ES2088254T5 - DETERGENT COMPOUND AND METHOD FOR MANUFACTURING. - Google Patents

Abstract

Detergent composition comprising the compounds represented by the formula (I) + (II) wherein the weight ratio of mono, di and tri-ester is 46-90/9-30/1-15, <CHEM> wherein: - "B" represents "H" or the group represented by <CHEM> provided that R represents alkyl or alkenyl group having C6-22. R' represents H or CH3, and each of n, m and 1 independently represents an integer from 0 to 40; being m+n+1=2-100 preferebly 9-19. The new detergent composition shows outstanding biodegradable, non-toxic, non-irritant performance, foam stability and better dye inhibition transfer maintaining and even improving detergency.

Description

Detergent compound and method for its manufacturing.

Sector of the technique to which the invention belongs

The present invention relates to new biodegradable, non-toxic and liquid detergent compounds non-irritating, improving its detergent character, stability of the foam and color protection in case of detergents for service Heavy and for light duty. These detergent compounds are particularly useful for the formulation of shampoos, shampoos Body products, washing products, cleaning products general use and detergents of the types called for Heavy duty and light duty.

Actually, the present invention relates to formulations for cleaning products comprising a compound No specific ionic.

In addition to this, the present invention relates to a method for the preparation of the non-ionic compound previously mentioned.

Description of priorities

Most detergent compounds have a combination of anionic, amphoteric and / or surfactants non-ionic, to get better properties according to the final product in terms of irritation, detergent and foam behavior.

One of the current problems in the field of Chemicals is the issue of ecotoxicity and duality cleaning / damage, that is, how to get a good performance without serious interaction with the surface to which it apply (tissues or human skin).

The nonionic agents used conventionally in detergents have been nonylphenols ethoxylated, C 12-18 alcohols ethoxylated with about 12 moles of ethylene oxide and lately alcohols C 12-15 ethoxylates with 2 to 9 moles of oxide ethylene and EO / OP derivatives.

For example:

The published Japanese application No. 55-86894 discloses the use of alcohols C_ {6-14} secondary ethoxylates with 4-15 moles of ethylene oxide on average.

The published Japanese application No. 52-22007 and published Japanese Patent No. 83037356 disclose the use of an ethoxylated intermediate alcohol of formula R 1 O (C 2 H 4 O) nH, in which R 1 it is a straight or branched chain alkyl radical and n has value 1-12 on average in detergent compounds.

European Patent No. 80749 discloses the use of alkyl ethoxylated phenols in compounds detergents

US Patent 4908150 discloses the use of polyethylene glycol ether of a glycerol compound ester.

Published Japanese Patent No. 55-133495 discloses the use of an oil of castor hardened with polyoxyethylene or a fatty acid ester thereof, a fatty acid ester of polyoxyethylene glyceryl ether, a polyoxyethylene trimethylol propane fatty acid ester and a polyoxyethylene alkyl ether diester N-lauroylglutamic, etc., in compounds detergents

However, the use of these agents does not ionic deteriorates the detergency capacity of the compound Detergent. Also, in the case of liquid detergents of type called heavy and light it tends to cause transfer of color, especially after repeated washing. In addition to what previously mentioned, it should be noted that non-ionic agents current cause skin and eye irritation and present also toxicity to fish, immobilization of marine plants such as oleanders and algae, not being acceptable given the current environmental requirements.

Other patents disclose the use of specific non-ionic compounds other than usual, in applications and / or particular conditions.

US Patent 4247425 discloses the use of glycerol alkoxylated partial esters of an acid Detergent grade grease in type detergent compounds light.

European Patent 0007120 discloses a emulsification system to be used in a compound for washing hands consisting essentially of mono and diglycerides of acids higher natural fatty acids and ethoxylated glycerin esterified by fatty acids.

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US Patent 4897214 discloses the use of fatty acid monoesters with derivatives of polyoxyethylene hexitan in skin cleansing preparations.

WO 92/00945 discloses the use of octadienyl glycerin ethers with polyoxyethylene

English Patent 2197338 discloses the use of polyoxyalkyl alkyl- or alkenyl ethers and esters of polyoxyalkylene glycerol fatty acid in compounds detergents

In none of the patents above a non-ionic agent of the type that is mentioned is disclosed described in the present invention.

The inventors have carried out investigations about the development of a detergent compound that shows extraordinary characteristics of biodegradation, lack of toxicity and absence of irritating character, foam stability and better inhibition in color transfer, keeping e even improving the detergent character.

It has been discovered that the demands mentioned above can be met when the non-ionic compound specified in the detergent compound.

