concentration of amine oxide and non-ionic surfactants is generally in the range of about 5 to 25 weight percent, preferably about 10 up to 14 percent by weight. Be more than about

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If 20% by weight of the mixed surfactants are used, this can lead to processing difficulties. The increase in washing power is very low when you compare it with the additional costs incurred for both the additional amounts of active ingredients than must also be used to overcome any processing difficulties.

All nonionic surfactants can be used in the detergents of the invention. Many of these surfactants are known and commercially available. In general, these are condensation products of organic compounds which contain a hydrophobic group and a hydrogen atom which is reactive toward an alkylene oxide, generally ethylene oxide. Examples of suitable nonionic compounds are Condensation products of alkylphenols, preferably with about 6 to 16 carbon atoms in the alkyl radical, with ethylene oxide, generally 5 to 25 EO (ie 5 to 25 ethylene oxide units per molecule), condensation products of aliphatic (preferably Cgjg) natural or synthetic alcohols with ethylene oxide , generally 5 to 15 EO ^ and condensation products of polypropylene glycol with ethylene oxide. Other nonionic compounds that can be used are the condensation products of diols with alkylene oxides, in particular ethylene oxide, for example alkane (Cj _O _ _2O ) diol-5-12 EO condensates mixed nonionic compounds can be used. Many other suitable nonionic surfactants are described in the literature, for example in "Surface Active Agents and Detergents", Vol. 1 and 2 by Schwartz, Perry and Berch.

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Any amine oxide surfactant can be used. The more conventional compounds have the general one formula

mean in R. a C ^ ₀ _ ₂₂ alkyl or alkenyl group and R "and R, C.. alkyl radicals, or Cp ^ -hydroxyalkyl. R ₁ is preferably a linear alkyl radical and R 1 and R 1 preferably denote the same radical, for example methyl groups. Special amine oxides are hardened dimethyl? »Fatty amine oxide and dimethyl coconut amine oxide. Further examples are amine oxides which contain a benzene nucleus in the radical R .., where Rp van R, have the aforementioned meaning, for example dimethyl- (Cn, _Q ) -alkylbenzylamine oxide.

are

Other suitable amine-oxide compounds in which the nitrogen atom is contained in a heterocycle, for example N-alkylmorpholine-N-oxides. Further types of amine oxides are described in the literature, for example in the aforementioned book "Surface Active Agents and Detergents", and many special amine oxides, some of which are new compounds, are contained in the following examples. Known amine oxides have a semi-polar bond and the like, therefore, do not share "nonionic surfactants" for the purposes of the invention, although amine oxides are sometimes assigned to that term in the literature.

Bs has been proposed so far, in detergents at least

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to use the more common types of amine oxides, particularly those amine oxides with long alkyl groups ( _C18 and above) that have useful fabric softening properties. However, the advantage of using amine oxides in the detergents of the invention is rather to mitigate the disadvantages of sodium carbonate as a builder and for this purpose amine oxides which otherwise do not have suitable fabric softening properties are effective. The use of amine oxides leads to other valuable advantages, as described in detail in the examples.

In addition to the essential ingredients, it is generally It is desirable to add some alkali metal silicate, in particular sodium silicate, e.g. basic sodium silicate or to the detergents Metasilicate, to be incorporated. A low level of silicate, e.g., from about 5 to 15 weight percent, is generally beneficial for the Reduction of corrosion of metal parts contained in textile washing machines is an advantage. The presence of silica can also contribute to reduced inorganic deposition and, with higher contents, lead to an improvement in detergency. the However, the amount of silicate should generally be about 30 percent by weight of detergent. The amount and type of silicate also have an influence on the pH of the detergent, which is preferably within the range of about pH 10 to 11 for a 0.1 percent by weight aqueous solution of the detergent.

The detergents of the invention can contain the usual, optionally present ingredients, such as fragrances, dyes, textile

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Softeners, fungicides, germicides, enzymes, optical Brighteners ", the redeposition counteracting substances such as SCMC, hydrotropic substances and, in the case of liquid detergents, opacity-imparting substances and organic solvents, such as lower ^ aliphatic alcohols. If necessary, other components, such as chemical Bleaching, e.g. sodium perborate, together with or in the absence of peracid precursors, chlorine-releasing bleaches and inorganic salts such as sodium sulfate and sodium chloride are present be. The detergents generally also contain water e.g. in the range of about 5 to 15 weight percent in the case of detergent powders.

