CN115368978B

CN115368978B - Concentrated detergent with high-power dilution and thickening performance and preparation method thereof

Info

Publication number: CN115368978B
Application number: CN202210776954.6A
Authority: CN
Inventors: 郭宁; 屠吉利; 刘�英; 邱金丹; 张蕾
Original assignee: Nice Zhejiang Technology Co ltd; Nice Group Co Ltd
Current assignee: Nice Zhejiang Technology Co ltd; Nice Group Co Ltd
Priority date: 2022-06-30
Filing date: 2022-06-30
Publication date: 2023-09-12
Anticipated expiration: 2042-06-30
Also published as: CN115368978A

Abstract

The invention relates to the field of detergents, and discloses a concentrated detergent with high dilution and thickening properties and a preparation method thereof, wherein the concentrated detergent comprises 40-70wt% of active substances and water; the actives include the following components, based on the total weight of the concentrated detergent: 10-20wt% of alkanolamide surfactant, 3-8wt% of long-chain unsaturated fatty acid with carbon chain number more than or equal to 18, 3-5wt% of organic amine, 3.0-6.0wt% of inorganic salt and 30-50wt% of other surfactants except the alkanolamide surfactant; the other surfactant at least contains an anionic surfactant. The invention optimizes the types and the contents of the raw materials such as the surfactant, the inorganic salt, the fatty acid and the like in the concentrated detergent, and obtains the concentrated detergent with excellent thickening performance after high-power dilution in a narrow formula range.

Description

Concentrated detergent with high-power dilution and thickening performance and preparation method thereof

Technical Field

The invention relates to the field of detergents, in particular to a concentrated detergent with high-power dilution and thickening performance and a preparation method thereof.

Background

In daily life, consumers often subjectively relate the viscosity to the level of detergent products, so concentrated products having a certain viscosity are favored. However, currently highly concentrated detergents are often low viscosity, fast dissolving liquids in appearance and tend to be less viscous when diluted for use, and thus consumers are not able to subjectively and practically feel the concentrated nature of the product to some extent. If the concentrated detergent has dilution and thickening properties, namely the product initially keeps low viscosity, but after the concentrated detergent is diluted to the concentration of the conventional liquid laundry detergent, the viscosity of the product is increased to the viscosity of the conventional common liquid laundry detergent, so that a consumer can not only normally use the concentrated product according to the dosage of the common liquid laundry detergent, but also intuitively feel the concentration properties of the product, and the product applying the technology has a great market development prospect.

The prior published patents show that liquid detergents with a dilution thickening function are technically achievable, as disclosed in CN1079225478B as detergent compositions consisting of hydroxyalkyl methylcellulose ether, acrylic acid (fatty acid) ester polymers and surfactants, which are capable of retaining higher viscosity after dilution 2-fold or 3-fold; as also disclosed in CN 101563443B, a dishwashing detergent product with about 30% active substance formed by AES, sulfonic acid, betaine surfactant has a dilution thickening property without viscosity drop and reverse rise after dilution by 2 times; also, as disclosed in CN107446711B, a highly concentrated detergent containing comb polyether, which is prepared by mixing conventional surfactants such as alkylbenzenesulfonic acid, FMEE, AOS, and isomeric alcohol ether with comb polyether polymers of specific structure, has a higher viscosity after 4-fold dilution.

As can be seen from the above published patents, the realization of the dilution and thickening functions of concentrated detergent products has two main technical development directions at present: one is by way of finding and adding functional polymers of specific structure, such as cellulose ethers in CN1079225478B, acrylate copolymers and comb polyether polymers in CN 107446711B. However, the polymer itself does not have decontamination performance and is generally expensive, so that the polymer is temporarily not suitable for practical popularization; the other is to avoid the traditional raw materials such as AES and AEO by compounding the surfactant ₉ Gel region per se, with addition of specific thickener ingredients, achieving final production in a small rangeDilution thickening of the product, as in CN 101563443B, without the use of conventional fabric washing stock AEO ₉ The product is diluted and thickened by 2 times at about 30% of active substances by applying AES, sulfonic acid and CAB-35 in specific proportions. It is possible that the CAB-35 used, as well as the AES, itself has a gel interval, limiting the active range of the final product and thus retaining a higher viscosity only at low (2-fold) dilution. Therefore, there is a need to develop concentrated detergents that still have excellent thickening properties at high dilution.

