Highly stable, environmentally friendly gel balls and method for manufacturing the same

Abstract

Highly stable, environmentally friendly gel balls and a method for producing the same. The highly stable, environmentally friendly gel balls contain the following components in the following mass fractions: surfactant A, surfactant B1, surfactant B2, a basic neutralizer, an auxiliary agent, and water. Organic solvents are completely replaced with different types of naturally derived surfactant compositions, and a stable, uniform gel ball inner solution can be prepared by combining other naturally derived surfactants, auxiliary agents, a basic neutralizer, and water. The blend and synergistic effect of the plant-derived anionic and nonionic surfactants results in a stable, uniform gel ball product with good cleaning effect, high naturalness and active ingredient content, and environmental friendliness.

Description

Technical Field

[0001] The present invention belongs to the technical field of household detergents, and particularly relates to an environmentally friendly gel ball with high stability and a method for producing the same.

Background Art

[0002] With the development of the economy and the improvement of the consumption level, the product form of fabric detergents has also evolved and changed. It has developed from the initial soap to detergents and then to the recent laundry liquids. By 2015, Procter & Gamble first launched a gel ball, a new type of laundry product, in China. As a new generation of fabric washing products, gel balls have characteristics such as concentration, convenience, strong decontamination power, easy rinsing, and quantitative packaging. In 2021, the industry standard QB / T5658 was also distributed. According to the industry standard QB / T5658 of gel balls and the requirements for production, storage, transportation, etc., gel balls must meet the requirements such as stress resistance, decontamination power, solubility, etc. It has also been found that there are significant differences between gel balls and ordinary laundry liquids.

[0003] For gel balls, not only the gelation problem arising from the surfactant formulation, but also the compatibility between the gel ball's internal liquid and the water-soluble membrane, i.e., the stability of the gel ball product, must be considered. In the case of typical gel balls, solving the gelation problem of the gel ball's internal liquid can generally be achieved by rationally blending anionic and nonionic surfactants and adding a large amount of solvent to form a uniform and stable gel ball internal liquid. However, this is limited to compatibility with the water-soluble membrane. Therefore, in order to prevent gelation in the gel ball's internal liquid, ensure good compatibility with the water-soluble membrane, and not affect the stability of the gel ball, it is necessary to add a large amount of organic solvent to the gel ball's internal liquid. This organic solvent not only results in high production costs but also contributes little to the cleaning function. In the case of natural gel balls, the selection of naturally derived solvents and surfactants is limited. Many naturally derived anionic surfactants contain a large amount of water, and considering the unstable effects that arise between the water content and the water-soluble membrane, these raw materials are not suitable for producing highly natural gel balls. Furthermore, bases manufactured using only naturally derived nonionic surfactants tend to gel easily or undergo large viscosity changes, making it difficult to seal the film and preventing the production of stable, highly natural gel balls.

[0004] For example, patent publication CN111040894A discloses mini gel balls containing many organic solvents and surfactants entirely derived from the petrochemical industry. Patent publication CN105861193B discloses a natural soda laundry solution, which uses naturally derived surfactants in its composition, but also incorporates many non-natural inorganic salts, resulting in an overall anionic composition that is not applicable to gel ball products. Patent publication CN109957470A discloses a concentrated natural amino acid surfactant laundry solution for infants and a method for producing the same. While the types and range of raw materials included in this patent publication allow for the production of relatively natural gel ball bases, the absence of organic solvents and the fact that many of the surfactants used are long-chain aliphatic alcohol surfactants result in poor stability of the resulting base. For these reasons, many of the disclosed inventions do not mention features relating to gel ball products that are naturally derived and free of organic solvents.

[0005] Therefore, a major challenge in this field is how to utilize naturally derived carbon surfactants with cleaning properties as a substitute for organic solvents and surfactants entirely derived from the petrochemical industry, in the case of gel balls made from natural materials without the addition of organic solvents.

[0006] Therefore, in order to solve the above problems, the present invention provides technical means relating to highly stable, environmentally friendly gel balls. [Overview of the project] [Problems that the invention aims to solve]

[0007] To overcome the shortcomings of conventional technology, the present invention provides a highly stable, environmentally friendly gel ball and a method for producing the same, which solves the problem of using a surfactant derived from natural carbon instead of organic solvents and surfactants derived entirely from the petrochemical industry in conventional technology. [Means for solving the problem]

[0008] One embodiment of the present invention provides a highly stable, environmentally friendly gel ball.

