Detergent composition comprising a mono-, di- and tri-ester mixture and method of manufacturing same

A detergent composition comprising a mixture of mono-, di- and tri-ester nonionic compounds represented by formula (I) and a nonionic compound represented by formula (II), wherein the weight ratio of said mono-, di and tri-ester nonionic compounds is 46-90/9-30/1-15, ##STR1## wherein B represents a hydrogen atom or a ##STR2## group and R represents an alkyl or alkenyl group having 6 to 22 carbon atoms, R' represents H or a CH.sub.3 group, and each of n, m and p independently represents an integer from 0 to 40 and m+n+p=2-100; said detergent composition exhibiting outstanding biodegradability, non-toxicity, non-irritancy, foam stability and better dye inhibition transfer, while maintaining and even improving detergency.

FIELD OF THE INVENTION 
The present invention relates to novel liquid detergent compositions which 
are biodegradable, non-toxic, and non-irritating detergency, foam 
stability and colour protection in case of heavy and light duty detergent. 
These detergent compositions are particularly useful in formulating 
shampoos, body shampoos, washing up, all purpose cleaners, and heavy and 
light duty detergents. 
In fact, the present invention relates to cleaning formulations comprising 
a specific nonionic mixture. 
In addition, the present invention relates to a method for preparing the 
above mentioned nonionic mixture. 
DESCRIPTION OF PRIOR ART 
Most detergent compositions use a combination of anionic, amphoteric and/or 
nonionic surfactants, in order to obtain a final product having better 
properties in terms of irritation, detergency and foam profile. 
One problem in the field of chemicals is the question of ecotoxicity and 
how to get good performance without serious interaction with the surface 
of fabrics or skin. 
The nonionic compounds conventionally employed in employed in the detergent 
compositions are ethoxylated nonylphenols, C.sub.12-18 alcohols 
ethoxylated with approximately 12 moles of ethylene oxides, and lately, 
C.sub.12-15 alcohols ethoxylated with 2 to 9 moles of ethylene oxides and 
EO/OP derivatives. 
For example 
Japanese Patent Laid-Open No. 55-86894 discloses the use of a secondary 
C.sub.6-14 alcohol ethoxylated with 4-15 moles of ethylene oxides on 
average. 
Japanese Patent Laid-Open No. 52-22007, and Japanese Patent Publication No. 
83037356 disclose the use of an ethoxylated middle alcohol of the formula 
R.sub.1 O(C.sub.2 H.sub.4 O)nH, wherein R.sub.1 is a straight or branched 
chain alkyl and n is 1-12 on average in detergent compositions. 
European Patent No. 80749 discloses the use of ethoxylated alkyl phenols in 
detergent compositions. 
U.S. Pat. No. 4,908,150 discloses the use of polyethylene glycol ether of a 
glycerol ester compositions. 
Japanese Patent Laid-Open No. 55-133495 discloses the use of a 
polyoxyethylene hardened castor oil or fatty acid ester, thereof, 
polyoxyethylene glyceryl ether fatty acid ester, polyoxyethylene 
trimethylol propane fatty acid ester and polyoxyethylene alkylether 
diester of N-lauroylglutamic acid in detergent compositions. 
However, use of such nonionic compounds deteriorates the detergency ability 
of detergent formulations, and in the case of heavy and light duty liquid 
detergents tends to cause dye transfer, especially upon repeated 
laundering. In addition to the above mentioned points, current nonionic 
compounds cause skin and eye irritation, and the toxicity to fish daphnia 
inmobilization and algae are unacceptable under the present environmental 
requirements. 
Other patents describe the use of specific nonionic compounds, different 
from the usual ones, in particular applications and/or conditions. 
U.S. Pat. No. 4,247,425 discloses the use of alkoxylated partial glycerol 
esters of a detergent grade fatty acid in light duty detergent 
compositions. 
EP Patent 0007120 discloses an emulsifying system, to be used in a 
handwashing composition, mainly consisting of mono- and diglycerides of 
higher natural fatty acids and ethoxylated glycerine esterified by fatty 
acids. 
