Patent Application
20250215352
With increasing awareness on sustainable development, a highly concentrated and unit-dose detergent formulation is a clear market trend in both home care and industrial cleaning applications. In the highly concentrated and unit-dose detergent formulation, a total surfactant contents could reach around 50%-70% by weight or even higher, which makes saving on packaging materials, less water in production and transportation, etc. However, a high surfactant content may cause the formulation with high viscosity and difficulty in handling and use, prolong its dissolution time in cold water, cause gel formation during its dissolution, and consequently increase energy consumption in cleaning.
Generally, the highly concentrated detergent formulations mainly contain anionic surfactants, nonionic surfactants, some organic solvents, and other ingredients, Despite good detergency of the anionic surfactants in cleaning, the popular anionic surfactants, such as AES (alcohol ether sulfate, particularly sodium laureth sulfate) and LAS (linear alkylbenzene sulfonate), often form a gel at high concentration (30-70% by weight). Therefore, the organic solvents are added into the formulations to reduce viscosity and maintain its handling property. However, the organic solvents would not bring equivalent detergency as the surfactants. In contrast, they increase the cost of the formulations and would likely cause odor issues. Linear primary alcohol ethoxylate (e.g., L-PAE-9) is the most popular nonionic surfactant, and it indeed offers good detergency performance among the commercially available nonionic surfactants, but its water solution at high concentration of 30-60% by weight is also a gel. In consequence, L-PAE-9 in the highly concentrated or unit-does detergent formulations would also increase the viscosity. Branched alcohol initiated alkoxylated nonionic surfactants, such as ECOSURF™ EH-9 and LUTENSOL® XL-80, are flowable at a high concentration in water (e.g., in a concentration of 40-60% by weight). They have been broadly used in the highly concentrated or unit-dose detergent formulations as viscosity controller, but their detergency is weaker compared with L-PAE-9.
Therefore, there is still an urgent request for cleaning customers to have nonionic surfactants which can offer a remarkable combination of good detergency and strong viscosity controlling in the highly concentrated and unit-dose detergent formulations. In addition, if a good viscosity reduction can help the formulators decrease the solvent amount, this will be an interesting and welcome performance. Besides, low foaming formulations are often preferred in the Industrial & Institutional (I&I) cleaning; and in home care cleaning, this turns to be a need as well, because high foaming may extend rinsing time and increase water consumption. In the surfactant selection criteria, the biodegradability also becomes a required property for cleaning customers.
After persistent exploration, the inventors have surprisingly developed a primary or secondary alcohol-initiated nonionic surfactant, as well as a detergent composition and a liquid laundry product comprising the same, which exhibits good detergency, improved viscosity controlling (i.e., better flowability and no gel being formed during its dissolution in water) at highly concentrated and unit-dose detergent formulations, and lower foaming property (i.e., quick foam collapse).
In a first aspect of the present disclosure, the present disclosure provides a primary or secondary alcohol-initiated nonionic surfactant, which has the formula (I):
Where R′ is selected from the group consisting of a linear primary alcohol moiety having a C16-18 alkyl chain or secondary alcohol moiety having a C8-18 alkyl chain; R″ is a methyl or ethyl group; x is an integer selected from 2 to 4; y is an integer selected from 1 to 25; and z is an integer selected from 1 to 50.
In a second aspect of the present disclosure, the present disclosure provides use of the primary or secondary alcohol-initiated nonionic surfactant in a detergent composition.
In a third aspect of the present disclosure, the present disclosure provides a detergent composition, comprising:
In a forth aspect of the present disclosure, the present disclosure provides a liquid laundry product comprising the detergent composition.
In the present disclosure, the primary or secondary alcohol-initiated nonionic surfactant as well as the detergent composition and liquid laundry product comprising the surfactant may exhibit improved detergency, good viscosity controlling at highly concentrated and unit-dose detergent formulations, and lower foaming property. Further, they also exhibit better flowability and would not form gel when being dissolved in water.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. As disclosed herein, “and/or” means “and, or as an alternative” or “additionally or alternatively”. All ranges include endpoints unless otherwise indicated.
In the present disclosure, the primary or secondary alcohol-initiated nonionic surfactant has the formula (I):
The term “C16-18 alkyl chain” herein refers to alkyl chain having from 16 to 18 carbon atoms; and the term “C8-18 alkyl chain” herein refers to alkyl chain having from 8 to 18 carbon atoms. In an embodiment of the present disclosure, the C16-18 alkyl chain in the linear chain can be selected from n-hexadecyl, n-heptadecyl, n-octadecyl or mixture thereof.
