DE1617226A1 - Phosphate-free cleaning agent - Google Patents

Description

1817221

C 393 Eondon

Unilever ΙΓ.ΤΓ ·

Museum Park t, Rotterdam / Holland

Phosphate-free cleaning agent

Priority: USA patent application Mr. 564 556 of July 12, 1966

The invention involves an alkaline phosphate free detergent <>

In AEEN recent years, the public has become increasingly concerned with the effect of modern synthetic detergent to the water pollution.

Phosphate additives are widely used, especially in heavy duty detergents intended for use in laundries. These are not subject to bacterial degradation, and it has occasionally been observed in some lakes and rivers which take up considerable "amounts of phosphate-containing sewage that an excess of algae growth is present, which tends to completely _reduce the available oxygen in the water consume.

It has therefore become important in the detergent oil industry to provide phosphate-free detergent dentifrices of good effectiveness.

New documents (Article 7glAbg, 2Nr. lSatz3des Ändenina «« fc? .4. * Iie |

10880 / t »Sf

1617228

The invention creates a phosphate-free cleaning agent, which Birni characterized in that it is a detergent compound wherein two anionic functional Groups attached to a group having an acyclic hydrocarbon group of 15-20 carbon atoms are, and a water-soluble ionizable harmless one Salt of calcium »magnesium, aluminum, strontium or barium, in which the molar ratio of the Metal ion to the detergent compound is at least 1.2: 1.

The above remedy is based on the discovery of a phenomenon which is completely unexpected in detergent technology is. It has been recognized for many years that sulfate and sulfonate detergents in general are used in hard water can be used and that, because their metal salts are soluble, they are not detrimental Soap precipitates will form. It was also in general assumed that the presence of such salts, which is typically due to the hardness of the water, tended to reduce the cleaning power of these detergents. In the present invention, however, was surprisingly wise found, in complete contradiction to normal expectations that the above-mentioned metallic salts act as effective builders for the dianionic detergents. Ebeno contradicting the previous technology have the usual inorganic additives, namely the inorganic phosphates, a adverse effect on the cleaning power of the dianionic detergents,

As a result of these completely unexpected findings, it is now possible to produce detergent sets which "have the same effect" as "the alkylbenzenesulfonate detergents generally used up to now for grubwashing agents and additional phosphates". The dianionic detergent can be selected from biodegradable active ingredients, and because the amount of metal salt required is relatively small and only slightly larger than the normal

109808/1957

BATH ORIGINAL

1617228

is wisely present in hard water, calibration does not result noticeable contamination of surface and ground water from the cleaning agents according to the invention in batches.

A typical cleaning agent approach according to the original rind comprises from 4-85 $> of the dianionic detergent and from 1-8OvS of the metal salt present, with the remainder being water or any of the other common cleaning agent additives "includes ¹¹ phosphate-containing additives.

In the context of the invention, the expression “dianionic detergents” means that the compounds in question contain two anionic functional groups. This is not to be confused with the valence of the two anionic functional groups, each of which can be monovalent or polyvalent. The water-solubilizing cations include the usual cations known in cleaning agent technology, these are the alkali metals (for example Li, Ha, K _ff Rb and Gs), ammonium, substituted ammonium (for example friethanol ammonium, corpholine) and the alkaline earth metals as well like other metals in groups HA, HB, IHA and IVB of the periodic table, with the exception of boron, usually the water-solubilizing cation is sodium, potassium or ammonium.

Suitable dianionic detergents bind the disulfonates, Disulphates or mixtures thereof »which by the formain

) M _{f R} (so ₄ ) ₂ M ₂ , R (SO ₃ ) (SO ₄ ) Ii ₂

can be represented, in which R is an acyclic aliphatic hydrocarbon radical with 15-20 carbon atoms and M is a water-solubilizing cation, for example the G ^ ₅ to Ooq disodium-1 _f 2-alkftli: disulfate, C ₁₅ -C ₂ Q dipotassium-1,2 -alkeXtdisulfonate or -disulfate,

1098.0 * / 195.7

O ₁ c Cpo Eiammonium-I »8-alkyldisulfate, disodium-1,9 -hexadeeylsulfate, O-ic-CpO ΕΙ * ¹³ · * ¹ "! ¹¹¹¹¹ "" ¹ , 2-alkyldisulfonate, disodium-1,9-stearyldisulfate and 6,10-octadecyl disulfate.

