ES2353656T3 - THICK - Google Patents

Abstract

A thickener comprising a fatty acid amide ether compound represented by the formula (1): ** (See formula) ** wherein R 1 represents a straight or branched chain alkyl or alkenyl group having 5 to 21 atoms of carbon and may be substituted with at least one hydroxyl group, R2 represents a straight or branched chain alkyl group having 1 to 12 carbon atoms and R3 represents an alkylene group having 2 to 12 carbon atoms.

Description

5

Field of the Invention

The present invention relates to a thickener that has a great thickening effect and a surfactant composition that It includes the thickener.

10

Background of the invention

Detergent compositions are improved by handling characteristics by allowing them to have a viscosity appropriate corresponding to each use or make them have a system

15 appropriately increased in viscosity to maintain dispersibility of water insoluble substances mixed in they. In general, alkanolamide surfactants, betaine type surfactants and semipolar type surfactants

20 (for example, alkyldimethylamine oxides) are known as thickeners and are used in many surfactant applications currently. The alkanolamide surfactants are classified into a monoalkanolamide type and a dialkanolamide type. Although the guy

25 monoalkanolamide has a greater thickening effect, it cannot be say that it is a compound that has great characteristics of I drive because it has a high melting point. On the other hand, the dialcanolamide type has excellent composition stability However, this type is inferior

30 in thickening effect with respect to the monoalkanolamide type and by so much is difficult to obtain a desired viscosity in an amount reasonable.

In this situation, a thickener having a high stability of composition, a great thickening effect, be 35 superior in foaming characteristics and used

preferably for detergent compositions and the like.

Meanwhile, JP-A No. 11-246500 discloses a method of produce an amide compound represented by the formula (I ’) and that this amide compound has high performance as surfactant

image 1

In the formula, R 11 represents an alkyl or alkenyl group linear or branched chain having 7 to 21 atoms of carbon, R12 represents an alkyl or alkenyl chain group linear or branched having 1 to 4 carbon atoms and R13

10 represents a hydrogen atom, an alkyl or alkenyl group linear or branched chain having 1 to 21 atoms of carbon, a straight chain alkyl or alkenyl group or branched that has 1 to 21 carbon atoms, which has two

or less hydroxy groups or alkoxy groups and excluding groups

15 represented by –CH2CH (OH) CH2OR12 or a group represented by - (A’O) n-H (where A ’represents an ethylene group or a group propylene and n represents a number from 1 to 10). However, this reference only discloses that the compound Amide is useful as a foaming agent. In addition, the

20 amide compounds specifically disclosed in the examples described in this reference are all amide compounds tertiary and therefore essentially different from the compound fatty acid amide ether according to the present invention.

Amide ethers of fatty acids are known as thickeners 25 of JP-A-2001 131132, EP-A-176151 and EP-A-1033363.

Compendium of the invention

The present invention is to provide a thickener that It has a great thickening effect and also to provide a 30 surfactant composition containing the thickener.

The inventors of the present invention have done studies serious and, as a result, have found that the addition of a fatty acid amide ether compound specified to various Surfactants produce a great thickening effect and characteristics

5 excellent foaming.

According to this, the present invention provides a thickener. containing a fatty acid amide ether compound (of hereinafter referred to as "compound 1") and also provides a surfactant composition containing the thickener and at

10 minus a surfactant:

image2

wherein R1 represents an alkyl or chain alkenyl group linear or branched that has 5 to 21 carbon atoms and may be substituted with at least one hydroxyl group, R2

15 represents a straight or branched chain alkyl group that it has 1 to 12 carbon atoms and R3 represents a group alkylene having 2 to 12 carbon atoms.

In particular, the present invention provides a thickener containing an acid amide ether compound 20 fatty represented by the formula (1-1) or (1-2):

image2

where R1 and R2 have the same meanings as above, respectively. In addition, the present invention provides a method of thicken a surfactant by mixing the amide ether compound of

5 fatty acids above with the surfactant and a use for the anterior fatty acid amide ether compound as thickener

Detailed description of the invention

In the compound (1) used in the present invention, R1 represents a straight chain alkyl or alkenyl group or branched that has 5 to 21 carbon atoms and that can be substituted with at least one hydroxyl group and is preferably a group having 7 to 17 carbon atoms.