Disclosure of Invention

In order to solve the technical problems, the invention provides a concentrated detergent with high-multiple dilution thickening performance and a preparation method thereof, and the concentrated detergent adopting the formula has excellent thickening performance after high-multiple dilution on the basis of excellent stability.

The specific technical scheme of the invention is as follows:

in a first aspect, the present invention provides a concentrated detergent having high dilution thickening properties comprising 40 to 70wt% active and water. The actives include the following components, based on the total weight of the concentrated detergent: 10 to 20 weight percent of alkanolamide surfactant, 3 to 8 weight percent of long-chain unsaturated fatty acid with carbon chain number more than or equal to 18, 3 to 5 weight percent of organic amine, 3.0 to 6.0 weight percent of inorganic salt and 30 to 50 weight percent of other surfactants except the alkanolamide surfactant; the other surfactant at least contains an anionic surfactant.

Preferably, the alkanolamide surfactant is typically characterized by having an amide bond structure in the molecule and one or more alcoholic hydroxyl groups in the hydrophilic group of the molecule, including one or more of coconut fatty acid diethanolamide (6501), fatty acid monoethanolamide (CMEA), fatty acid methyl monoethanolamide (CMMEA) and fatty acid amide MIPA. The long chain unsaturated fatty acids include one or more of oleic acid, linoleic acid, linolenic acid, and erucic acid. The inorganic salt includes one or more of potassium chloride, sodium chloride and sodium sulfate, and further preferably potassium chloride.

The concentrated detergents of the invention are highly concentrated formulations that require dilution by the consumer prior to use. After the liquid laundry detergent is diluted to the concentration of the common liquid laundry detergent, the viscosity of the product diluent is increased, which is equivalent to that of the common liquid laundry detergent sold in the market, so that consumers can intuitively perceive the 'concentration' and 'material presence' characteristics of the concentrated product. The key core components of the concentrated detergent disclosed by the invention are alkanolamide surfactant, long-chain unsaturated fatty acid, organic amine and high-addition inorganic salt, and the concentrated detergent has the following effects and beneficial effects:

(1) In conventional use cases, the inorganic salts in conventional detergent products are generally not more than 3.0wt%. In the present invention, however, a high addition amount of inorganic salt is an important component of the product that can be diluted and thickened. In the previous investigation and test of the team, the viscosity of the detergent can change along with the change of the content of certain inorganic salt, and in a certain salt adding range, the viscosity of the detergent shows a tendency of rising and then falling along with the increase of the salt adding amount. Thus, the nature of these inorganic salts provides a theoretical basis for achieving high-fold dilution thickening of concentrated detergents (inorganic salt content in the lower viscosity zone prior to dilution and just in the higher viscosity zone after dilution). Unfortunately, we have found in further experiments that in the undiluted state, excessive addition of salt to the concentrated detergent results in precipitation of the surfactant phase. Thus, although an excess of salt can act to reduce viscosity after dilution, it can also have an irreversible adverse effect on the stability of the detergent system. To overcome the instability problem of concentrated detergents at high salt levels. The invention limits the surfactant and the content thereof, selects organic amine to neutralize partial acidic raw materials (such as sulfonic acid, fatty acid and the like), and further limits the dosage of the organic amine, thus solving the problem of poor stability of the surfactant in a high-salt system. However, it was found in the test that the use of an organic amine in an excessive amount in a conventional concentrated detergent resulted in a problem of deterioration of thickening properties of the concentrated detergent after dilution, although the stability of the concentrated product was improved. Still further, we have studied the solution finally presented to make the organic amine and part of the anionic surfactant in the system exist in the form of organic amine counter ion coupled salt in the solution phase, the structure itself has better water solubility and higher salt tolerance, the salt tolerance of the whole formulation can be synchronously improved, and it becomes possible to make the concentrated detergent tolerant to more salt. In summary, the invention uses high-addition salt, which can keep the viscosity of the concentrated detergent lower before dilution, and ensure the low viscosity and instant property of the concentrated detergent, and simultaneously, the actual salt content can be effectively reduced to the concentration range of the thickening interval of the salt after high-time dilution (such as 3 times, 4 times, 5 times, 6 times, and the like) due to the addition of the salt, so that the final dilution and thickening of the product can be realized without adding other thickening polymers.