In addition to the nonionic surfactants and the amine oxides, the detergents of the invention can contain minor amounts of other surfactants contain, but preferably the detergents do not contain any anionic surfactants, since the presence of significant amounts on these connections, e.g. B. over 5 percent by weight, too reduced Detergency can lead. This is presumably due to an interaction with the amine oxide surfactants.

The detergents of the invention can optionally contain other builders than sodium carbonate, but generally in minor amounts Quantities, e.g. up to 10 percent by weight, based on the washing

these
medium, included. Examples of builders are sodium tripolyphosphate, sodium nitrile triacetate, sodium citrate, sodium salts of oxidized polysaccharides, sodium carboxymethyloxysuccinate, sodium oxydisuccinate, sodium hydrofuran tetracarboxylate, sodium mellithate and polyelectrolyte builders such as sodium copolyethylene

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maleate, as well as other precipitation builders such as sodium orthophosphate, sodium (X-sulfonated fatty acids and sodium (G _10-20 ) alkenyl succinates. Some of these builders, especially the complexing builders, can cause an inhibition of the inorganic deposition on the washed textiles Polyphosphates such as sodium tripolyphosphate are particularly effective in this regard.

triummellitate and sodium carboxymethyloxysuccinate Although they also inhibit inorganic deposition, they must, however, be used in higher amounts, e.g. from about 20 to 40 percent by weight, be used to achieve a noticeable effect, unless in conjunction with another, of deposition counteracting substances are used.

Other specific additives that are beneficial in detergents Examples of aromatic solvents that can be used in the invention include one or more substituted aromatic solvents Contain rings, which condensed in the latter case or can be linked to one another. Dibutyl phthalate and analog solvents are particularly effective. Become the solvent Used in significant amounts, it may be desirable to give the detergent a porous material for absorption incorporated into the solvent, e.g., a microporous silicon dioxide or aluminosilicate. The solvent can be used in an amount of about 4 percent by weight, based on the detergent, up to a maximum amount of 1 part of solvent be present on 1 part of the total surfactants *

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Furthermore, additives for acceleration can be used with advantage the precipitation of calcium carbonate, e.g. nucleating substances, such as finely ground calcite or aragonite can be used. To achieve the maximum effect, the additional amount should be as follows be as high as possible, e.g. about 10 to about 50 weight percent, be. It must be taken into account here, however, that some of these additives cause increased inorganic deposition can affect the textiles. On the other hand Additives to inhibit the inorganic deposition can lead to a reduction in detergency, so that For the detergents to have the best properties, it is necessary to balance the two effects.

The detergents of the invention can be solid detergents, e.g. in the form of powders, granules or tablets, semi-solid pastes or gels or liquids. The detergents can be made by conventional methods, e.g. by spray drying aqueous pulps for the production of Detergent powders. The nature of the amine oxide and non-ionic surfactants, however, can result in increased water contents of the aqueous pulps produced in this way require suitable ones Flow properties for pumping and spray drying are guaranteed.

In some cases, the amine oxide, in particular, may even be at Using small amounts will cause the pulp to thicken. In this case, other processing methods can be used to be appropriate. For example, the amine oxide and the nonionic surfactant can be added to the slurry together or separately.

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incorporated in bar prior to spray drying or on the particulate sodium carbonate in a suitable mixing vessel be sprayed on. In this pail there may be a slight Amount of solvent, such as isopropanol, containing the amine oxide or the mixture of the amine oxide and the nonionic surfactant is added to have a helpful effect. Since isopropanol is highly volatile, larger amounts should be avoided.

In conventional processes for the manufacture of detergents from aqueous pulp, it may be advantageous to use additives to reduce the content of non-ionic surfactants at higher levels the tendency of non-ionic surfactants to separate out during slurry production. examples for suitable inhibitors that inhibit the deposition of nonionic surfactants are ethylene maleic anhydride and vinyl methyl ether-maleic anhydride copolymers, their Use is described in detail in CA-PS 704 074. Are the powders obtained sticky, regardless of whether the Deposition inhibitors have been used or not, so it may be desirable to add additives to the powder obtained add to improve the flow properties. These are commercially available auxiliaries, such as "Alusil AN", a sodium aluminosilicate.