15 Specific examples of the alkyl or alkenyl group include residues obtained by removing a carboxyl group of acids fatty such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, 12-hydroxystearic acid and acid

20 isostearic. R2 represents an alkyl group having 1 to 12 atoms carbon Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, 2-ethylhexyl group, octyl group,

25 dodecyl group and the like and preferable examples are groups alkyl having 1 to 8 carbon atoms. R3 represents an alkylene group having 2 to 12 atoms carbon Specific examples of the alkylene group include an ethylene group, propylene group, isopropylene group,

30 butylene group, hexylene group, 2-ethylhexylene group, group octylene, dodecylene group and the like. The alkylene group is preferably alkylene groups having 2 to 8 atoms of carbon, more preferably alkylene groups having 2 or 3 carbon atoms and even more preferably alkylene groups

35 which have 3 carbon atoms.

Among the compounds (1), the amide ether compounds of fatty acids represented by the formula (1-1) above and the formula (1-2) above are particularly superior as the thickener

The compound (1) of the present invention can be produced

by reacting a higher fatty acid represented by the

formula (2):

image2

[where R1 has the same meaning as before and R4

10 represents an alkoxy group having 1 to 3 carbon atoms, a group represented by the formula: -CH2CH (OY) -CH2 (OZ) (where Y and Z represent, independently of each other, an atom of hydrogen, a linear or branched chain acyl group that it has 6 to 22 carbon atoms and that can be substituted

15 with at least one hydroxyl group) or a halogen atom] or its derivative (hereinafter referred to as "acid component fatty (2) ”) with an alkoxyamine (hereinafter referred to as as "amine (3)" represented by formula (3):

image3

where R2 and R3 have the same meanings as above, respectively. Examples of the fatty acid component (2) used in the Production of compound (1) include fatty acids such as

25 caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, acid ricinoleic, 12-hydroxystearic acid and isostearic acid; alkyl esters of these fatty acids, for example esters methyl and ethyl esters; glycerides of these fatty acids,

30 for example, natural oils and fats such as coconut, palm oil, palm kernel oil; and halides (by

example, chlorides and bromides) of these fatty acids. Between these components of fatty acids (2), fatty acids, esters fatty acid alkyl and fatty acid glycerides are particularly preferable because they are not accompanied by the

5 production of inorganic salts.

Examples of the amine (3) include 3-methoxypropylamine, 3-ethoxypropylamine, 3-isopropyloxypropylamine, 3-propyloxypropylamine, 3- (2-ethylhexyloxy) -propylamine, 2-methoxyisopropylamine and the like.

10 The reaction between the fatty acid component (2) and the amine (3) can be run under reaction conditions in general known and proceeds in the presence of a catalyst using a alcoholate and the like or also in the absence of a catalyst. For example, regarding the reaction temperature between

15 an alkyl ester of fatty acid, coconut oil or oil palm kernel and the amine (3), the reaction proceeds at a range of temperature from 50 to 130 ° C in the case of using methylate sodium as a catalyst and at a temperature range from 130 at 220 ° C in the case of not using catalyst. In addition, when used

20 a fatty acid as a starting material, the reaction proceeds to a reaction temperature of 120 to 220 ° C. In addition, a fatty acid halide can be reacted with the amine (3) using a known method. In this regard, for example, a reaction between fatty acid chloride and the amine

25 (3), the amine (3) is charged into an aqueous solution system in presence of an organic solvent or in a solution system aqueous and the fatty acid chloride and a alkali to the aqueous solution system simultaneously while controlling the pH of the system from 7 to 12 to run a

30 reaction at a reaction temperature of -20 to 50 ° C. The Examples of the organic solvent in this case include acetone, isopropyl alcohol, diethyl ether and the like. The examples Alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and the like.