[0009] The aforementioned highly stable, environmentally friendly gel balls contain the following components in the following mass fractions: Surfactant A 10%~60% Surfactant B 10%~50% Basic neutralizing agent 0.01%~10% Additives 0.1%~10% water remainder The surfactant B includes surfactant B1 and / or surfactant B2. The surfactant B1 is represented by the general formula of structural formula I and / or structural formula II, [ka] [ka] The surfactant B1 can be selected from AkzoNobel's alkyl glucoside AG series products.

[0010] Preferably, the surfactant B1 is selected from AG6206 and AG6202.

[0011] The surfactant B2 is represented by the general formula of structural formula III, [ka] Here, R is selected from either sodium ions, potassium ions, or calcium ions.

[0012] Preferably, the surfactant B2 can be selected from AkzoNobel's Elfan series products.

[0013] Preferably, the surfactant B2 is selected from ElfanAT84C.

[0014] Furthermore, the surfactant A is one or more selected from fatty acids, cocoyl glycinate, fatty acid methyl ester sulfonate, aliphatic alcohol alkoxide, and polyoxyethylene oleate.

[0015] Furthermore, the fatty acid includes saturated fatty acids and unsaturated fatty acids, and the saturated fatty acids are one or more selected from capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and arachidic acid.

[0016] The unsaturated fatty acids are one or more selected from linoleic acid, linolenic acid, and arachidonic acid.

[0017] Furthermore, the structural formula of the cocoyl glycinate is as follows.

Chemical formula

[0018] Preferably, the cocoyl glycinate can be selected from the cocoyl glycinate series of Korea's Miream Commercial Co., Ltd. or Sino Lion.

[0019] Furthermore, the structural formula of the fatty acid methyl ester sulfonate is as follows.

Chemical formula

[0020] Preferably, the fatty acid methyl ester sulfonate can be selected from the HC series products of Petroliam Nasional Berhad such as HC701 and HC501.

[0021] Furthermore, the general formula of the aliphatic alcohol alkoxide is as follows. [ka] Here, the aliphatic alcohol portion is selected from natural sources, n is 8-20, x indicates the average degree of ethoxylation and is 1-16, and y is Propoxi This represents the degree of transformation, ranging from 0 to 16.

[0022] Preferably, the aliphatic alcohol ethoxylate can be selected from NEODOL-based linear aliphatic alcohol ethoxylate products of Malaysian Petroleum Company or Shell, and the aliphatic alcohol ethoxypropoxylate can be selected from NS, GENAPOL-based products of Clariant or DOW.

[0023] Furthermore, the general formula for the polyoxyethylene oleate ester is as follows: [ka] Here, the oleyl alcohol portion is selected from natural sources, the ethylene oxide portion is selected from natural sources, and n is between 8 and 16.

[0024] Preferably, the polyoxyethylene oleate ester can be selected from CRODA's ECOBRIJ® series of polyoxyethylene oleate ester products.

[0025] Preferably, the surfactant A is selected from a composition of fatty acids, ECOBrijO10, AEO7, GENAPOLEP2454, NS-669, sodium cocoyl glycinate, and HC501.

[0026] Furthermore, the weight ratio of surfactant A to surfactant B is 1 to 5:1 to 5.

[0027] Furthermore, the weight ratio of surfactant B1 to surfactant B2 is 1 to 10:1.

[0028] Furthermore, the aforementioned basic neutralizing agent is an inorganic basic neutralizing agent.

[0029] Preferably, the mass fraction content of the basic neutralizing agent is 1% to 8%.

[0030] Furthermore, the cation of the inorganic neutralizing agent is at least one selected from sodium ions, potassium ions, calcium ions, and magnesium ions.

[0031] Preferably, the anion of the inorganic neutralizing agent is at least one selected from hydroxides, oxides, carbonates, and bicarbonates.

[0032] Preferably, the inorganic neutralizing agent is sodium hydroxide.

[0033] Furthermore, the auxiliary agent includes at least one of the following: an enzyme preparation, a regulator, a chelating agent, a coloring agent, a color stabilizer, or an essence.