U.S. Pat. No. 4,897,214, discloses the use of monoesters of fatty acids 
with polyoxyethylene hexitan derivatives in skin cleaning preparations. 
FIELD OF THE INVENTION 
WO Patent 92/00945 discloses the use of octadienyl glycerin ethers with 
polyoxyethylene. 
UK Patent 2197338 discloses the use of polyoxyalkylene alkyl- or alkenyl 
ethers and polyoxyalkylene glycerol fatty acid esters in detergent 
compositions. 
None of disclosures mentioned above teaches the mixture of nonionic 
compounds according to the present invention. 
The present inventors have carried out research to develop a detergent 
composition that exhibits outstanding biodegradability, non-toxicity, 
non-irritant foam stability and better dye inhibition transfer, while 
maintaining detergency, and even having improved detergency. 
It was unexpectedly found that the above mentioned requirements can be 
satisfied when the specified mixture of nonionic compounds of the present 
invention is incorporated into a detergent composition. 
This finding has led to the present invention. 
SUMMARY OF THE INVENTION 
Accordingly, the present invention relates to a detergent compositions 
comprising a mixture of mono-, di-and tri-ester nonionic compounds 
represented by formula (I), wherein the weight ratio of the mono-, di- and 
tri-ester nonionic compounds is 46-90/9-30/1-15 
##STR3## 
wherein B represents a hydrogen atom or a 
##STR4## 
group, R represents an alkyl or alkenyl group having 6 to 22 carbon atoms, 
and at least one B is an ester group; 
p, n and m have a value between 0 and 40 and (p+n+m)=2-100 preferably 9-19; 
and 
R' represents H or CH.sub.3 group; and a nonionic compound represented by 
formula (II) 
##STR5## 
wherein p, n and m have a value between 0 and 40 and (p+n+m)=2-100 
preferably 9-19; and 
R' represents H or a CH.sub.3 group. 
The high content of ethoxylated monoester represented by formula (I) and 
the ratio of compounds represented by formula (I) and the compound 
represented by formula (II) are the key parameters in obtaining the above 
mentioned properties. 
The weight ratio of the nonionic compounds represented by formula (I) to 
the nonionic compound represented by formula (II) in the detergent 
composition may have a value between 3 to 0.33, preferably 1.3 to 0.75. 
A mixture of the nonionic compounds represented by formula (I) and the 
nonionic compound represented by formula (II) in can be obtained by 
conventional methods. 
For example, the mixture can be obtained by the following reaction 
processes. 
(A) The interesterification reaction between triglyceride and glycerine, in 
a molar ratio of 0.1-10/1, preferably 0.15-3.5 (in the presence of an 
alkaline catalyst), and the reaction with a C.sub.2-3 alkylene oxide, or 
viceversa will lead to a mixture of mono-, di- and triglyceride nonionic 
compounds represented by formula (I) and the nonionic compound represented 
by formula (II), having the desired ratio of compounds represented by 
formula (I) to the compound represented by formula (II), due to migration 
and an exchange phenomena, with an HLB higher than 2. 
(B) The reaction of glycerine with a C.sub.2-3 alkylene oxide, in the 
presence of alkaline catalysts, and the later reaction with fatty acid in 
a molar ratio of 0.1-10/1, preferably 0,7-3.5/1 in the presence of an 
acidic or alkaline catalyst will lead to a mixture of mono- di- and 
triglyceride nonionic compounds represented by formula (I) and the 
nonionic compound represented by formula (II) due to a migration and 
exchange phenomena, with an HLB higher than 2. 
Triglycerides that can be used in process (A) include natural fat and oil, 
as well as synthetic triglyceride. 
The fat and oil include vegetable oil, such as coconut oil, palm oil, and 
soybean oil; animal fat and oil, such as beef tallow, and bone oil; 
aquatic animal fat and oil; hardened oil and semihardened oil thereof. 
In the present invention the mixture of nonionic compounds represented by 
formula (I) and the nonionic compound represented by formula (II) can be 
incorporated in an amount of from 0.2% to 40%, preferably from 3% to 20% 
by weight based on the total weight of the detergent composition. 