35 The molar ratio ((2) :( 3)) of the fatty acid component

(2) to the amine (3) is in a range preferably from

1: 1 to 1: 1.3 and more preferably from 1: 1 to 1: 1.1 when the fatty acid component (2) is a compound Different from fatty acids. It is preferably in an interval from 1: 3.0 to 1: 3.9 and more preferably from 1: 3.0 to

5 1: 3.3 when the fatty acid component (2) is a fatty acid from the point of view of reactivity and from a point of view economic.

The compound (1) of the present invention obtained after if the reaction is over it may contain unreacted products 10 and by-products up to a level that these products avoid using

real of the compound of formula (1).

The compound (1) of the present invention can increase the viscosity of the composition of compounds in combination with a surfactant and is therefore useful as a thickener for these

15 compositions In addition, the compound (1) has the effect of improve foaming property. Examples of the surfactant include surfactants anionic, amphoteric surfactants, cationic surfactants, nonionic surfactants, semipolar surfactants, and the like

20 (for example, alkyldimethylamine oxides). You get one significant thickening action particularly in a system of anionic surfactant.

Examples of the anionic surfactant used herein invention include alkyl sulfates, alkyl ether sulfates 25 polyoxyethylene, alkylbenzene sulphonates, alkyl salts of fatty acids, alkyl phosphates, acylated salts of amino acids, alkylamide ether sulfates and the like. The alkyl groups of these anionic surfactants are preferably those having 5 to 30 carbon atoms and 30 more preferably those having 8 to 18 carbon atoms and the acyl groups of these surfactants are preferably those that have 6 to 31 carbon atoms and more preferably those having 7 to 17 carbon atoms. The Examples of salt include alkali metal salts, salts of

35 ammonium, alkyl or alkenylamine salts having in total 1 to 22 carbon atoms, alkanolamine salts that you have in

total of 1 to 22 carbon atoms and amino acid salts basic. The salt is preferably alkali metal salts and more preferably sodium salts and potassium salts.

In the surfactant composition containing the compound

5 (1) and a surfactant according to the present invention, the content of the compound (1) is preferably 0.1 to 50% by weight and more preferably 0.5 to 20% by weight. In addition, the content of the surfactant is preferably 0.5 to 90% by weight and more preferably from 1 to 50% by weight.

The compound (1) of the present invention can be formulated in detergents, cosmetics and the like. The proportion of compound (1) to be formulated in these detergents or cosmetics it is preferably 0.1 to 50% by weight and more preferably 0.5 to 20% by weight in these detergents or cosmetics although

15 no particular limitation is imposed on the proportion. In addition, a two component system containing the compound (1) and various surfactants or the compound (1) to a combination of these various surfactants after use according to the use of detergent.

twenty

Brief description of the figures

Figure 1 is an infrared absorption spectrum of a fatty acid amide ether compound obtained in the example of synthesis 1; Y

25 Figure 2 is an infrared absorption spectrum of a fatty acid amide ether compound obtained in the example of synthesis 7.

Examples

30 In the synthesis examples, the value of saponification (VS) and the total amine value in the following methods

<Saponification value>

35 A known amount of 0.5 N KOH (added in an amount in excess of 50 to 60% to the sample) at a

known quantity of the sample to holder the sample using 0.2 N HCl in an automatic potentiometric titrator (AT-310J, manufactured by Kyoto Denshi (sha)) and then the saponification value (VS) according to the following equation.

5 VS = (11.22 x HCl factor 0.2 N x titer (cc) *) / Sample (g) *: 0.2 N HCl title required from the inflection point of first phase to the point of inflection of the second phase.

10 <Total Amine Value> A known amount of the sample was poured into a solution of ethanol to which BCG indicator (green of bromocresol) to titrate the sample until the color in the system changed from green to yellow to determine the value

15 total amine according to the following equation.