[0034] Another object of the present invention is to provide a method for producing highly stable and environmentally friendly gel balls, the production method comprising the steps of: dissolving a basic neutralizing agent in deionized water under room temperature conditions; adding surfactant B1 and surfactant B2 and stirring uniformly; adding surfactant A and stirring to dissolve it; waiting until the temperature drops below 50°C; adding an auxiliary agent; stirring uniformly until the appearance is uniform to obtain the gel ball liquid; and wrapping the gel ball liquid with a PVA film to obtain a finished gel ball product. [Effects of the Invention]

[0035] The highly stable, environmentally friendly gel balls provided by the present invention have the following beneficial effects.

[0036] 1. The present invention combines a plant-derived, non-ethoxylated, sulfate-free anion with a short-chain alkyl glucoside to form a complex surfactant, resulting in excellent synergistic effects. This provides good affinity between the components, enhances dispersibility, and delivers a strong solubilizing effect. The resulting gel ball product has a uniform appearance, good high and low temperature stability, and avoids the risk of "extra-film precipitation" of the gel ball product due to excessive sulfate content in the system. Surprisingly, the gel ball of the present invention also exhibits significantly improved decontamination power, achieving a P value of 1.08 for carbon black, 1.28 for protein, and 1.17 for sebum, representing a clear improvement over prior art. Furthermore, the gel ball of the present invention has a high water content, which not only helps reduce the overall cost of the product but also helps stabilize the formulation by dissolving some of the auxiliary agents and surfactants, thus achieving the effect of replacing petrochemical-derived solvents in gel ball products. The highly stable, environmentally friendly gel balls of the present invention have the advantages of being highly natural, having a high active ingredient content, high stability, and excellent cleaning effect, and have promising application prospects.

[0037] 2. The present invention also allows for the use of a surfactant composition instead of an organic solvent, thereby providing the gel ball with highly concentrated properties, and all surfactants used in the present invention are of natural origin. Therefore, the gel balls encapsulated in PVA have advantages such as a high degree of naturalness, high active substance content, high stability, and excellent cleaning effect.

[0038] 3. The present invention can completely replace organic solvents with different types of naturally derived surfactant compositions, and can prepare a stable and uniform gel ball liquid by combining other naturally derived surfactants, auxiliary agents, basic neutralizing agents, and water. Through the combination and synergistic action of plant-derived anionic and nonionic surfactants, the final prepared gel ball product is stable and uniform, has good cleaning effect, is highly natural, has a high active ingredient content, and is environmentally friendly. [Modes for carrying out the invention]

[0039] To more clearly illustrate the technical concept of the present invention, the following examples are given. Unless otherwise specified, the raw materials, reactions, and post-treatment methods shown in the examples are all commonly available raw materials on the market and technical methods well known to those skilled in the art.

[0040] In this invention, "naturally derived" means that the carbon-containing structure of the carbon-containing raw materials used is of natural origin. In this invention, naturalness (RCI) refers to the Renewable Carbon Index, where the naturalness (RCI) of a raw material is the ratio of the number of renewable carbons to the total number of carbons in its structure, and the naturalness (RCI) of a product is the ratio of renewable carbon to total organic carbon in the product.

[0041] The surfactant B1 in the embodiments of the present invention can be selected from AkzoNobel's alkyl glucoside AG products.

[0042] In the embodiments of the present invention, the surfactant B1 is preferably AG6206 and AG6202.

[0043] The surfactant B2 in the embodiments of the present invention can be selected from AkzoNobel's Elfan series products.

[0044] In the embodiments of the present invention, the surfactant B2 is preferably Elfan AT84 C.

[0045] The cocoyl glycine salt used in the embodiments of the present invention can be selected from the cocoyl glycine salt systems of Korea Miwon Trading Co., Ltd. or Sino Lion Co., Ltd.

[0046] In the examples of the present invention, fatty acid methyl ester sulfonates can be selected from HC-based products of Malaysian oil companies, such as HC701 and HC501.

[0047] In the embodiments of the present invention, the aliphatic alcohol ethoxylate can be selected from NEODOL-based linear aliphatic alcohol ethoxylate products of Malaysian Petroleum Company or Shell, and the aliphatic alcohol ethoxypropoxylate can be selected from NS, GENAPOL-based products of Clariant or DOW.

[0048] Table 1 shows the components in the gel balls of Examples 1 to 3 and their corresponding mass fractions.

[0049] [Table 1]

[0050] The methods for producing gel balls in Examples 1 to 3 include the following steps.