In an embodiment of the present disclosure, the secondary alcohol comprises, but not limited to, 2-octanol, 3-octanol, 4-octanol, 2-nonanol, 3-nonanol, 4-nonanol, 5-nonanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-undecanol, 3-undecanol, 4-undecanol, 5-undecanol, 6-undecanol, 2-dodecanol, 3-dodecanol, 4-dodecanol, 5-dodecanol, 6-dodecanol, 2-tridecanol, 3-tridecanol, 4-tridecanol, 5-tridecanol, 6-tridecanol, 7-tridecanol, 2-tetradecanol, 3-tetradecanol, 4-tetradecanol, 5-tetradecanol, 6-tetradecanol, 7-tetradecanol, 2-pentadecanol, 3-pentadecanol, 4-pentadecanol, 5-pentadecanol, 6-pentadecanol, 7-pentadecanol, 8-pentadecanol, 2-hexadecanol, 3-hexadecanol, 4-hexadecanol, 5-hexadecanol, 6-hexadecanol, 7-hexadecanol, 8-hexadecanol, 2-heptadecanol, 3-heptadecanol, 4-heptadecanol, 5-heptadecanol, 6-heptadecanol, 7-heptadecanol, 8-heptadecanol, 2-octadecanol, 3-octadecanol, 4-octadecanol, 5-octadecanol, 6-octadecanol, 7-octadecanol, 8-octadecanol, 9-octadecanol, or any combinations thereof.
In an embodiment of the present disclosure, the secondary alcohol comprises 2-dodecanol, 3-dodecanol, 4-dodecanol, 5-dodecanol, 6-dodecanol, 2-tridecanol, 3-tridecanol, 4-tridecanol, 5-tridecanol, 6-tridecanol, 7-tridecanol, 2-tetradecanol, 3-tetradecanol, 4-tetradecanol, 5-tetradecanol, 6-tetradecanol, 7-tetradecanol or any combinations thereof.
In an embodiment of the present disclosure, x is an integer selected from 2, 3 and 4. In an embodiment of the present disclosure, y is an integer selected from 1 to 25, from 1 to 20, from 1 to 16, from 1 to 12, from 1 to 9, from 1 to 4, from 4 to 25, from 4 to 20, from 4 to 16, from 4 to 12, from 4 to 9, from 9 to 25, from 9 to 20, from 9 to 16, from 9 to 12, from 12 to 25, from 12 to 20, from 12 to 16, from 16 to 25, from 16 to 20, and from 20 to 25. In an embodiment of the present disclosure, z is an integer selected from 1 to 50, from 1 to 40, from 1 to 30, from 1 to 20, from 1 to 10, from 1 to 5, from 5 to 50, from 5 to 40, from 5 to 30, from 5 to 20, from 5 to 10, from 10 to 50, from 10 to 40, from 10 to 30, from 10 to 20, from 20 to 50, from 20 to 40, from 20 to 30, from 30 to 50, from 30 to 40 and from 40 to 50.
In an alternative embodiment of the present disclosure, the sum of x and z is an integer selected from 3 to 54, from 3 to 50, from 3 to 40, from 3 to 30, from 3 to 20, from 3 to 10, from 3 to 5, from 5 to 54, from 5 to 50, from 5 to 40, from 5 to 30, from 5 to 20, from 5 to 10, from to 54, from 10 to 50, from 10 to 40, from 10 to 30, from 10 to 25, from 10 to 20, from 10 to 15, from 15 to 54, from 15 to 50, from 15 to 40, from 15 to 30, from 15 to 25, from 15 to 20, from 20 to 54, from 20 to 50, from 20 to 40, from 20 to 30, from 20 to 25, from 25 to 54, from 25 to 50, from 25 to 40, from 25 to 30, from 30 to 54, from 30 to 50, from 30 to 40, from 40 to 10 54, from 40 to 50, and from 50 to 54.
In an alternative embodiment of the present disclosure, the number of y is less than that of the sum of x and z. Alternatively, y may be equal to the sum of x and z, or y may be greater than the sum of x and z. In an alternative embodiment of the present disclosure, y is equal or greater than 8, 12, 16 or 20. In an alternative embodiment of the present disclosure, the sum of x and z is greater than 20, 24, 28 or 32.
In the present disclosure, the linear C16-18 primary alcohol or C8-18 secondary alcohol initiated triblock nonionic surfactants can increase the total surfactant concentration in the detergent formulations to a level which is much higher than that in the prior art, and the concentration of anionic surfactant in the detergent composition can also be increased to a level which is much higher than that in the prior art. In this regards, the inventors may apply the primary or secondary alcohol-initiated nonionic surfactant to a detergent composition comprising anionic surfactants, so as to increase the total surfactant concentration and reduce solvent content. In the present disclosure, the detergent composition is characterized by reduced solvent content, increased surfactant content, low viscosity, quicker dissolution, good detergency, improved viscosity controlling (i.e., better flowability and no gel being formed) at highly concentrated and unit-dose detergent formulations, and lower foaming property (i.e., quick foam collapse). or a combination of two or more thereof.