(2) The long-chain unsaturated fatty acid (carbon chain number is more than or equal to 18) screened in the invention has important effects on the viscosity increase and sample stability of the product after dilution. In general, saturated fatty acid soaps having longer carbon chains (carbon chain number. Gtoreq.18) have higher Krafft points per se and therefore have limited application in detergent formulations. However, according to the theory of stacking parameters of the surfactant forming micelles in the solution, when hydrophilic groups are certain, the length of the hydrophobic chain is increased, microscopically, the stacking and conversion of surfactant molecules from spherical micelles into rod-shaped micelles with higher viscosity are facilitated, and macroscopically, the viscosity of the formula is increased. Therefore, the long-chain unsaturated fatty acid is necessary to be selected in the invention, which is beneficial to improving the viscosity of the diluted sample. The unsaturated bond structure in unsaturated fatty acid improves the water solubility of fatty acid, so that good stability can be maintained in the product solution system before and after dilution.

Preferably, the organic amine comprises one or more of tetramethyl ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, and 1-isopropanolamine.

Preferably, the other surfactant is compounded by anionic surfactant and nonionic surfactant with the mass ratio of more than 1:1.

Further preferably, the anionic surfactant is an anionic surfactant that does not contain a gel region, including, but not limited to, one or more of alkylbenzene sulfonate, saturated fatty acid salt, sodium alpha-alkenyl sulfonate, modified grease ethoxylate sulfonate, and N-fatty acyl amino acid salt; the nonionic surfactant comprises one or more of fatty alcohol polyoxyethylene ether-9, alkyl glycoside and modified grease ethoxylate.

Preferably, the water content is less than 45wt% and the pH of the concentrated detergent is from 7.0 to 8.5 (before dilution).

Preferably, the concentrated detergent further comprises one or more of a co-solvent, a pH adjuster, a pigment, a preservative, a fragrance, a solubiliser and an enzyme preparation.

In a second aspect, the present invention provides a process for preparing the concentrated detergent described above: the inorganic salt is dispersed and dissolved in water in advance, organic amine and cosolvent are added, other surfactants are added after the inorganic salt is completely dissolved, alkanolamide surfactants are added after the other surfactants are stirred and dissolved, stirring is continued, the pH value of the system is regulated to be proper after stirring and dispersing, and finally functional small materials (if any) such as essence, enzyme preparation, preservative and the like are added, and concentrated detergent is obtained after stirring uniformly.

Compared with the prior art, the invention has the following technical effects: the invention optimizes the types and the contents of the raw materials such as the surfactant, the inorganic salt, the fatty acid and the like in the concentrated detergent, and obtains the concentrated detergent with excellent thickening performance after high-power dilution (such as 3 times, 4 times, 5 times, 6 times and the like) in a narrow formula range.

Detailed Description

The invention is further described below with reference to examples. Unless otherwise specified, percentages are weight percent (wt%) and temperatures are in degrees celsius. Unless otherwise specified, the operation is carried out at room temperature (20 to 25 ℃). "alkyl" is a substituted or unsubstituted saturated hydrocarbon radical having one to twenty two carbon atoms in a linear or branched arrangement. Unless otherwise specified, alkyl groups are unsubstituted.