[0051] The above method for manufacturing gel balls involves dissolving a basic neutralizing agent in deionized water under room temperature conditions, adding surfactants B1 and B2 according to their mass fractions, stirring uniformly, then adding surfactant A according to its mass fraction and stirring until dissolved, waiting until the temperature drops below 50°C, adding auxiliary agents according to their mass fractions, stirring uniformly until the appearance is uniform to obtain the gel ball liquid, and finally wrapping the gel ball liquid in a PVA film to obtain the finished gel ball product.

[0052] Comparative Examples 1 to 5 were established based on Example 1, and the components and mass fractions of Comparative Examples 1 to 5 are shown in Table 2.

[0053] [Table 2]

[0054] The differences between the comparative examples and the examples are as follows: Comparative Example 1 had an organic solvent and an excess of inorganic base added to reduce the content of surfactant B; Comparative Example 2 had an organic solvent added and adjusted the ratio of surfactant B1 to surfactant B2; Comparative Example 3 had an organic solvent added but no surfactant B1 added; Comparative Example 4 had a large amount of organic solvent added; and Comparative Example 5 had a large amount of solubilizing raw material added.

[0055] Test Example 1

[0056] Stability tests were conducted on the appearance of the gel balls in Examples 1-3 and Comparative Examples 1-5 during storage. The specific test methods and evaluation criteria are as follows.

[0057] High-temperature stability: The gel balls were placed in the designated packaging, left in an environment of 45°C ± 1°C, and left at a constant temperature for one month. After returning to room temperature of 25°C ± 5°C, the gel balls were deemed to have passed the high-temperature stability test if there was no significant change in the appearance of the gel balls, no damage or leakage, and no phase separation, turbidity, gelation, or precipitation in the liquid inside the gel balls.

[0058] Low-temperature stability: Gel balls were placed in the designated packaging, left in an environment of -5°C ± 2°C, and then left at a constant temperature for one month. After removal, they were immediately observed. If there was no significant change in the appearance of the gel balls, no breakage or leakage, and no phase separation, turbidity, gelation, or precipitation in the liquid inside the gel balls, the low-temperature stability was deemed satisfactory.

[0059] Freeze-thaw cycle stability: Gel balls were placed in designated packaging, left in an environment of -15°C to -20°C, left at constant temperature for 24 hours, removed, and left in an environment of room temperature (25°C ± 5°C) for 24 hours. This constituted one cycle, and the cycle was repeated five times consecutively, with the state of the composition observed each time. This experiment is a freeze-thaw cycle experiment. If there is no significant change in the appearance of the gel balls, no breakage or leakage, and no phase separation, turbidity, gelation, or precipitation in the liquid inside the gel balls, then the gel balls are considered stable. Freeze-thaw cycle stability You pass.

[0060] Room temperature stability: After placing the gel balls in the designated packaging and leaving them at room temperature (20°C to 30°C) for one month, if there is no significant change in the appearance of the gel balls, no damage or leakage, and no phase separation, turbidity, gelation, or precipitation in the liquid inside the gel balls, the product is considered to have passed the room temperature stability test.

[0061] Table 3 shows the measurement results of the stability and uniformity of gel balls in the examples and comparative examples of the present invention. Here, the method for measuring the naturalness of the composition is: Naturalness of product composition (RCI) = Number of renewable carbons in the composition / Total number of organic carbons × 100%.

[0062] [Table 3]

[0063] As is clear from Table 3, Examples 1-3 use a large amount of naturally derived raw materials and therefore have a high degree of naturalness (RCI > 60%). From the stability test results of Examples 1-3, it was found that the gel balls of Examples 1-3 can ensure sample stability at each test temperature. Furthermore, the inventors discovered the following during the experiments: although Examples 1-3 had a total water content of ≥ 15% due to the introduction of a large amount of free water into the composition, the long-term weight loss rate of the gel ball product wrapped in PVA film during storage was ≤ 15%, thus meeting the weight stability requirements for gel balls in QB / T5658.

[0064] In Comparative Example 1, precipitation of the sample occurred due to excessive addition of inorganic base and insufficient addition of surfactant B (containing AG6202, AG6206, and ElfanAT84C). In Comparative Example 2, the gel balls were soft and crumbled, resulting in poor stress resistance, due to problems with the blending ratio of surfactant B1 (AG6202, AG6206) and surfactant B2 (ElfanAT84C). In Comparative Example 3, gelation occurred in the sample due to problems with the blending of each component of the surfactants and the absence of surfactant B1 (containing AG6202, AG6206). On the other hand, in Comparative Examples 4 and 5, by using general surfactants and blending a certain amount of organic solvent, the surfactant content of the gel balls themselves reached a high level. Although the overall clarity decreased to some extent, it was basically judged to be acceptable, and the overall naturalness of the composition was low due to the types of surfactants selected.