The detergents of the invention are particularly suitable for Washing textiles, but they can also be used for other general or special cleaning purposes. In the Use for textiles should be noted that the action of the sodium carbonate to remove the Oalciums from hard

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Water in the form of calcium carbonate can last a short time. It can therefore be desirable to remove the laundry first then to be added to the wash liquor when the content of free Calcium has dropped to an acceptable level, which is e.g. 0.5 and under unfavorable conditions up to 5 minutes or ger can take. This measure can, to improve the The detergent's detergency and reduced inorganic deposition contribute.

The detergents of the invention are based on the following " Examples explained. All parts information refer to the Weight unless otherwise stated.

example 1

It becomes a detergent powder by a conventional method (Spray drying of an aqueous pulp) according to the following recipe made:

Component percent

hardened dimethyl fatty amine oxide ("Aromox" DMHTD) '8,

secondary alcohol (C _11-1 C)

("Tergitol" 15-S-7) 'TO

Sodium Carbonate '65

Sodium metasilicate ~ 10

Sodium carboxymethyl cellulose 1

optical brightener 1

Water, added to 100

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This detergent is compared with a commercially available detergent powder, which contains sodium carbonate as a builder and has a comparable formulation with the exception of the absence of the amine oxide, in terms of washing power, the grip of the textiles, the inorganic deposition and the soil anti-redeposition properties using identical washing conditions in each pail. Pur these investigations 6 dirty tea towels, pillow cases and soiled 6 6 dirty towels in a domestic washing machine at 0.15 percent product concentration in water of 18 ° French hardness washed at 50 ⁰ C (Ca: 1: Mg = 2). The washed items of laundry were initially assessed on their appearance by an examination board, which found overall a very slight preference for the items of laundry washed with the detergent of the invention over the items of laundry for comparison.

When the same items of laundry are washed repeatedly, the extent of the inorganic deposition on the items of laundry is determined. It can be seen here that with the detergent according to the invention there is an increase up to a maximum of about 0.85 percent in 10 to 15 washing cycles, while with the laundry items washed with the comparison detergent based on carbonate, the deposition progressively increases significantly above this value if the number of washing cycles increases to 25. The evaluation of the handle of the laundry items was carried out by a 24-member examination committee, which decided with a majority of on average over 22: 2 that those with the

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• detergent of the invention washed items of laundry according to 1, 5 and 110 wash cycles have a softer feel.

When determining the dirt-carrying capacity of detergents become clean test fabrics of their own variety of different types washed together with the aforementioned soiled items of laundry. Here..shows that the on the test fabrics from The amount of dirt absorbed by nylon and polyester fibers when using the detergent according to the invention is considerably lower is. "...-.

The detergent in this example is also tested in a machine wash test against a commercially available detergent powder that contains 40 percent sodium tripolyphosphate as a builder and • 16 percent sodium linear secondary alkylbenzenesulfonate, 5 percent basic silicate and the usual optical brighteners and substances that counteract redeposition. The results show an improvement in the washing power for the detergent of the invention based on amine oxide / ndctitionogenic surfactant, while the handle of the textiles and the wearability of both detergents is very satisfactory _:

! Example- 2 _: i

To the washing power of mixed. Amine oxide and nonionic Detergents containing surfactants with detergents that contain the same compounds alone and with commercially available detergents

I ■ 'ι-

To compare comparison detergents, a number of detergents are manufactured whose washing power is carried out using a variety of soiled standard test fabrics

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Standard conditions at 0.15 percent product concentration in water of 18 ° French hardness is determined at 5O ⁰ C (Ca: 1: Mg = 2). The results are shown in Table I.

Table I.

Percent washing power with different test fabrics

AS9 ^2j ERTC 41 77.6 85.7

Recipe percent 60 Process 10 VCD ^ A. 6th 44.4 sodium 6th basic silicate 100. Amine oxide ⁴ ) non-ionic, - \
Surfactant ⁰⁾ 60 Water, supplements too 10 B. 12th 39.6 sodium 100 basic silicate Amine oxide ⁴ ^ 60 Water, supplements too 10 C. 28.8- Sodium basic silicate

gc
Surfactant ^p; 12th

Water, added to 100

73.6 82.3

67.2 79.7

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Tabel 15 -
I (continued) 2215371 Recipe percent ■ percent washing power with
test fabrics. various VCD ¹ * AS9 ² ^ ERTC 41 A ⁵ ^

D * .. 45.4 68.5 86.0

commercial product

based on sodium '■

tripolyphosphate, such as
described in Example 1

B 27.2 78.7 86.1

commercial product
based on sodium carbonate j as in
Example 1 described

'65 percent, "Dacron" polyesters / 35 percent cotton "-Testge-. Weave soiled with vacuum cleaner dirt.