The aliphatic part of the disulfates or disulfonates is generally essentially linear, which is desirable, among other things, because it is desirable to be biodegradable Property gives the detergent. Because the disulfates and oisulfonates. Typically by Adding a sulfate or sulfonate group to a unsaturated bond are produced, these disulfate and disulfonate detergents are essentially saturated simply because of their production. Substantial satiety but is not a critical feature of the present invention.

Another class of dianionic detergents are compounds in which one of the anionic groups is attached to the aliphatic group is linked by a low molecular weight linking group · Such compounds can be represented are given by the empirical formula

RX (A) ₂

where A SOJK, SO.M or ΡΟ, Μρ ^ΐ8Ϊ » ^{R and M are as} defined above and X is the connecting group, for example the AmIdO, amidoalkyl / .en-, phenyleneoxyalkylene, polyoxyalkylene, hydroxyalkylene, phenylalkyl, carboxylic acid ester and phenoxy group · One of the sulfonate, sulfate or phosphonate groups is attached to the linking group. The other can be attached to the linking group or to the R radical.

The ester bond can for example be formed by reacting isäthionaten (for example beta-Hydroxyäthylsulfonate) old bucket of fatty acid. Yet another class of leterrerbindnngegruppem is formed by using partial Glyeeride, for example C ₁₈ Mömoglyceriden. One of the free hydroxyl groups of the oleic ester can be sulfated

BAD ORIGIfOAU

10Ö808 / 1957

be and a sulfate or sulfonate group additionally to be added to the C.g part. Many other linking groups which contain a carboxyl moiety (e.g. -G00-) and from 1-5 carbon atoms can to be used.

The amia bond (eg-CONH-), which can be used in combination with a CtO ₂ hydrocarbon radical, can be produced by sulfating a monoethanol amide. Compounds of the same general class can also be prepared by reacting a beta-aminosulfate or a taurine (e.g., a beta-aminosulfanatase) si / fc G-15-C ₂₀ fatty acids which contain a sulfatable or sulfonatable functional group . Compounds of the same general type can be made by reacting higher molecular weight fatty amines with lower molecular weight carboxylic acids. For example, suitable compounds can be prepared by reacting a hydroxy fatty acid amine with a hydroxycarboxylic acid, for example lactic acid. The resulting lactyl amide can then be converted into a disulphate by reaction with a sulphating agent.

Ether bonds can be made by reacting a pettalcohol with a C.-Cj- alkylene oxide, especially ethylene oxide, getting produced. In this class of compounds X has an ether (-0 -) -! Function and has from 1-5 Hydrocarbon atoms, and is present 1-50 times, with ether formation can also be derived from Glycerinäthem will. In such compounds, the two free hydroxyl groups of the oleic moiety can be converted into a sulfonate or Sulphate salt are transferred.

Yet another class of compounds within the general formula are the alkylbenzenesulfonates of following formula

(SO _x M) ₀

Connect

109808/1917

BATH

-δι
votin R and M are as defined above · In this class of compounds the aromatic nucleus is roughly analogous to the linking group X of the class of compounds discussed above.