The reason why the detergent composition of the present invention exhibits 
outstanding biodegradability, non-toxicity and non-irritancy, without 
deterioration of its detergeny is uncertain, but it appears that good 
performance of the present composition results partially from the 
existence of fatty acid groups that facilitates biodegradability and very 
low skin irritation, oral toxicity, fish toxicity, algae and daphnia 
inmobilization, as compared with conventional nonionic compound. 
Furthermore incorporation of the mixture described herein considerably 
improves the foam profile, anti dye transfer and perfume solubilization 
properties of a detergent composition, when compared with conventional 
formulations, a high EO monoglyceride ratio and the synergistic effect 
between the compounds represented by formulae (I) and (II). 
Other surface active agents such as anionic, other nonionic, and amphoteric 
agents and other additive useful in the practice of this invention may be 
used depending on the kind of final product to be formulated. These other 
surface active agents and additives so they are standard items of commerce 
so they will be not further comments upon herein.

EXAMPLE 
The present invention is described in detail by way of the following 
examples. The present invention, however, is not limited to these 
examples. 
REFERENTIAL EXAMPLE 1. 
The mixture of nonionic compounds represented by formula (I) and the 
nonionic compound represented by formula (II) is obtained, for instance by 
the following process: 
##STR6## 
wherein B represents a hydrogen atom or a 
##STR7## 
and group; p+m+n=15; represents a coco alkyl chain; and the weight ratio 
of nonionic compounds represented by formula (I) to the nonionic compound 
represented by formula (II) is 1. 
500 g (0.76 moles) of coco TRG, 210.7 g (2.29 moles) of glycerine 99% and 
1.2 g of KOH 85% as a catalyst are placed in a 3 kg flask properly 
equipped. The system is purged several times with N.sub.2, vacuum stripped 
until 110.degree. C., and heated to 140.degree. C. When the temperature 
reaches 140.degree. C., the reactor is pressurized to 2-3 kg/cm.sup.2, and 
ethylene oxide is added until a total of 2013 gr (45.7 moles). 
After the final charge of ethylene oxide, the reaction mixture is allowed 
to react for about 1/2 hour; the reaction mixture is then cooled and 
discharged from reactor. A mixture of nonionic compounds represented by 
formula (I) and the nonionic compound represented by formula (II) is 
obtained. 
REFERENTIAL EXAMPLE 2. 
The mixture of nonionic compounds represented by formula (I) and the 
nonionic compound represented by formula (II) is obtained, for instance by 
the following process: 
##STR8## 
wherein B represents a hydrogen atom or a 
##STR9## 
group; p+m+n=10; R' represents a CH.sub.3 group; 
R represents a tallow alkyl chain; and the weight ratio of compounds 
represented by formula (I) to the compound represented by formula (II) is 
1.3. 
14.3 g (0.1554 moles) of glycerine 99% and 1.2 g of KOH 85% as a catalyst 
are placed in a 250 gr flask properly equipped. The system is purged 
several times with N.sub.2, vacuum stripped until 110.degree. C., and 
heated to 140.degree. C. When the temperature reaches 140.degree. C., the 
reactor is pressurized to 2-3 kg/cm.sup.2 and ethylene oxide is added 
until a total of 67.9 gr (1.54 moles). After the final charge of ethylene 
oxide, the reaction mixture is allowed to react for about 1/2 hour; 52.3 
gr (0.15 mol) of a methyl ester of fatty acid derived from tallow is added 
and mixed for 45 minutes. Finally, the product is cooled and discharged 
from reactor. Thus a mixture of nonionic compounds represented by formula 
(I) and the nonionic compound represented by formula (II) is obtained. 
______________________________________ 
EXAMPLE 1. 