'Cotton test fabric soiled with a mixed grease soiling (90 percent) and particulate! Dirt (10 percent) from Indian ink and iron (IIl) oxide

* 'Cotton poplin test fabric, soiled with 4 parts of grease soiling and egg albumin as well as 1 part particulate! dirt

"Aromox" DMCDW (dimethyl coconut amine oxide) »Tergitol» 15-S-9 (sec.-Alkohal (C _11-1

These results show that the amine oxide / nonionic surfactant mixture Formulation A is better than any formulations containing the amine oxide or nonionic surfactant alone, and that over the entire range of the test fabric, the detergent of the invention has better properties than the commercially available ones

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Laundry detergent.

Examples 3 to 7

A number of detergents are produced to determine the optimal content of amine oxide and nonionic surfactants. The detergents have the following formulation:

Component percent

Dimethyl coconut amine oxide χ '

sec-alkyl (C ₁₁ _ ₁₅₎ -9EO

("Tergitol» 15-S-9) x ¹ ^

Sodium carbonate 60

basic silicate 10

Water, supplements too. 100

4, 5, 6, 7 or 8 percent in Examples 3 to 7, as shown in Table II.

The detergency of the detergents is measured according to standard methods using the same variety of test fabrics as in Example 2 described, determined. The results are compiled in Table II, which also contains the results for a comparative product A, which contains sodium tripolyphosphate as a builder (as described in Example 1).

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221537 '

X W-. 4th ! Table II Washing power with
Test fabrics different example
No. • 5 percent 'ASjJ, ERTG 41A 6th VCD . 76 77 3 7th 37 * . 76 77 ' 4th 8th '39; 78 84 5 > duct A 44 77 85 6th 45 78 85 7th jprc 43 72 84 Comparison 47

• These results show the increase in detergency up to one Total concentration of amine oxide and non-ionic compound of 12 percent in Example 5. Furthermore, any additional surfactants provide little benefit.

example

Another batch of the detergent from Example 5 is applied to examined their detergency using a variety of test fabrics under the standard conditions described in Example 2, however, the total product concentrations are varied. The same investigations are used for comparison purposes with a commercially available sodium tripolyphosphate as a builder containing detergent powder, A, as described in Example 1, carried out. The results are shown in Table III where the detergency for the comparative detergent powder A in each case in brackets after the values for the inventive one

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Detergent is indicated.

Table III

Product concentration percent detergency for various test fabrics

VOD AS9 29 (17) 72 (59) 36 (31) 73 (62) 38 (38) 78 (68) 44 (47) 78 (72) 47 (49) 81 (77) 48 (52) 85 (78)

ERTC 41 A 52 (24). 62 (.45) 82 (63) 84 (84) 88 (94) 88 (95)

0.75 0.1 0.125 0.15 0.2 0.4

all in all

These results show that the detergency of the detergent according to the invention is "considerably better than that of the comparative detergent at lower product concentrations and generally comparable at higher product concentrations, although in the latter case one would expect a much poorer detergency than that of the detergent based on sodium tripolyphosphate.

Example 9

After conventional spray drying, a detergent is produced according to the following recipe:

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Component '■ percent

Dimethyl coconut amine oxide

("Aromox" DMCDW). 6th

sec. -AIlCyI (C ₁₁ ^ ₁₅ ) -9BO

("Tergitol" 15-S-9) 6

Sodium carbonate, 60

SCMC 1

optical brightener 1

Water, added to 100

This detergent is compared to in terms of detergency, textile feel and inorganic deposition investigated the commercial products described in Example 1 based on sodium carbonate and sodium tripolyphosphate. When the detergency test described in Example 1 is used, a comparison with the commercially available one gives Detergent powder based on sodium tripolyphosphate with the detergent of the invention a significantly better appearance halved items of laundry.

When examining the halved laundry items for their feel, an experienced review board showed only a slight preference for the commercially available detergent based on sodium tripolyphosphate, while conventional products based on sodium carbonate generally have a significantly poorer quality The grip of the textiles yielded.