Total amine value = (11.22 x 0.2 N HCl factor x titer (cc)) / sample (g)

20 Synthesis Example 1 (Synthesis of amidopropyl methyl ether of coconut oil fatty acid) A 1 L reaction container equipped with a thermometer, a agitator, a tube for bubbling nitrogen and a condenser of reflux was charged with 217 g (Pm: 657.5, 0.33 mol) of oil

Coconut and 97 g (Pm: 89.1, 1.09 mol) of 3-methoxypropylamine. The mixture was raised to 95 ° C while nitrogen is bubbled in the container and 5 g of sodium methylate was added to the mixture 28% After that, the resulting mixture was maintained as I was for 3 hours. The termination of the reaction is

30 confirmed by determining, using gas chromatography, that the amount of residual coconut oil was less than 3%. The excess of amine was distilled under reduced pressure.

The VS (saponification value) and the total amine value of amidopropyl methyl ether of coconut oil fatty acid 35 resulting were 5.7 and 6.0, respectively. A infrared absorption spectrum as shown in figure 1.

Synthesis Example 2 (Synthesis of amidopropyl methyl ether of lauric acid)

The same reaction container that was used in the example of

5 synthesis 1 was loaded with 214 g (Pm: 214, 1 mol) of laurate of methyl and 98 g (1.1 mol) of 3-methoxypropylamine. The mixture is rose to 95 ° C while nitrogen is bubbling in the container and added to the mixture 5 g of 28% sodium methylate while nitrogen is bubbled into the container. After that, the mixture

The resulting 10 remained as it was for 3 hours. The termination of the reaction was confirmed by determining, using gas chromatography, that the residual methyl laurate was less than 3% and excess amine was distilled under reduced pressure.

15 Synthesis Example 3 (Synthesis of amidopropyl methyl ether of palm kernel fatty acid) The same reaction container that was used in the example of Synthesis 1 was loaded with 226.4 g (Pm: 686.0, 0.33 mol) of oil of palm kernel and 97 g (1.09 mol) of 3-methoxypropylamine. The

The mixture was raised to 95 ° C while nitrogen is bubbled in the container and 5 g of sodium methylate was added to the mixture 28% After that, the resulting mixture was maintained as I was for 3 hours. The termination of the reaction is confirmed by determining, using gas chromatography, that the

25 residual palm kernel oil was less than 3% and the excess of amine was distilled under reduced pressure.

Synthesis Example 4 (Synthesis of propyl ethyl ether of amide lauric acid)

The same reaction container that was used in the example of Synthesis 1 was loaded with 214 g (1 mol) of methyl laurate and 113.5 g (Pm: 103.2, 1.1 mol) of 3-ethoxypropylamine. Mix it was raised to 95 ° C while nitrogen is bubbled into the container and 5 g of 28% sodium methylate were added to the mixture. After

35 of this, the resulting mixture remained as it was for 3 hours. The termination of the reaction was confirmed by determining,

using gas chromatography, that residual methyl laurate it was less than 3% and excess amine was distilled under pressure reduced

5 Synthesis example 5 (Synthesis of amidopropyl 2-ethylhexyl ether lauric acid)

The same reaction container that was used in the example of Synthesis 1 was loaded with 214 g (1 mol) of methyl laurate and 206 g (Pm: 187.3, 1.1 moles) of 3- (2-ethylhexyloxy) propylamine. The

The mixture was raised to 95 ° C while nitrogen is bubbled into the container and 5 g of sodium methylate was added to the mixture 28% After that, the resulting mixture was maintained as I was for 3 hours. The termination of the reaction is confirmed by determining, using gas chromatography, the laurate

15 residual methyl was less than 3% and the excess amine was distilled under reduced pressure.

Synthesis Example 6 (Synthesis of amidopropyl isopropyl ether of coconut fatty acid)

The same reaction container that was used in the example of Synthesis 1 was loaded with 217 g (0.33 mol) of coconut oil and 127.5 g (Pm: 117.1, 1.09 mol) of 3-isopropyloxypropylamine. The mixture was raised to 95 ° C while nitrogen is bubbled in the container and 5 g of sodium methylate was added to the mixture

25 28%. After that, the resulting mixture was maintained as I was for 3 hours. The termination of the reaction is confirmed by determining, using gas chromatography, that the residual coconut oil was less than 3% and excess amine was distilled under reduced pressure.