HDPD 
COMPOSITION 
Raw materials 1 2 3 4 5 6 
______________________________________ 
Na dodecyl benzene sulphonate 
10 10 10 10 10 10 
Ethoxylated (7) C.sub.13--15 alcohol 
9 -- 6 -- 9 -- 
Nonionic mixture of present 
-- 9 -- 6 -- 9 
invention (from referential example 2) 
Coco fatty acid -- -- 2 2 -- -- 
Silicone 0.2 0.2 0.1 0.1 0.2 0.2 
Zeolite 35 35 -- -- 35 35 
STPP -- -- 35 35 -- -- 
Polycarboxilated 5 5 5 5 5 5 
CMC 1.5 1.5 1.5 1.5 1.5 1.5 
Perborate mono hydrate 
15 15 13 13 15 15 
Na Carbonate 12 12 15 15 12 12 
Na Silicate 2 2 2 2 2 2 
PVP -- -- -- -- 0.8 0.6 
Enzyme 0.7 0.7 0.7 0.7 0.7 0.7 
TAED 4 4 4 4 4 4 
Sodium sulphate B. B. B. B. B. B. 
Perfume 1 1 1 1 1 1 
______________________________________ 
Note: 
B means balance. 
Note: B means balance. 
Detergency evaluation test: 
Washing machine: 
Temperature: 30.degree. C. and 60.degree. C. 
Dosage: 6 gr/l. 
Water hardness: 20.degree. HF and 40.degree. HF. 
Washing load: 2 kg of non-soiled cotton-polyester cloth and EMPA 101, 104, 
117+particulated soil. 
No pre-washing program. 
Detergent ability was evaluated for the detergent compositions appearing in 
Table 1. 
With all variables taken into consideration, that is, temperature, water 
hardness and soil type, the nonionic mixture described herein demonstrate 
in the worst of cases, equivalent efficiency in terms of detergency. 
However, on the other hand, compositions containing the nonionic mixture of 
the present invention provide a more superior colour care than the 
conventional ethoxylated alcohol. 
The following tests have been conducted at 30.degree. C. 
1.- Using Reactive dyestuff. 
After 15 washings, differences appeared in terms of colour transfer. 
Dye transfer was evaluated measuring delta E values (L.sup.2 +a.sup.2 
+b.sup.2).sup.1/2 by Hunter-Lab. The resulting discolouration of fabrics 
is shown in the table below: 
TABLE 1 
______________________________________ 
Compositions 
Blue Green Red 
______________________________________ 
1 8.0 14.0 6.0 
2 5.7 10.3 5.0 
3 6.0 8.0 4.5 
4 5.0 6.5 4.0 
5 1.3 0.9 0.5 
6 1.2 1.0 0.5 
______________________________________ 
The lower delta E, the better the composition is able to prevent dye 
transfer. Therefore it can be concluded from the above results that the 
nonionic mixture according to the present invention performs better than 
alcohol ethoxylated in preventing dye transfer and it is possible to save 
on the amount of polyvinylpirrolidone used (a typical dye-transfer 
inhibitor). The specific amount to be saved will depend on the effect of 
other components, or, in other words, on formulation design. It appears to 
the inventors that a synergistic effect exists between the nonionic 
mixture of present invention and PVP. 
2.- Using Direct dyestuff. 
______________________________________ 
References: 
Yellow: Solar Yellow 3LG 160% 
Blue: Solar Blue 2GLN 350% 
Formulations: Blue Green Yellow 
______________________________________ 
Solar Blue 2GLN 350% 
1% 1% -- 
Solar Yellow 3LG 160% 
-- 1% 1% 
SO.sub.4 Na.sub.2 
20 g/l 20 g/l 20 g/l 
Sandofix R 3% 3% 3% 
______________________________________ 
After 3 washings, differences appeared in terms of colour transfer. 
Dye transfer was evaluated measuring delta E values (L.sup.2 +a.sup.2 
+b.sup.2).sup.1/2 by Hunter-Lab. The resulting discoloration of fabrics is 
shown in the table below: 
TABLE 2 
______________________________________ 
Compositions 
Blue Green Yellow 
______________________________________ 
1 2.0 2.5 4.0 
2 1.3 1.7 3.0 
3 1.6 8.0 3.2 
4 0.9 6.5 2.0 
5 1.3 0.9 0.7 
6 1.2 1.0 0.7 
______________________________________ 
The results of tests 1 and 2, were corroborated by a 5 person panel, who 
evaluated the results according to a scale. 
______________________________________ 
EXAMPLE 2. 