When washing the same halved laundry repeatedly with the detergent of the invention, the following increase in inorganic deposition is obtained, also for comparison purposes

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ν
. ι ■ JO 11 1 20th 22nd 0.56 0.73 0.82 6th , 03 1.06 0.80 2.10 _ , 4

the considerably poorer ash values for the comparison product based on sodium carbonate are listed:

inorganic deposition in percent for the specified number of washing cycles

Product of
Example 9
Comparative product

These results show a very marked improvement for the detergent of the invention.

Examples 10 to 21

A number of detergents are manufactured according to the following recipe:

Component percent

sec-alkyl (O ₁₁ _ ₁₅₎ -9EO

("Tergitol" -15-S-9) *. '6

Amine oxide ¹ ) 6

Sodium carbonate 60

basic sodium silicate 10

Water, added to 100

The amine oxide in each example is made according to the following Table IV varies. In a control product, the 6 percent amine oxide is replaced by another 6 percent of the same replaced non-ionic compound.

The extent of inorganic deposition when washing Terry toweling with these detergents is

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Determination of water with 18 ° French hardness (Ca ⁺⁺ : Mg ⁺⁺ = 2: 1) at 50 ° C and a product concentration of 0.15 percent, the laundry load, as in all wash tests of the examples ^ in each case 30 Seconds after the detergent is added. The results after 10 and 20 washing cycles are summarized in Table IV.

Table IV Amine oxide ia anorffanische Deposition example
No. 10
Pyridine N-oxide Washing cycles 20
2.8 Washing cycles
6.1 10 Dimethyl coconut amine oxide 1.6 2.1 11 double hardened
Dimethyl fatty amine oxide 1.5. 2.0 12th Dimethyl-N- (heptylamido) -
propylamine oxide 1.9 2.1 13th Dimethyl-N- (uridecylamido) -
propylamine oxide 1.6 1.9 14th Dimethyl-N- (tricLecylamido) -
propylamine oxide ' 1.3 1.6 15th Dimethyl-N- (heptadecyl-
ami do) propylamine oxide 1.4 M. 16 Dimethyl-N- (tridecoyl-
ethyl) amine oxide 1.7 1.8 17th Amine oxide of acetylated
Polyethyleneimine ¹ ' ³ 1.7 18th N-dodecyl-morpholine-N-
oxide 1.4 19th Dimethyl sec-alkyl
(C ₁ o_ij) amine oxide .3.0 6.0 20th 1,3-diaminopropane-li
stearoyl-N * -diiffethyl-
N'-oxide 1.4 21st Control attempt 4.0 8.0

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These results show the very substantial reduction the inorganic deposition for several of the amine oxides, although two of these amine oxides when used alone, i.e. in the Examples 10 and 20 give no reduction to the extent desired.

Examples 22 to 3 4

A series of laboratory tests are carried out using both an AmJnCQdLdS and sodium tripolyphosphate to inhibit inorganic deposition. The general recipe used is the same as described in Examples 10-21 except for the addition of 0.3 percent sodium tripolyphosphate. Using the same conditions as described in Examples 10 to 21, no noticeable inorganic deposition is obtained after 5 washing cycles with the following amine oxides:

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example

No. _ ". Amine oxide

22 _; . N, N-dimethyl-2-hydroxy-hexadecylamine dioxide

23 NjN-Dimethyl ^ -hydroxy-dodecylamine oxide

24 bis (N-2-hydroxyethyl) -2-hydroxy-hexadecylamine oxide

25th Bis- (N-2-hydrbxyethyl) -2-hydroxydodecylamine oxide

26 dimethyl-N- (heptylamidopropyl) amiioxide

27 Dimethyl N - (- undecylamidopropyl) amine oxide

28 Dimethyl-N- (heptadegylamidopropyl) -amine oxide

29 • Dimethyl-N-cheptadecylamidopropyl-amine oxide

30 amine oxide of methylated tetraethylene pentamine

31 amine oxide of polyethyleneimine

32 N-dodecyl-morpholine-N-oxide

33 1f3-diamino-propane-N, H ', N ^f -trimethyl-N-stearyl-

N.N'-diamine oxide

34 dimethyl-N-ctridecoylethyl) amine oxide

Examples 35 i) i s 38

The procedure of Examples 22-34 is followed using four amine oxides repeated, which under the conditions of Examples 22 to 34 a considerable inorganic deposition but the amount of sodium tripolyphosphate in Examples 35 and 36 is set to 0.4 percent and in Examples and 38 increased to 0.8 percent. No inorganic deposition can be detected under these conditions.