In the present disclosure, the detergent composition may comprise (a) at least one anionic surfactant; and (b) at least one primary or secondary alcohol-initiated nonionic surfactant. In the present disclosure, the detergent composition may further comprise (c) at least one organic solvent.
In an embodiment of the present disclosure, the anionic surfactants to be used in the present invention as the component (a) includes alkylsulfates, alkyl ether sulfates, alkylsulfonates, fatty acid salts, dialkylsulfosuccinates, alkylbenzenesulfonates, alkylphosphate, fatty acid soaps, and α-olefinsulfonates, though it is not particularly limited. The anionic surfactants are preferably selected from among alkylsulfates, alkyl ether sulfates, alkylbenzenesulfonates, alkanesulfonates, fatty acid salts, dialkylsulfosuccinates and any combinations thereof. In an embodiment of the present disclosure, the anionic surfactants are substantially free of any intermediate polarity spacers inserted between a hydrophilic moiety and a hydrophobic moiety of the anionic surfactants. In the present disclosure, the intermediate polarity spacers generally comprise chain of propylene oxide (PO), chain of butylene oxide (BO) or any combination of ethylene oxide (EO), PO and BO in block or random order.
As to the optional organic solvents, they may be used alone in the detergent composition, or used in combination with other organic solvents in the detergent composition. In an embodiment of the present disclosure, the organic solvents may be at least one solvent selected from the group of alcohols, glycols, and glycol ethers, for example, ethanol, isopropyl alcohol, propylene glycol and etc.
In an embodiment of the present disclosure, components (a) and (b) are in amount of at least 50% by weight, at least 60% by weight, at least 70% by weight or at least 80%, based on the total weight of the detergent composition.
In an embodiment of the present disclosure, component (a) is in amount of at least 50% by weight, at least 60% by weight, at least 70% by weight or at least 80% by weight of the sum of components (a) and (b).
In an embodiment of the present disclosure, the detergent composition comprises less than 20% by weight, less than 15% by weight, less than 10% by weight, less than 5% by weight, or less than 1% by weight of component (c).
In the present disclosure, the detergent composition can be diluted with water to provide a liquid laundry product. In the present disclosure, the detergent composition can contain some water, and the amount of water may be adjusted according to actual need of cleaning. In one embodiment of the present disclosure, the amount of water is generally low for highly concentrated detergent formulation. On the other hand, the unit-dose detergent formulation generally cannot contain too much water, since the packaging material of the unit-dose detergent formulation is water soluble. For example, the unit-dose detergent formulation may comprise 5-10% by weight of water.
The present disclosure provides nonionic surfactants which may deliver the following properties:
Besides remarkable combination of detergency and viscosity controlling in the highly concentrated and unit-dose detergent formulations, it can effectively reduce the solvent usage in the formulation, which meets the sustainable development trend and helps formulators reduce formulation cost.
Some embodiments of the invention will now be described in the following examples, wherein all parts and percentages are by weight unless otherwise specified.
The information of the raw materials used in Examples is listed in the following Table 1:
The nonionic surfactants in the present disclosure can be obtained in conventional manners by reacting an alcohol with alkylene oxides, such as ethylene oxide (EO) and propylene oxide (PO), in the presence of a catalyst. Polymerization can be bulk polymerization or solution polymerization. Catalysts suitable for polymerization of alkylene oxide can be found in literature, for example F. E. Bailey, Jr., Joseph V. Koleske, “Alkylene Oxides and Their Polymers” Marcel Dekker, New York, 1991, p. 35, including anionic or basic catalysts, acid or cationic catalysts, and coordinate catalysts, for example, postassium hydroixde (KOH), boron trifluoride, or double metal cyanide complex (DMC) catalysts such as zinc hexacyanocobaltate. The alkylene oxides are typically fed into a reactor containing dried initiator and the catalyst at temperatures varying from 50 to 160° C. When the pressure in the reactor returns to approximately the same pressure before feeding the alkylene oxides, the polymerization is usually considered complete. The catalysts can be neutralized, removed by known means, for example filtration, adsorption, and ionic exchange, or left in the products depending on the products and applications.
9. After cooling down to around 40° C., the desired product was obtained.
Synthesis Example 2 was conducted similar to synthesis example 1, except that in step 6,the last portion of EO in 15 moles (corresponding to 15 molar equivalents of L-C16-18 alcohol) was fed into the reactor slowly.
Synthesis Example 3 was conducted similar to synthesis example 1, except that in step 6, the last portion of EO in 25 moles (corresponding to 25 molar equivalents of L-C16-18 alcohol) was fed into the reactor slowly.