General examples

A concentrated detergent with high-dilution thickening performance comprises 40-70 wt% of active and water. The actives included the following components, based on the total weight of the concentrated detergent: 10 to 20 weight percent of alkanolamide surfactant, 3 to 8 weight percent of long-chain unsaturated fatty acid with carbon chain number more than or equal to 18, 3 to 5 weight percent of organic amine, 3.0 to 6.0 weight percent of inorganic salt and 30 to 50 weight percent of other surfactants (at least containing anionic surfactant) except the alkanolamide surfactant.

Preferably, the alkanolamide surfactant comprises one or more of coconut oil fatty acid diethanolamide (6501), fatty acid monoethanolamide (CMEA), fatty acid methyl monoethanolamide (CMMEA) and fatty acid amide MIPA. The long chain unsaturated fatty acids include one or more of oleic acid, linoleic acid, linolenic acid, and erucic acid. The inorganic salt includes one or more of potassium chloride, sodium chloride and sodium sulfate, and further preferably potassium chloride. The organic amine comprises one or more of tetramethyl ethylenediamine, monoethanolamine, diethanolamine, triethanolamine and 1-isopropanolamine.

Preferably, the other surfactant is compounded by anionic surfactant and nonionic surfactant with the mass ratio of more than 1:1. Wherein the anionic surfactant is an anionic surfactant that does not contain a gel region, including, but not limited to, one or more of alkylbenzene sulfonate, saturated fatty acid salt, sodium alpha-alkenyl sulfonate, modified grease ethoxylate sulfonate (SNS-80), and N-fatty acyl amino acid salt; the nonionic surfactant comprises one or more of fatty alcohol polyoxyethylene ether-9, alkyl glycoside and modified oil ethoxylate (SOE-N-60).

Preferably, the water content is less than 45wt% and the initial (pre-dilution) pH of the concentrated detergent is from 7.0 to 8.5.

The preparation method of the concentrated detergent comprises the following steps: the inorganic salt is dispersed and dissolved in water in advance, organic amine and cosolvent are added, other surfactants are added after the inorganic salt is completely dissolved, alkanolamide surfactants are added after the other surfactants are stirred and dissolved, stirring is continued, the pH value of the system is regulated to be proper after stirring and dispersing, and finally functional small materials (if any) such as essence, enzyme preparation, preservative and the like are added, and concentrated detergent is obtained after stirring uniformly.

The technical scheme of the present invention will be described in further detail below with reference to the specific embodiments, but the present invention is not limited thereto.

The raw materials used in the invention are all commercial products, and the specific main surfactant raw material information is as follows: AES (2 EO), 70%, zhejiangyan; sulfonic acid (primary product), 96%, jin Tong petrochemical; AEO (AEO) ₉ 99%, sanjiang chemical industry; 6501 (1:1 type), zhejiang zanyu; isostearamide 1-isopropanolamine (IMIPA), 99%, cantonese technology; APG,50%, medium and light chemical; SNS-80, 70%, medium and light chemical industry; triethanolamine, 99%, ancient field chemical industry; monoethanolamine, 99%, ancient field chemical industry; tetramethyl ethylenediamine, 99%, aladine; refined oleic acid, 99%, feng Yi oil; distilling coconut fatty acid (DC 1218), 99%, feng Yi oil; propylene glycol, 99%, fine chemical engineering of ridge.

The surfactant materials in the following examples and comparative formulations of the present invention are all pure, unless otherwise specified.

TABLE 1 formulations (content/wt%) of examples 1-3 and comparative examples 1-2

Group of	Example 1	Example 2	Example 3	Comparative example 1	Comparative example 2
						Triethanolamine salt	5	5	5	5	5
KOH	1.4	1.4	1.4	1.4	1.4
						Sulfonic acid	10	10	10	10	10
AEO ₉	18	18	18	18	18
						6501	10	15	20	9	21
Refined oleic acid	4	4	4	4	4
						DC1218	2	2	2	2	2
Propylene glycol	10	10	10	10	10
						KCl	3.5	3.5	3.5	3.5	3.5
Citric acid/KOH monohydrate	Adjusting pH	Adjusting pH	Adjusting pH	Adjusting pH	Adjusting pH
						Acid-resistant blue	0.001	0.001	0.001	0.001	0.001
NIC-42 essence	0.5	0.5	0.5	0.5	0.5
						Kathon	0.2	0.2	0.2	0.2	0.2
Deionized water	Allowance of	Allowance of	Allowance of	Allowance of	Allowance of
						Apparent duty cycle/%	50	54	58	48	60
PH (stock solution)	8.0	8.0	8.0	8.0	8.0

The results of the above examples and comparative examples are shown in Table 2, with a viscosity of 25℃and a dilution test with Hangzhou tap water, and detergency test with QB/T1224.