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Example no , amine oxide .

35 Dimethyl-N- (p-octyrbenzyl-sulfonamido-propyl) -

arable oxide

36 1,2-diaminoethane-N, N, N -trimethyl-N- (heptadecyl-

amidoethyl) diamine oxide

37 pyridine N-oxide

38 tri- (2-hydroxyethyl) amine oxide

Example 39

A detergent according to the invention, which can be formulated into a powder with difficulty using conventional methods with the preparation of the pulp, is produced by first preparing an aqueous pulp from all components with the exception of the amine oxides and the nonionic surfactants, which by spray drying to a powder with low Moisture content (3 percent) is processed. On this atomizing. Dried powder is a mixture of 8 parts of "Tergitol" 15-S-7 (sec.-Alcohol ^. ^ ₁₅ MEO), 6 parts of "Aromox" DMCDW (dimethyldicocoamine oxide) and 3 parts of isopropanol in a mixing kettle

and thoroughly mixed in,
Sprayed on at 70 C, with the isopropanol evaporating. A powder is obtained with a fairly 'high bulk density (0.55 g / cc) that is slightly sticky and has the following composition:

Component percent

Sodium carbonate - 65

Sodium silicate ¹⁰

"Tergitol" 15-S-7 8

"Aromox" DMCDW 6

optical brighteners 1

Sodium carboxymethyl cellulose. 0.5 Water, added to 100

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The addition of 2 percent "Alusil" AN as a flow aid results a considerable reduction in tack and a corresponding improvement in flow properties.

In a further manufacturing experiment it was found that the Addition of 2 percent fatty soap, a product with a lower bulk weight (0.37 g / ccm) without affecting the other Properties results.

Examples. 40 'to 54

A number of detergent solutions are used with various proportions of amine oxide (Aromox DWCDW) and various nonionic surfactants, all of which make up 12 percent total, or 12 percent of one of the surfactants alone, for comparison purposes, with either 30 percent (in the examples 40 to 42 and the comparative products (a) and (b)) or 40 percent (in Examples 43 to 54 and Comparative Examples (c) to (j)) sodium carbonate and prepared with 10 percent basic sodium silicate. The detergents are measured for their textile washing power using an ^M Terg-0-Tometer "at a product concentration of 0.15 percent in water of 18 ° French hardness (Ca" ¹ " ¹ " ι Mg ⁺⁺ a 2: 1) 5O ⁰ C examined. The test fabrics described in Example 2 are used, which are always added after the detergent. The wash is carried out for 10 minutes, followed by a 1-minute rinse. The percentage washing power is determined by calculation from the light reflections of the test fabrics before and after washing.

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The results are summarized in Table V '.

Tabel ' 20th 6th non-ionic 9 96 $> Detergency ERTC41A Example of non-ionic Amine oxide 9 Connection (<&) VGD 77 No connection 0 9 29 70 40 Tergitol 15-S-9 ^{1) X} 3 12th
_ \ 6th 32 70 " 41 " 6th ³⁾ 3 3 34 65 42 » 9 6th 12th 30th 66 Comparison
example (a) ^M 0 9. 0 32 71 Comparison
example (b) » 12th 0 9 ' 37 74 43 " 3 12th 6th 38 71 44 " 6th 3 3 37 68 45 " 9 6th 12th 33 68 Comparison
example (c) · » 0 9 0 33 72 Comparison
example (d) 12th 0 9 33 75 46 DobanoX 45-9EO ² * 3 12th 6th 38 73 47 ^w 9 8 4 3/0! 3 37 70 48 ^M. V 12th 33 69 Comparative
example (s) » O 34 73 Comparison
example (f) " 9 38 76 49 Alfol 1412-8E0 6th 39 * 72 50 ^w 3 39 70 51 ^M. 12th 34 70 Comparative
example (g) " 0 ' 33 72 Comparison
example (h) " 9 36 77 · 52. TEA-11 EO ⁴ ' 6th 35 74 53 ^M. 3 35 67 54 ^w 12th
I. 32 69 Comparative
example (i) " 0 • 33 Comparison case
game (j) "

'seki-linear alcohol κ ^ λλ ,, λκ)

² 'alcohol (C ₁ , ₁₅ ) -9EO (80 percent linear alcohol, 20 percent oi -methyl-branched-chain alcohol)

^Jl primary linear alcohol (Cj ₂ ⁴ ^ pettethanolamide-11E0

A comparison of the results shows that the better detergency is generally achieved with the examples according to the invention, in particular Examples 41, 44, 47, 50 and 53, in which the amounts of amine oxide and non-onogenic surfactants are the same. This indicates a synergistic effect.