Typical compounds of the aforementioned general classes include, but are not limited to, the following to be:

(t) R-CH CH ₂ . BB.R - C _13-18 H

SO ₅ M SO ₅ MM = Na

(2JR-CH-CH ₂ SO ₄ M e.g. R = C _13-18 I £ 2 £ CH ₂ SO ₄ MM = Na

(3) R-CHCON (CH ₃ ) CH ₂ Ch ₂ SO ₃ M e.g. R = C ₁₆ H ₃₃ SO ₃ MM = Na

U) R-CH-CO-O-CH ₂ CH ₂ SO ₃ M
SO ₃ M

(5) R - ^ - SO ₃ M e.g. R = G ₁₅ . ₁₈ H ₃₁ _ ₃₇

O ₃ MM = Na

(6) R0 - <^ - S0 ₃ M e.g. R = C ₁₆ H ₃₃

M = Na

O ₃ M

(7) RCHCH ₂ OCH-CH ₂ So ₃ M

OH CH ₂ SO ₃ M

(8) R-CHCH ₀ OCH ₀ CHCH ₀ SO ^ m e.g. R = C ₁ , - H,

I 2 2, 2 3 16

SO ₃ M OH M = Na

(9) CH ₃ (CH ₂ ) ₇ CHj-CH (CHg) ₇ CON (CH ₃ ) CH ₂ CH ₂ SO ₃ M

H, SO ₃ M

(10) R-CHGH ₂ OCH ₂ CH ₂ SO ₃ M

O ₃ M

BATHROOM 0R1G5NAL

109808/195?

(11) ROCHgCH-CH-CHgSOjM

(OCHgGHg) _x SO j H

(12) RCHCHgSOjM

(13) ROCH ₀ CHCH ₉ SO-M

2.2 3

OSOjM

(14) RCHCONHCHgCHgOSOjM

SOYM

(15) RCHCHgN (CHj) CHgCHgSOjM

OSOjM

(16)

W] (I.

(23) R-CH-CHgOCHgPOjMg CHgOCHgPOjMg

(24) R-CH-OH ₂ OCHgPOjMg

CH ₂ OSO ₃ M

e.g. R β * Ϋ4- | -6 Η 16 33 I. M « Well ³¹ " ^{33 β} ° 16-18 ^H 33-3 ' 1 .R = ⁰ 16 ^H 33 = Well M = N / A E.g. . R ■ e.g. R M.

(17) R-CH-CHgOSOjM e.g. R = Ct3-18 ^H 31-3 '

OCHgOHgOHgSOjM M «Well

(18) RCH-CHgOCHgCHgOHgSOjNa

OSOjNa

(19) R-CHCH ₂ OCHgOHgSOjM

OSOjM

(20) R-CH-CHgSOjM e.g. R «° 12-15 ^H 31

CHgOSOjM M = Na

(21) RO-CHgOH-CH ₂ SOjM e.g. R * C ₁ ^ ₂₀ HjJ _-

(OCHgCHg) _x OSOjM M «Na, χ» 3

(22) R.

BAD OR / GINAL '

(25) R-CH-GH ₂ OOH ₂ PO ₅ M ₂

(26) R-OCH ₂ -CH-CH ₂ SO ₃ O

CH-CH ₂ SO OCH ₂ PO ₃ M

(27) R-CH-CH ₂ SO ₃ M OCH ₂ PO ₃ M ₂

(28) R-NHP-CH ₉ SO ^ M

OM

(29) RCHCH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OSO ₃ Na

OSO ₂ Na

e.g. ^R = ^C H-16 ^H 31 M-Na e.g. R = C ₁₈ H ₃₇ M * Well e.g. R = C ₁₃ . ₁₈ H31

Of the above general classes, certain compounds are made because of their greater detergency and because they are economical can be preferred. In general, preferred compounds are aliphatic acyclic Hydrocarbon chain of 16-18 carbon atoms. Alkyl disulfates or sulfonates, of which Formula (1) or (2) above are examples, and sulfoalkyl-N-methyltaurine and sulfoalkyl isethionates (formulas (3) and (4) above) are preferred classes of dianionic Detergents.