Synthesis Example 4 was conducted similar to synthesis example 1, except that TERGITOL™ 15-S-3 was used, instead of L-C16-18 alcohol; step 4 was omitted since TERGITOL™ 15-S-3 already contains 3 moles of EO in each molecule; in step 5, PO in 10 moles (corresponding to 10 molar equivalents of TERGITOL™ 15-S-3) was fed into the reactor slowly and in step 6, the last portion of EO in 10 moles (corresponding to 10 molar equivalents of TERGITOL™ 15-S-3) was fed into the reactor slowly.
As shown in Table 2, the surfactants in Inventive Examples (IE) 1-4 and Comparative Examples (CE) A-F were tested or evaluated according to the measurements described below.
64a
aCloud point data was measured at 10% wt. aqueous solution.
bFoam heights at 0 and 5 minutes.
As shown in Table 3, all the four Inventive Examples IE-1, IE-2, IE-3 and IE-4 had low CMC values, which could bring good surfactant efficiency. The Ross-Miles foam heights in Table 3 and
Highly concentrated liquid laundry detergent formulations were formulated according to the following steps:
Different Inventive Examples (IE) 1-4 and Comparative Examples (CE) B-D as “nonionic surfactant” were evaluated in the highly concentrated liquid laundry detergent formulation.
As shown in
Unit-dose laundry liquid detergent formulations were formulated according to the following steps:
The formulations in Table 5 contained very high total surfactant contents at about 80% by weight in the unit-dose laundry formulations. The solvent amount (propylene glycol) and water content were at 10% by weight and 10% by weight (due to AES (70%) containing water as well), respectively. In addition, the formulation contained very high content of anionic surfactants at 60% or 70% based on the total weight of the surfactants. In the formulation with anionic/nonionic surfactant at 60/40 by weight, the IE-2/IE-3 demonstrated higher detergency, compared with the CEs, as shown in
Original formulation in the viscosity controlling study
#Nonionic surfactant used in formulation of Table 6.
Compared with the formulation in Table 6, the formulation in Table 8 didn't contain any solvent (propylene glycol), which could be more challenging to maintain the formulation with a good flowability. In addition, L-PAE-9 was also replaced and included in “Nonionic surfactant”. On evaluating different IEs and CEs as “nonionic surfactant”, we measured the formulation viscosities at 2 different temperatures (5° C. and 20° C.) and the results are listed in Table 9.
#Nonionic surfactant used in formulation of Table 8.
Based on the data in Table 7 and Table 9, it was found that in the highly concentrated liquid laundry detergent formulation, the 4 inventive surfactants always offered the formulations with lower viscosity than the comparative surfactants. Also, the formulation stability with IEs was more stable. In addition, such a performance advantage could be more interesting at low temperature, which could be beneficial in low temperature storage.
The formulations with CEs and IEs were prepared according to Table 5. Then, the viscosity of the formulation before and after dilution with different amounts of water was measured. For an unit-dose laundry formulation, if it forms a gel during dissolution, it will slow down its dissolution and consequently affect its detergency.
As shown in
Surface tension was measured on KRUSS Force Tensiometer K100C. The whole test was conducted at room temperature,
The test procedure was referred to ASTM D97-12 with the equipment YuTong (YT-S10E-3). The test procedure included the steps described as here below:
Washing process:
Formulation viscosity was measured with Brookfield LVDV-II. The samples with viscosity lower than 1000 were conducted by #62 spindle at 30 rpm; the ones with viscosity higher than 1000 were measured by #62 spindle at 10 rpm.
2 mL unit dose formulations were added into 8 mL glass tubes. The initial viscosity was measured by High throughput TADM method which is a pressure-based parallel viscosity measurement method developed by Dow. It estimates the viscosity of samples by monitoring pressure change in a pipette. After viscosity measurement, 1 mL deionized water was added into the tubes and the mixtures were mixed until homogeneous. Then, their viscosity was measured by TADM method again. The process of water addition and viscosity measurement was repeated two times until 3 mL deionized water was mixed into unit dose formulations.
Based on all the above performance comparison, the triblock nonionic surfactants of the present invention exhibited unique and interesting surfactant properties: low CMC, medium foam with quick foam collapse. The evaluations in different types of detergent formulations showed these triblock nonionic surfactants delivered an exceptional combination of detergency and viscosity controlling, none of the comparative benchmark was able to offer such a good balanced performance. More particularly and interestingly, the inventive triblock nonionic surfactants containing unit-dose detergent formulations exhibiting low solvent and water contents could keep better flowability in the dissolution stage and improved detergency.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/087041 | 4/15/2022 | WO |