Further detergents according to Examples 41, 44, 47, 50 and 53 are used with regard to the inorganic deposition according to 10 and 20 washing cycles for cotton terry toweling using the same washing process in a "Terg-O-Tometer" examined. The following results are obtained:

Percent inorganic deposition example no1

41 44 47 50

53 ■■ '. ■■

If no amine oxide is present in the detergents, i.e. as in the comparative products (a), (c), (e), (g) and (i), the extent of the inorganic deposition is in all cases about 4 percent after 10 washes and θ percent after 20 washes.

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10 washes 20 washes 1.1 1.4. .1.0 . . 1.4 1.2 1.6 Λ 1 »3 1.3 0.9 1.0

Examples 5 4 to '57

Four detergents with mixed builders are produced and based on their properties with regard to inorganic deposition according to the procedure described for Examples 41, 44, 47, 50 and 40. The results are in the the following table VI compiled; all detergents have the following recipe:

Component percent

non-ionic surfactant (Alfol 1412-8E0) 6

Amine Oxide (Aromox DMCDW) 6

Sodium carbonate 40

additional builder (according to table VI) 10

basic sodium silicate 10

Water, added to 100

! Table VI

example
No. additional
Builder 54 Sodium nitrile triacetate 55 Sodium tripolyphosphate 56 Sodium citrate 57 Sodium carboxymethyloxy
succinate

yes inorganic deposition 10 * washing 20 washing 0.5 ' 0.7 0.1 0.1 0.5 0.6

0.7: 0.9

The figures illustrate the significantly lower inorganic deposition when a small amount of an additional one is added complex builders. Sodium tripolyphosphate is particularly effective in this regard

209 843/0996

■■ " ²⁹ " 2245371

B e i s ρ i. '. E le 58 Hs 6 1

Four detergents are produced, two of which contain a solvent, dibutyl phthalate, to improve the detergency with regard to Pettan soiling on synthetic fabrics. The detergents are tested on a "Terg-O-Tometer" to determine percent detergency using a 65 percent "Dacron" polyester / 35 percent cotton test fabric soiled with used oil from an automobile crankcase. To do this, a method is used in which the test fabric is first rubbed with a stiff (70 percent) paste of the product, rinsed and then washed and usually rinsed using water of 18 ° French hardness (Ca ⁺ *: Mg ⁺⁺ = 2: 1) at 50 ⁰ C and a product concentration of 0.2 percent can be used. The recipes and the washing power are summarized in the following table:

component

non-ionic compound (Tergitol 15-S-7) double hardened dimethyl fatty amine oxide (Aromox DMHTD / W) sodium carbonate basic sodium silicate dibutyl phthalate water, added to percent washing power

Percent -in Sä every example £ 1 10 .60 10 10 6th 10 8th • 6 60 8th · 60 60 8th 60 8th 8th - 8th - - 5 100 6th 100 100 63.7 100 61.0 73.6 74.6

20984370996

These results are very good for a dirt that is difficult to remove. The addition of the solvent brings you clear advantage. Further experiments show that the advantage achieved with the solvent does not agree with one another other amine oxides in the Gemisoh with nonionic compounds or with. Use of hardened dimethyl fatty amine oxides Can be achieved as a surfactant alone. It turns out that for a noticeable improvement in detergency a minimum amount of about 4 percent of the dibutyl phthalate is required and that an excess of the nonionic surfactant over the amine oxide, however, no more than about 7 parts of the nonionic compound for every 2 parts of the amine oxide should be present.