The metal salts used as additives in the invention are the water-soluble ionizable salts of calcium, barium, strontium, magnesium or aluminum with harmless acids. The expression "harmless acid" is understood to mean that the acid content of the Salt is chosen so that it is free from adverse effects Color or toxicity which would interfere with the intended use of the detergent, and is free from groups that are disadvantageously having

109808/1957

BAD ORSGiMAL

the other components of the detergent formulation would react. - For example, arsenates would be used for Use in household cleaning agents, perchlorates because of their tendency with organic compounds spontaneously to react and permanganates are unsuitable because of their purple color. Suitable metal salts are calcium and Magnesium acetate, calcium and magnesium benzoate, gaoium metaborate, Magnesium orthoborate, barium strontium calcium and Magnesium bromide, calcium butyrate, calcium and magnesium chloride, Calcium cinnamate, calcium citrate, calcium ethyl sulfate, Calcium and magnesium malate, calcium maleate, Calcium malonate, barium, aluminum, strontium, calcium and magnesium nitrate, calcium propionate, calcium and magnesium salicylate, aluminum, calcium and magnesium sulfate, Magnesium and strontium tartrate and calcium and magnesium thiosulphate »Sometimes hypochlorites can occur to the extent that it is suitable that it is not just a metal ion deliver, but also produce a bleaching effect. However, as is well known, when approaching at the same time cleaning and bleaching mixtures on α the Possibility of reaction of the cleaning agent and the bleaching agent with each other must be taken into account.

A proportion of the required metal ion can if desired by using the dianionic detergent in the form of its calcium or magnesium salt will. However, this will only be approximately 1 mole of inorganic metal ion for every mole of dianionic Deliver detergent. Thus the most satisfactory results * To obtain nits, provision must be made for supplementary ionosable Metal connections must be made. Cleaning supplies-

represent
Formulations within the present invention can contain up to 16 moles of metal ion per 1 mole of dianionic detergent. Preferred agents have from 2-8 moles of metal ion per mole of detergent.

Although the aluminum salts, for example aluminum sulfate,

109808/1 ^ 67

BATH

- ίο -

will lead to relatively acidic mixtures found that as long as the pH of the washing solution is not critical for other reasons (e.g. compatibility with sodium silicate, a common detergent additive), is the ale Bolge of using The acidity resulting from aluminum salads is irrelevant.

The salt should be in water to the extent of at least about 0.1 # in the presence of the other ingredients, which are present in the washing solution »be soluble. Ionizable salts are generally used for this purpose suitable. .

The invention is further illustrated by the following examples.

Examples 1-5

A series of approaches have been made by combining a disodium ri, 2-alkyl disulfate, which contains a mixture of C-Jc _- C ₂₀ alkyl groups, with calcium chloride in proportions of

Example no.

1 0.8 moles calcium / mole disulfate

2 1.6 moles calcium / mole disulfate

3 3.2 moles of calcium / mole of disulfate

This ^Ä eIHE mixtures old together a cleaning agent containing either only the pure disulfate (Control A) or alkylbenzene (control B) were tested spotted on cleaning ability on Foster D.Snell laundry in a Terg-O-Tometer with an initial reflectance of the test pattern of 19.5. * -other additives were used. Distilled water was used in all cases with the following results:

BAD OR! G / _NAL

, 0 32.7 35.4 37.8 19.09t Cg ₊ ^{R äC} 15-18 ^H 31-37 1617226 15,0Jt 4d) RCHCHgOGH ₂ CH ₂ ¹ BOj-Na ^{R sC} 15-17 ^H 31-35 - 11- -
Control control example
Net assets AB 12 3 according to the invention 0.35t OSOj-Na ^{+ R = 0} 15-18 ^H 31-37 at $ 0.05 applied _{22 Q} g «
Lot '' is indicated by the following example: 0.075t (e) RCHGHgSOj-Na ⁺ Example 4 3) disodium 1,2 C ₁₅ -G ₂₀ alkyl disulfate 6.0Ji OSOj-Na ⁺ A typical cleaning agent approach " Calcium and magnesium sulfates 1005t (f) RGH ₀ OGH ₀ CHGH ₀ SO ₅₁ -Na ⁺
I 2 j 2 3 ^{R = iC} 15-16 ^fi 31-33 Carbocymethyl cellulose OSOj-Ha ⁺ Optical brightener To apply the invention to a manifold (g) RCHGHgSOj-Na ⁺
SOy-Na ^{+ R} * ° 15-16 ^H 31-33 Hatriura silicate C molar ratio 2.0) of dianionic detergents are explained below, the sodium sulfate and miscellaneous
to fill up following connections established! R = C ₁₆ Hj3 Example 5 j (b) RCH (CHgOSOj-Ha ⁺ ) g ^{R = C} 15-16 ^H 31-33 Cc) RCHCHg (OCHgCHg) ₂ OSOj-Ha ⁺ OSO ^ -Ha ⁺