This discovery has led to the present invention.

Accordingly, the present invention will be refers to detergent compounds comprising the compounds mono-, di- and triester represented by the formula (I), in which the proportion of mono-di-tri-ester is from 46-90 / 9-30 / 1-15

5

in the that:

-

"B" represents "H" or the group represented by

\uelm{C}{\uelm{\dpara}{O}}

--- R---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- R

whenever R represent a C 6-22 alkyl or alkenyl group. It should be borne in mind that at least one of "B" is a group ester.

-

"n", "m" and "l" can have a value between 0 and 40 provided that (n + m + l) = 2 - 100, preferably 9-19.

-

R ' represents H or CH 3 respectively and the compound represented by the formula (II)

6

in the that:

-

"n", "m" and "l" can have a value between 0 and 40 provided that (n + m + l) = 2 - 100 preferably 9-19.

-

R ' represents H or CH 3 respectively.

Being the high content of the monoester ethoxylated compound (I) and proportion (I) / (II) parameters key to get the aforementioned properties.

The proportion (I) / (II) can have a value between 3 and 0.33, preferably between 1.3 and 0.75.

The mixture compound of the formula (I) + (II) of The present invention can be obtained by conventional methods of preparation.

For example, the compound can be obtained by The next reaction process.

(TO)

Intersterification reaction between triglycerides and glycerin, 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 oxide of C_ {2-3} alkylene or vice versa will lead to a mixing ratio of mono-, di- and triglycerides (I) and (I) / (II) of specific composition and structure due to phenomena of emigration and exchange, with an HLB greater than 2.

(B)

The reaction of glycerin with alkylene oxide C 2-3 in the presence of alkaline catalysts and the latter's reaction with fatty acids in a molar ratio from 0.1-10 / 1, preferably 0.7-3.5 / 1 in the presence of acid catalysts or alkaline will lead to a mixture of mono-, di- and triglycerides of a specific composition and structure, due to phenomena of emigration and exchange, with an HLB greater than 2.

The triglycerides that can be used in the process (A) comprise natural fats and oils as well as a synthetic triglyceride

Fats and oils comprise vegetable oils such as coconut oil, palm oil, soybean oil and fats and animal oils such as beef tallow, bone oil, fats and aquatic animal oils, hardened oils and semi-hardened of them.

In the present invention, the compound of formula (I) + (II) can be incorporated in an amount between 0.2% and 40%, preferably 3% to 20% by weight, based on the Total detergent compound.

The reason why the present invention shows the extraordinary biodegradable character, non-toxic and not irritating, without deteriorating its detergent character is not good known, but the applicant believes that the good performance of current compounds comes partially from the fact that the existence of fatty acid groups facilitates their biodegradability and its very reduced character in terms of skin irritation, oral toxicity, toxicity to fish, immobilization of algae and oleanders compared to non-ionic agents conventional.

In addition, the incorporation of the new formula non-ionic agent described in the patent considerably improves the foam behavior, anti-transfer characteristics of color and solubilization of perfumes compared to conventional formulations, due to the high proportion of ethoxylated monoglyceride and the synergistic effect between (I) and (II).

Surfactants such as anionic, other nonionic, amphoteric, etc. and the rest of additive useful in the practice of the present invention are highly dependent part of the type of the final product to be formulated. The same time is a standard element in commerce so that it is not will comment further.

Examples

The present invention is described more fully. detailed based on the following examples. However, the The present invention is not limited thereto.

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Reference Example one

The mixing compound ((I) + (II)) is obtained, for example, by the following process:

Phase (C)

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one

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Phase (d)

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2

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in the that:

- "B" represents "H" or the group represented by

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\uelm{C}{\uelm{\dpara}{O}}

--- R---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- R

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and l + m + n = fifteen.

- "R" represents a coconut chain I rent.

- The proportion (I) / (II) has a value of 1.

500 g (0.76 mol) of TRG coconut, 210.7 g (2.29 moles) of 99% glycerin and 1.2 g of 85% KOH as catalyst placed in a 3 kg container properly equipped. He system is purged several times with N2, extracting in vacuum up to 110 ° C and continuing heating to 140 ° C. When the temperature reaches 140 ° C the reactor is subjected to pressure at 2-3 kg / cm2 with ethylene oxide addition up to a total of 2013 grams (45.7 moles).

After the final loading of ethylene oxide, the reaction mixture is allowed to react for half an hour, it cooled and discharged from the reactor. A product ((I) + (II) is obtained ).