30 Synthesis example 7 (Synthesis of amidoisopropyl methyl ether of lauric acid)

The same reaction container that was used in the example of Synthesis 1 was loaded with 200 g (1 mol) of lauric acid and 98 g 35 (Pm: 89.1, 1.1 mol) of 2-methoxyisopropylamine. The mixture is rose to 165 ° C for 2 hours while nitrogen is bubbling in

the container After that, the mixture was aged for 2 hours. Then, 30 g of 2-methoxyisopropylamine were added dropwise over 30 minutes and the resulting mixture It remained as it was for 3 hours. The termination of the

5 reaction was confirmed by determining, using chromatography of gases, residual lauric acid was less than 3% and the excess of amine was distilled under reduced pressure.

The VS (saponification value) and the total amine value of the resulting lauric acid amidoisopropyl methyl ether were 10 8.0 and 4.0, respectively and a spectrum of

infrared absorption as shown in figure 2.

Synthesis Example 8 (Synthesis of amidopropyl isopropyl ether of palm kernel fatty acid)

15 The same reaction pack that was used in the example of Synthesis 1 was loaded with 226.4 g (0.33 mol) of oil palm kernel and 97 g (1.09 mol) of 3-isopropyloxypropylamine. The mixture was raised to 95 ° C while nitrogen is bubbled in the container and 5 g of sodium methylate was added to the mixture

20 28%. After that, the resulting mixture was maintained as I was for 3 hours. The termination of the reaction is confirmed by determining, using gas chromatography, that the residual palm kernel oil was less than 3% and the excess of amine was distilled under reduced pressure.

25 Synthesis Example 9 (Synthesis of amidopropyl isopropyl ether of lauric acid)

The same reaction container that was used in the example of Synthesis 1 was loaded with 214 g (1 mol) of methyl laurate and 129 30 g (1.10 mol) of 3-isopropyloxypropylamine. The mix went up at 95 ° C while nitrogen is bubbling in the container and They added 5 g of 28% sodium methylate. After that, the Mix remained as it was for 3 hours. The termination of the reaction was confirmed by determining, using chromatography of

35 gases, that the residual methyl laurate was less than 3% and the excess amine was distilled under reduced pressure.

Synthesis Example 10 (Synthesis of amidopropyl propyl ether of coconut oil fatty acid)

The same reaction container that was used in the example of

5 synthesis 1 was loaded with 217 g (0.33 mol) of coconut oil and 127.5 g (Pm: 117.1, 1.09 mol) of 3-propyloxypropylamine. The mixture was raised to 95 ° C while nitrogen is bubbled in the container and 5 g of 28% sodium methylate were added. After Of this, the mixture remained as it was for 3 hours. The

Reaction termination was confirmed by determining, using gas chromatography, that residual coconut oil was lower 3% and excess amine was distilled under reduced pressure. It should be noted that in synthesis examples 2 to 10, confirmed that each compound was a target compound from

15 measures the saponification value and the total value of amine and infrared absorption spectrum in the same way than in the synthesis example 1.

Example 1

The viscosity of an aqueous solution obtained was determined by formulating each of the ether compounds of fatty acid amide obtained in synthesis examples 1 to 10 or a thickener selected from the comparative compounds a the concentration shown in table 1 in a sulfate of

25 polyoxyethylene lauryl ether (average number of moles added of OE = 2) sodium in the following condition. In addition, the melting point of each thickener according to a method of hair warming The results are shown in Table 1.