Table 2 test results for examples 1-3 and comparative examples 1 and 2

The test results in Table 2 show that the amount of alkanolamide surfactants used in the present invention has a large effect on the dilution thickening performance of concentrated detergents. Taking 6501 as an example, the test shows that when the dosage of 6501 is too high, as in comparative example 2, the freeze-thaw recovery stability of the concentrated detergent is significantly reduced, presumably because the content of the fatty acid glyceride contained in 6501 (1:1) just reaches the critical content, the dissolution cannot be sufficiently dispersed in the solution phase, and thus the freeze-thaw recovery performance is poor. On the other hand, when the 6501 content is too low, the viscosity of the 5-fold diluent is 115mPa.s, and the dilution thickening performance is affected. Therefore, the amount of the alkanolamide surfactant used has a large influence on the performance of the concentrated detergent of the present invention, and it is preferable that the amount of the alkanolamide surfactant added is 10 to 20% in the preliminary step.

TABLE 3 expanded formulation and test results for example 3

The alkanolamide surfactant in the formula is expanded in Table 3, and other components are unchanged. The substitution of 6501 for other types of surfactants, such as IMIPA, CMMEA, CMEA, etc., results indicate that similar highly concentrated formulations formed from similar alkanolamide surfactants all have similar dilution thickening properties.

Table 4 formulation tables and test results for examples 4 and 5 and comparative examples 3-7

Table 4 based on example 2 (the amount of other materials is unchanged), the effect of the amount of organic amine in the formulation on the performance of the concentrated detergent is examined, and the result shows that the amount of triethanolamine has a larger effect on the low-temperature stability of the concentrated detergent, and when the amount is too high, the low-temperature stability of the concentrated product is good, but the dilution and thickening performance is poor; and when the amount of triethanolamine is low, the freezing and thawing recovery is poor. Therefore, it is presumed that the amount of the organic amine in the concentrated detergent product having the dilution thickening property is maintained only in a small range, and the preferable amount of the organic amine is 3 to 5%.

TABLE 5 expanded formulation and test results for example 5

The replacement of the organic amine in the formulation with other organic amines such as monoethanolamine, methyl monoethanolamine, tetramethyl ethylenediamine in table 5 shows that similar organic amines may exhibit similar functions. Although the viscosity of the diluted solution formed after neutralization of different organic amines may be slightly different, the stability of the concentrated detergent as a whole can still reach the standard, so that the organic amine in the formula is presumed to be correspondingly popularized to other organic amines of the same type.

TABLE 6 formulations and test results for examples 6-8 and comparative examples 8-10

As shown in the results of Table 6, the contents of the surfactant and oleic acid in the concentrated detergents were finely adjusted in examples 6, 7 and 8, and it was found that the viscosity of the diluted solution increased to some extent as the oleic acid content increased. Oleic acid was shown to be a source of natural long carbon chain unsaturated fatty acids, which have an important role in maintaining the viscosity and stability of the samples after high dilution compared to natural saturated fatty acids (such as stearic acid in comparative example 10). When the oleic acid content in the formulation was too low (comparative example 8), the dilution thickening performance was poor, and when the oleic acid content was too high (comparative example 9), the stability of the product was poor. Thus, the oleic acid content in concentrated detergents with good dilution thickening properties should preferably be approximately in the range of 3 to 8%.