HDL 
COMPOSITIONS 
Raw materials 1 2 3 4 
______________________________________ 
Na lauryl sulphate 
-- -- 4 4 
Na dodecyl benzene 
10 10 5 5 
sulphonate 
Ethoxylated (7) -- 5 -- 15 
C.sub.13--15 alcohol. 
Nonionic of present 
5 -- 15 -- 
invention. (from refe- 
rential example 2) 
Potasium coconut soap 
5 5 10 10 
Ethanol -- -- 3 3 
Propylenglycol 7 7 7 7 
Perfum 1 1 1 1 
Enzyme 0.7 0.7 0.5 0.5 
Na formiate 1 1 1 1 
Na phosphonate 0.8 0.8 0.8 0.8 
TEA 85% Req. Req. Req. Req. 
NAOH 50% Req. Req. Req. Req. 
Cl.sub.2 Ca 1% 2 2 2 2 
Water B. B. B. B. 
______________________________________ 
Note: 
B means balance. 
Req. means required amount. 
Following the same test conditions explained above for HDPD, (adapting the 
dosage according to the composition) the following results were obtained: 
Sufficient detergency in all cases. 
Colour appearance results are shown in Table 3. 
TABLE 3 
______________________________________ 
Compositions 
Blue Green Red 
______________________________________ 
1 0.9 4.0 3.2 
2 1.5 5.0 3.8 
3 1.6 5.1 3.8 
4 3.0 6.0 4.5 
______________________________________ 
Compositions containing the nonionic mixture of the present invention 
better prevent colour transfer, even in HDL where the pH is neutral and no 
optical brighters are used. (Note that HDL was used as colour saving 
detergents before the use of the new segment of colour saving H.D.P.D.). 
______________________________________ 
EXAMPLE 3. 
WASHING UP. 
COMPOSITIONS 
Raw materials 1 2 3 4 
______________________________________ 
Na lauryl ether sulphate 
10 10 7 7 
Na Alfa-olephine sulphonate 
-- -- 4 4 
Alkyl amido propyl betaine 
5.3 4.5 5.7 2.5 
Ethoxylated (7) C.sub.13--15 alcohol 
13 -- -- -- 
Nonionic of present invention. 
-- 7 -- 7 
(from referential example 1) 
Coconut diethanol amide 
5 -- -- -- 
Amine oxide -- -- 3.3 -- 
Perfume 1 1 1 1 
Water bal. bal. bal. bal. 
______________________________________ 
TABLE 4 
______________________________________ 
Composition 1 2 3 4 
______________________________________ 
No of dishes: 28 33 29 34 
Fat dispersion (*) 
R QG G VG 
______________________________________ 
(*) Key: R regular; QG quite good; G good enough; VG Very good. 
Compositions containing Levenol show good detergency and fat dispersion, by 
permitting a substitution of nitrogen derivatives (alkanol amide and amine 
oxide), thereby avoiding the use of products containing nitrosamines. 
Another advantage of the composition is that due to the reduction in 
irritation of the composition when combined with an anionic surfactant, it 
is possible to substitute betaine. The mixture of nonionic compounds of 
the present invention gives a creamy foam compared to other compositions. 
In order to evaluate the effect on the skin of the mixture of nonionic 
compounds of the present invention, a primary skin irritation test was 
conducted: 
______________________________________ 
COMPOSITION IRRITATION INDEX 
______________________________________ 
EXAMPLE 4. 
1. Sodium lauryl 6.25% 1.88 
sulphate 
2. Sodium lauryl 4.25% 
sulphate 
+ 
Nonionic (1) 2.00% 1.00 
3. Sodium lauryl 4.25% 1.38 
sulphate 
EXAMPLE 5. 
1. Sodium lauryl 4.25% 
sulphate 
Coco imidazoline 
2.00% 1.08 
betaine 
2. Sodium lauryl 4.25% 
sulphate 
+ 
Alkylamide 2.00% 0.96 
propyl betaine 
3. Sodium lauryl 4.25% 
sulphate 
+ 
Nonionic (1) 2.00% 1.00 
______________________________________ 
(1) Represents the nonionic mixture of the present invention from 
referential example 2. 
From the comparison of the above compositions, the mild effect of the 
nonionic of the present invention can be inferred.