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Reference Example 2

The mixture compound ((I) + (II)) is obtained for example through the following process:

Phase (and)

3

Phase (F)

4

in the that:

"B" represents "H" or the group represented by

\uelm{C}{\uelm{\dpara}{O}}

--- R---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- R

and l + m + n = 10.

R 'represents CH 3.

R means an alkyl tallow chain.

Proportion (I) / (II) = 1.3.

14.3 g (0.1554 mol) of 99% glycerin and 1.2 g of 85% KOH as catalyst are placed in a 250 gram bottle properly equipped. The system is purged several times with N2, vacuum extraction up to 110 ° C and continuing the heating up to 140 ° C. When the temperature reaches 140 ° C, the reactor is subjected to pressure at 2-3 kg / cm2 with ethylene oxide additive up to a total of 67.9 grams (1.54 moles) After the final loading of ethylene oxide, the mixture of reaction is allowed to react for about half an hour; be add 52.3 grams (0.15 moles) of fatty acid methyl ester tallow derivative and mixed for 45 minutes. Finally the product is cooled and discharged from the reactor. This way you get the mixture compound of formula (I) + (II).

Example 1 HDPD

Compound Subjects cousins one 2 3 4 5 6 Dodecil benzene sulfonate Na 10 10 10 10 10 10 Alcohol C_ {15-15} ethoxylated (7) 9 - - 6 - - 9 - - Agent nonionic of the present invention - - 9 - - 6 - - 9 (of the reference example 2) Acid fatty of coconut - - - - 2 2 - - - - Silicone 0.2 0.2 0.1 0.1 0.2 0.2 Ceolite 35 35 - - - - 35 35 STPP - - - - 35 35 - - - - Polycarboxylate 5 5 5 5 5 5 CMC 1.5 1.5 1.5 1.5 1.5 1.5 Perborate monkey hydrous fifteen fifteen 13 13 fifteen fifteen Carbonate Na 12 12 fifteen fifteen 12 12 Silicate Na 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 Sulfate sodium B. B. B. B. B. B. Fragrance one one one one one one Note: B means rest.

Detergency assessment test

Washing machine:

Temperature: 30ºC and 60ºC.

Dosage: 6 gr / l

Water hardness: 2 mmol / L Ca 2+ and 4 mmol / L Ca 2+ (20ºHF and 40ºHF).

Washing load: 2 kg of clothes Polyester cotton without dirt and EMPA 101,104,117 + especially dirty.

Without prewash program.

The detergent capacity was evaluated in the detergent compounds listed in table 1.

Considered all the variables, that is, the temperature, water hardness and type of dirt the non-ionic agent described in this patent shows in the worst case a equivalent effectiveness in terms of detergency.

However, on the other hand, the compounds that contain the nonionic agent of the present invention provide better color care than usual ethoxylated alcohol.

The following test has been carried out at 30 ° C

1.- Use of a reactive dye

After 15 washes, differences appear in terms of color transfer.

The color transfer is evaluated by measuring delta values E (L2 + a2 + b2) 1/2 through Hunter-Lab. The discoloration resulting from The tissues are indicated in the following table:

TABLE 1

Compounds blue Green Red one 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

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When smaller is delta E, the better the composition in terms of preventing color transfer. For the both the conclusion of the previous results can be reached that the nonionic agent of the present invention behaves better than ethoxylated alcohol preventing color transfer. further it is possible to save a certain amount of polyvinylpyrrolidone (typical transfer transfer inhibitor agent color). The specific amount to be saved will depend on the effect of other components, that is, the design or concrete form of the formulation. The applicant believes that there is a synergistic effect between the non-ionic agent of the present invention and PVP.

2.- Use of a direct dye

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References: Yellow: Solar Yellow 3LG 160% Blue: Solar Blue 2GLN 350% Formulations: blue Green Yellow Solar Blue 2GLN 350% one% one% - - Yellow Solar 3LG 160% - - one% one% SO_ {4} Na_ {2} 20 g / l 20 g / l twenty g / l Sandofix R 3% 3% 3%

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After 3 washes, differences appeared in terms of color transfer.

The color transfer was evaluated by measuring the delta values E (L2 + a2 + b2) 1/2 per Hunter-Lab The resulting discoloration of Tissues are shown in the following table:

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TABLE 2

Compound blue Green Yellow one 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

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These test results 1 and 2 were checked using a panel consisting of 5 people who evaluated The results according to a scale.