Mti _BATH

(η) ROH-CO-OH ₂ OH ₂ SO ₅ -Na ⁺ I ι

^{R = C} 16 ^H 33

S0 - Na ⁿ

The compounds were tested by the method according to Example 1 using water with hardeners corresponding to between 180 and ir parts per million, calculated as calcium carbonate. The hardness was created by adding a mixture of calcium and magnesium sulfate to the tea and the detergents were tested at a concentration of 0.03 i> (except as noted) .

Purification ability of Dianionice with metal ions (1)

1 * Harder (ppm) (Ca ⁺⁺ / 720 7.7 2 180 360 540 - 17.5 2 15.9 18.3 - 8.1 2 5.5 7.4 7.6 3.6 2 9.8 14.4 17.1 10.0 2 6.1 7.5 8.6 2.8 2 2.6 3.2 3.4 - 1 10.3 11.1 10.5 - 2 1.9 2.4 2.6 - 3 19.4 19.6 - 9.0 - 10.7 23.9 24.5 23.5 (ρ
Connection ^K (a) (o * o5%) (b) (c) (d) (β). (f) (G) (H) (H) (H)

(1) The detergency is measured by the increase in reflectant in the test samples.

(2) Code numbers refer to the connections described above.

(3) Three different samples of Poster D. Quickly soiled laundry were used during this test.

109808/1951

BATH

During the previous test · using a * mixture of MgSO ₄ and CASO. have been carried out, fcaim are expected to replace their ersata with equal amounts of salts, such as Sr (H ¹ Oj)

would give similar results.

BaOIg and

Example 6

A test for cleaning performance, as in Example 1 was described using the dianionic Jeteifgene

1-0-0-CH ₂ OH ₂ SO ₃ Na

o, o5 wt.? 6 in aqueous solution in combination with aluminum sulfate (added as Al ₂ SO ₄ , 18BgO),

The results were x

lile per million Al cleaning power

0 23 »1-

360
28.2

540 29.1

109808/1957 '

BATH

Claims (1)

- ■ 14 - U -Pfcoaphat-free ^ Rainigi »§eei * tt £ f thereby g · k β η η -a ti ο b st» that ei tint DttergeniTerbind, in which swqi anionieohe functional group * at one group with tin · »aoyoliaohen coal vaporizer group with 15-20> Carbon atoms are bonded, and «in water-soluble ioniiitrtoar · »harmless SaXs το» calcium, magnesium, Strontium or 3ariu », in which the molar ratio de «Medallions to the detergent compound at least t, 2 $ t iit _y uefmee-k. 2, means to A "ipruoh 1, characterized ekennseichn λ g · tt that the, Dettrgen · in amounts τοη 4-65 wt. ^ Je and the Sal" in Men T] Dn are augegen 1-80 Gew.5t · 3 «means according to inapruoh 1 or 2, thereby, g e k β η η - a e is worthwhile and β ι 1 data dan molar ratio between 2: 1 4. Means according to df η previous »claims, thereby Labeled without the fact that the detergent is a sulfate or sulfonate with a · »hydrophilic anion. 5. Agent according to claims 1-3, characterized in that the detergent is «in sulfoalkyl-N-methyltaurine. -. 6. Agent according to claim 1-3, characterized in that the detergent is a sulfoalkylisethionate. 7 · Means according to the Torhergoing claims, thereby characterized that the acyclic »hydrocarbon group is an alkyl. 109600/19 ^ 7 BADORiGiNAL