Examples 62 to 6 5

Four detergents are produced according to a similar recipe, however, as an optional component, either calcium carbonate (in the "form of finely ground aragpnite" or Oalcite), additional sodium carbonate or sodium sulfate are used will. The following basic recipe is used:

Component percent

non-ionic surfactant (Alfol 1412-ΘΕ0) 6

Amine Oxide (Aromox DMCDW) 6

Sodium carbonate 40

basic sodium silicate 8

Addition (see Table VIl) 50

Water, added to 100

209843/0996

The detergent are returned to their washing power in a "Terg-O-Tometer" using the procedure described in Example 2 standard test fabrics with water of 18 ° French hardness <Ca ^++: Mg ⁺⁺ = 2: 1) hei'5O ⁰ C and a product concentration of 0.15 percent. "The results are summarized in Table VII."

Table VII percent Detergency example VCD BRTC41A No. £ J UO el ν 2 45 79 62 Calcite 44 81 63 Aragonite 44 82 64 sodium 40 75 65 Sodium sulfate

These results show the benefit of presence either of calcite or aragonite or of additional sodium carbonate, at least at the low product concentrations of the test conditions. It should be noted here that the detergents of Examples 62 and 63 have a lower pH than the detergent of example 64 and therefore offer greater security for household use.

Claims

209843/0996

Claims (21)

Patent claims 1. detergents that contain a builder and surfactants,
characterized in that the builder is about 25 "to 90 percent by weight of an alkali carbonate and the surfactants are about 5 to 25 percent mixed
Amine oxides ... and non-ionic surfactants. : 2. Detergent according to claim 1, characterized in that the alkali carbonate builder is sodium carbonate. 3. Detergent according to claim 1 or 2, characterized in that the amount of alkali metal carbonate is about 25 to 75 percent by weight of the detergent. 4. Detergent according to claim 3 »characterized in that the amount of alkali metal carbonate is about 45 to 70 percent by weight
of the detergent. 5. Detergent according to one of the preceding claims, characterized in that the ratio of the amine oxide surfactant to the nonionic surfactant is about 3: 1 to 1:10 parts by weight. 6. Detergent according to claim 5 »characterized in that
that the ratio of the amine oxide surfactant to the nonionic
Surfactant is about 3: 1 to 1: 3 parts by weight. 7 * detergent according to claim 6, characterized in that the ratio of the amine oxide surfactant to the nonionic
Surfactant is about 1: 1 parts by weight. 209843/0996 - 55 - 8. detergent according to one of the preceding claims, characterized in that the amine oxide surfactant has the general formula - N - ^ O in which R _{1 is} a C _1Q _ ₂₂ -alkyl or -alkenyir radical and R ₂ and R- are identical or different and are Cj, -alkyl radicals or C ₂ -hydroxyalkyl radicals. 9. Detergent according to claim 8, characterized in that the radical R .. is a linear alkyl radical and the radicals R ₂ and R are methyl groups. 10. Detergent according to one of the preceding claims, characterized in that the nonionic surfactant is a condensation product of an aliphatic alcohol or one Is alkylphenol with ethylene oxide. 11. Detergent according to one of the preceding claims, characterized in that the amount of mixed amine oxide and non-onogenic surfactants about 10 to 14 percent by weight amounts to. - 12. Detergent according to one of the preceding claims, characterized in that they add about 10 to 50 Ge contain weight percent finely ground calcium carbonate. 209843/0996 13. Detergent according to one of the preceding claims, characterized in that it is also an aromatic Solvent in an amount from about 4 percent by weight to a level no greater than the total amount of Surfactants is included. 14. Detergent according to claim 13, characterized in that the solvent is dibutyl phthalate. 15. Detergent according to one of the preceding claims, characterized in that they additionally contain no more than about 10 percent by weight sodium tripolyphosphate. 16. Detergent according to one of the preceding claims, characterized ^ .that they additionally have about 5 to 15 percent by weight Contain sodium silicate. 17.. Detergent according to one of the preceding claims, characterized in that they are in particulate form. . ■ '·' 18. A method for producing a detergent according to claim 17, characterized in that an aqueous slurry is prepared which contains the Alkalicarbona.t builder, and either incorporating the mixed amine oxide and nonionic surfactants into the slurry immediately prior to spray drying, or the spray drying of the pulp is carried out separately and then the amine oxide and nonionic surfactants with the powder detergent base mixed. 209843/0996 19. The method according to claim 18, characterized in that the amine oxide and nonionic surfactants before mixing with the pulp or powder detergent base with each other mixed. * - 20. The method according to claim 19, characterized in that one of the mixed amine oxide and nonionic surfactants volatile solvent incorporated. 21. The method according to claim 20, characterized in that isopropanol is used as the volatile solvent « 209843/0996