Example 2 HDL

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Compounds Subjects cousins one 2 3 4 Lauryl sulfate Na - - - - 4 4 Dodecil benzene sulfonate Na 10 10 5 5 Alcohol C_ {15-15} ethoxylated (7) - - 5 - - fifteen Agent nonionic of the present invention 5 - - fifteen - - (of the reference example 2) Soap potassium of coconut 5 5 10 10 Ethanol - - - - 3 3 Propylene glycol 7 7 7 7 Fragrance one one one one Enzyme 0.7 0.7 0.5 0.5 Formate Na one one one one Phosphonate Na 0.8 0.8 0.8 0.8 TORCH 85% Req. Req. Req. Req. NaOH fifty% Req. Req. Req. Req. Cl_ {Ca} one% 2 2 2 2 Water B. B. B. B. Note: B means rest. Req. it means required quantity.

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Following the same test conditions as have explained previously for HDPD, (adapting the dosage of according to the composition), the following were obtained results:

-

Detergency good enough in all cases.

-

The appearance results in color are shown in the table 3.

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TABLE 3

Compounds blue Green Red one 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

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Simply put, the compounds they contain the nonionic agent of the present invention better prevent the color transfer even in HDL, the ph being neutral and not using optical brighteners. (It should be noted that the HDL were used as detergents to save the color before the new segment of H.D.P.D. to save the color).

Example 3 Washed

Compounds Subjects cousins one 2 3 4 Lauryl sulfate ether Na 10 10 7 7 Alpha olefin sulphonate Na - - - - 4 4 Rent propyl amido betaine 5.3 4,5 5.7 2.5 Alcohol C_ {15-15} ethoxylated (7) 13 - - - - - - Agent nonionic of the present invention - - 7 - - 7 (of the reference example one) Dietanol amide of coconut 5 - - - - - - Oxide amine - - - - 3.3 - - Fragrance one one one one Water Rest Rest Rest Rest

TABLE 4

Compound one 2 3 4 No. from dishes: 28 33 29 3. 4 Dispersion of fat (*) R QG G VG (*) Key: R regular; QG quite good; G good enough; VG very good.

Compounds containing Levenol® show a better detergent and fat dispersion character, allowing the suppression of nitrogen derivatives (alkanol amide and amine oxide) and also the complete substitution of ethoxylated alcohol. Another point Basic consists in the partial substitution of betaine. The agent Non-ionic of the present invention also provides a foam Creamy compared to other compounds.

To check the effect on the skin of the agent no ionic of the present invention a primary test was carried out Skin irritation:

Example 4

Compound Index of irritation one.- Lauryl sulfate sodium 6.25% 1.88 2.- Lauryl sodium sulfate 4.25% + No ionic (one) 2.00% 1.00 3.- Lauryl sodium sulfate 4.25% 1.38

Example 5

Compound Index of irritation one.- Lauryl sulfate sodium 4.25% + Imidazoline betaine from coconut 2.00% 1.08 2.- Lauryl sulfate sodium 4.25% + Propil betaine alkylamine 2.00% 0.96 3.- Lauryl sodium sulfate 4.25% + No ionic (1) 2.00% 1.00 (1) Represents the non-ionic agent of the present invention from the reference example 2.

By comparison of the above compounds you can conclude the mild effect of agent no ionic of the present invention.

Claims (4)

1. Detergent compound comprising mono, di and triester compounds represented by formula (I) in the weight ratio of mono, di and tri-ester is of 46-90 / 9-30 / 1-15 5 in the that: - "B" represents "H" or the group represented by ---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- R with the proviso that R represent an alkyl or alkenyl group with C_ {6-22}. R 'represents H or CH 3 and each of n, m and l independently represent an integer between 0 and 40; where n + m + l = 2-100, preferably 9 - 19, and by the compound represented by the formula (II) 6 in the that:

-

"n", "m" and "l" have a value between 0 and 40 with the proviso that (n + m + l) = 2 - 100 preferably 9-19.

-

R ' represents H or CH 3 respectively,

in which the weight ratio (I) / (II) has a value between 3 and 0.33.

2. Detergent compound according to claim 1, in which the proportion (I) / (II) has an included value between 1.3 and 0.75. 3. Method for the preparation of a compound detergent according to claim 1, using the following stages (a) and (b):

(to)

the mixture of triglyceride and glycerin is subjected to a reaction of intersterification,

(b)

the reaction mixture obtained in step (a) is subjected to alkoxylation using alkylene oxide having C 2-3 in the presence of an alkaline catalyst to produce the compounds represented by the general formula (I) + (II).

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4. Method for the preparation of a compound detergent according to claim 1, using the following stages (c) and (d).

(C)

be prepare the mixture of glycerin and alkylene oxide C 2-3, in the presence of catalysts alkaline,

(d)

the reaction mixture obtained in step (c) is reacted with methyl ester of fatty acid or with fatty acid.