TABLE 7 expanded formulation and test results for example 8

The carbon chain number of the long-chain unsaturated fatty acid is primarily expanded on the basis of example 8 in Table 7, and the rest components are unchanged. The results show that long-chain unsaturated fatty acids in the formula can be expanded into unsaturated fatty acids such as linoleic acid, erucic acid, linolenic acid and the like (C18 and above), but when 2-hexadecenoic acid with slightly lower carbon chain number (comparative example 11) is used, the viscosity of the sample is greatly reduced after dilution, and further the long-chain characteristic of the fatty acid is favorable for tackifying.

Table 8 formulations and test results for examples 9-11 and comparative examples 12-15

The development of the raw materials of the conventional anionic surfactants in table 8, such as APG, SNS-80 and SOE-N-60, is newly added in example 9 and example 10, and the results show that the formed concentrated detergent can still maintain a certain dilution and thickening performance, and the viscosity after 5-time or 6-time dilution is still equivalent to that of the common laundry detergent, and the formulation can be further popularized to other anionic and nonionic surfactants under the premise of controlling the core ingredients. Comparative examples 9, 10, 11 and comparative examples 12, 15, it was found that the salt content in the concentrated detergent system also had a certain effect on the stability of the concentrated product, and that the suitable salt content should be between 3.0 and 6.0%, with an excess of salt directly leading to a deterioration of the product stability (comparative example 12), while with an excessively low salt content the viscosity of the diluent is relatively low (comparative example 15). Since the inorganic salts exist in the form of ions in the solution phase, the common inorganic potassium salts and sodium salts of different species theoretically function similarly. The inorganic salts in the theoretical examples can also be replaced by common sodium salts such as sodium chloride and sodium sulfate and other types of common potassium salts, which are influenced by the cost limit of the products. In comparative examples 13 and 14, the most common AES materials were tried in such dilute thickened concentrate formulations, and the results showed that the samples were easily gelled during the preparation process after AES addition, presumably due to the broader gel interval of AES itself, the easier gelling, and the lower water content and the relatively higher salt content in the concentrate formulations. Therefore, it is presumed that other anionic surfactants having no gel section can be suitably preferable.

The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.

The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A concentrated detergent having high dilution thickening properties, characterized in that: comprises 40-70wt% of active substances and water; the actives include the following components, based on the total weight of the concentrated detergent: 10-20wt% of alkanolamide surfactant, 3-8wt% of long-chain unsaturated fatty acid with carbon chain number more than or equal to 18, 3-5wt% of organic amine, 3.0-6.0wt% of inorganic salt and 30-50wt% of other surfactants except the alkanolamide surfactant; the other surfactants are formed by compounding anionic surfactants and nonionic surfactants in a mass ratio of greater than 1:1; the highest multiple of the high-multiple dilution thickening is 6 times;

the anionic surfactant comprises one or more of alkylbenzene sulfonate, saturated fatty acid salt, alpha-sodium alkenyl sulfonate, modified grease ethoxylate sulfonate and N-fatty acyl amino acid salt;

the nonionic surfactant comprises one or more of fatty alcohol polyoxyethylene ether-9, alkyl glycoside and modified grease ethoxylate.

2. A concentrated detergent as claimed in claim 1, wherein: the alkanolamide surfactant comprises one or more of coconut oil fatty acid diethanolamide, fatty acid monoethanolamide, fatty acid methyl monoethanolamide and fatty acid amide.

3. A concentrated detergent as claimed in claim 1 or claim 2, wherein: the long chain unsaturated fatty acids include one or more of oleic acid, linoleic acid, linolenic acid, and erucic acid.

4. A concentrated detergent as claimed in claim 1 or claim 2, wherein: the inorganic salt includes one or more of potassium chloride, sodium chloride and sodium sulfate.

5. A concentrated detergent as claimed in claim 1 or claim 2, wherein: the organic amine comprises one or more of tetramethyl ethylenediamine, monoethanolamine, diethanolamine, triethanolamine and 1-isopropanolamine.

6. A concentrated detergent as claimed in claim 1, wherein: the water content is less than 45wt%, and the pH value of the concentrated detergent is 7.0-8.5.