30 <Viscosity measurement condition> Total concentration of thickener and surfactant: 20% in weight. Measuring pH: 7.0 Measuring temperature: 25ºC

35 Viscometer: type B viscometer.

Table 1

Thickener

Viscosity (mPa · s) Melting point (ºC)

Mixed amount * (% by weight)

0

one 3 5

Product of the invention

Fatty acid amide ether compound of synthesis example 1 8 33 950 21000 52

Fatty acid amide ether compound of synthesis example 2

8 25 250 6500 30

Fatty acid amide ether compound of synthesis example 3

8 30 520 11000 33

Fatty acid amide ether compound of synthesis example 4

8 Four. Five 1900 20000 47

Fatty acid amide ether compound of synthesis example 5

8 31 290 18500 43

Fatty acid amide ether compound of synthesis example 6

8 31 1100 7800 twenty-one

Fatty acid amide ether compound of synthesis example 7

8 27 1050 11500 43

Fatty acid amide ether compound of synthesis example 8

8 30 1250 18500 twenty-one

Fatty acid amide ether compound of synthesis example 9

8 31 750 12000 41

Fatty acid amide ether compound of synthesis example 10

8 28 470 5500 29

Comparative Product

Lauryl Acid Diethanolamine 8 twenty 156 3600 -

Coconut fatty acid monoethanolamine

8 35 1500 13000 70

Lauric acid monoethanolamine

8 38 1800 cloudy, shady 90

*: Concentration of each thickener in the aqueous solution.

Example 2 (Evaluation of surface activity)

5 0.5 g of rapeseed oil and 1.0 g of each were placed of the fatty acid amide ether compounds obtained in Synthesis examples 1 to 10 in a flask loaded with 50 g of ion exchange water and stirred by a mixer manual for one minute. Then the mixture was allowed to stand.

10 for 10 minutes and the state was visually observed

Rapeseed oil emulsified to evaluate according to the following standards: <Evaluation Standard>

x: Separated

image2 : cloudy and scattered

Table 2

Emulsification status

Fatty acid amide ether compound of synthesis example 1

image2

Fatty acid amide ether compound of synthesis example 2

image2

Fatty acid amide ether compound of synthesis example 3

image2

Fatty acid amide ether compound of synthesis example 4

image2

Fatty acid amide ether compound of synthesis example 5

image2

Fatty acid amide ether compound of synthesis example 6

image2

Fatty acid amide ether compound of synthesis example 7

image2

Fatty acid amide ether compound of synthesis example 8

image2

Fatty acid amide ether compound of synthesis example 9

image2

Fatty acid amide ether compound of synthesis example 10

image2

It is confirmed from table 2 that all compounds

obtained in the synthesis examples had activity

superficial.

Claims (5)

1. A thickener comprising an amide ether compound of fatty acid represented by the formula (1): image 1

where

R1 represents an alkyl or alkenyl group of

linear or branched chain that has 5 to 21 atoms of

carbon and can be substituted with at least one group

hydroxyl, R2 represents a straight chain alkyl group or

10

branched that has 1 to 12 carbon atoms and R3

represents an alkylene group having 2 to 12 atoms of

carbon.

2.

A thickener comprising an amide ether compound of

fifteen

fatty acid represented by the formula (1-1):

image2 where R1 and R2 have the same meanings as above, respectively. A thickener comprising an amide ether compound of fatty acid represented by the formula (1-2): image2 where R1 and R2 have the same meanings as above, respectively. 4. A surfactant composition comprising the thickener as it is claimed in any one of claims 1 to 3 and at least one surfactant. 5 5. The surfactant composition according to claim 4, in where the surfactant is an anionic surfactant. 6. Use of the fatty acid amide ether compound represented 10 by the formula (1) as a thickener: image2

where R1

It represents a alkyl group or alkenyl from

linear or branched chain that has 5 to 21 atoms of

carbon and can

to be replaced with to the less a group

fifteen

hydroxyl, R2 represents a straight chain alkyl group or

branched that has 1 to 12 carbon atoms and R3

represents an alkylene group having 2 to 12 atoms of

carbon.

twenty

7. A method of thickening a surfactant by mixing the compound

fatty acid amide ether represented by the formula (1)

with the surfactant

image2 wherein R1 represents an alkyl or chain alkenyl group 25 linear or branched having 5 to 21 carbon atoms and may be substituted with at least one hydroxyl group, R2 represents a straight or branched chain alkyl group that it has 1 to 12 carbon atoms and R3 represents a group alkylene having 2 to 12 carbon atoms.