[0065] Test Example 2

[0066] For Examples 1-3 and Comparative Examples 4-5 described above, decontamination power tests were conducted according to "GB / T 13174 2008 Measurement of Decontamination Power and Circulation Washing Performance of Laundry Detergents". In the decontamination test, the amount of sample added conformed to the requirements of "QB / T 5658 Gel Ball". The results obtained are shown in Table 3. Here, the R value represents the decontamination value, and the P value represents the decontamination ratio. Generally, a standard laundry solution is used as a reference sample, its decontamination ratio is set to 1.00, and the P value is obtained by dividing the R value of the other detergents by the R value of the standard laundry solution. A higher P value indicates better cleaning power. Here, the stability of Comparative Examples 1-2 all failed, and since phenomena such as softening, disintegration, phase separation, gelation, or turbidity were evident, there was no need to perform this test. The test results are shown in Table 4.

[0067] [Table 4]

[0068] As is clear from Table 4, the gel balls of the examples showed significantly superior decontamination effects against carbon black, protein, and sebum compared to the standard laundry solution and Comparative Examples 4 and 5. Among these, Comparative Examples 4 and 5 had lower naturalness and somewhat reduced clarity, but had a high overall surfactant content and strong decontamination power. The gel balls of the examples of the present invention have high decontamination power, and their overall washing effect is clearly superior to that of the standard laundry solution and Comparative Examples.

[0069] The present invention is not limited to the details of the exemplary embodiments described above, and it will be apparent to those skilled in the art that it can be realized in other specific forms without departing from the spirit or basic features of the invention. Therefore, in any respect, the embodiments are illustrative and non-limiting. The scope of the invention is limited not by the above description but by the appended claims, and all modifications within the meaning and scope of equivalents of the claims are intended to be incorporated into the invention.

[0070] Although this specification describes embodiments, each embodiment does not necessarily consist of only one independent technical means. This method of description is merely for clarity, and those skilled in the art should consider the specification as a whole, and the technical means in each embodiment may be combined as appropriate to form other embodiments that will be understood by those skilled in the art.

Claims

1. These are highly stable, environmentally friendly gel balls. The aforementioned highly stable, environmentally friendly gel balls contain the following components in the following mass fractions: Surfactant A 10% to 60% Surfactant B 10% to 50% Basic neutralizing agent 0.01% to 10% Additives 0.1% to 10% water remainder The surfactant B includes surfactant B1 and surfactant B2. The surfactant B1 is represented by the general formula of structural formula I and / or structural formula II, 【Chemistry 1】 【Chemistry 2】 The surfactant B2 is represented by the general formula of structural formula III, 【Transformation 3】 Here, R is selected from sodium ions, potassium ions, or calcium ions. The aforementioned basic neutralizing agent is an inorganic basic neutralizing agent. The surfactant A is one or more selected from fatty acids, cocoyl glycine salts, fatty acid methyl ester sulfonates, aliphatic alcohol alkoxides, and polyoxyethylene oleate esters. The weight ratio of surfactant B1 to surfactant B2 is 1 to 10:

1. A highly stable, environmentally friendly gel ball characterized by these features.

2. The highly stable, environmentally friendly gel ball according to claim 1, characterized in that the weight ratio of surfactant A to surfactant B is 1 to 5:1 to 5.

3. The stable, environmentally friendly gel ball according to claim 1, characterized in that the cation of the inorganic basic neutralizing agent is at least one selected from sodium ions, potassium ions, calcium ions, and magnesium ions, and the anion of the inorganic basic neutralizing agent is at least one selected from hydroxides, oxides, carbonates, and bicarbonates.

4. The aforementioned auxiliary agent is characterized by comprising at least one of an enzyme preparation, a regulator, a chelating agent, a coloring agent, a color stabilizer, and an essence, as described in claim 1, providing a highly stable and environmentally friendly gel ball.

5. The highly stable, environmentally friendly gel ball according to claim 1, characterized in that the water content is ≥ 15 wt%.

6. A method for producing a highly stable, environmentally friendly gel ball according to any one of claims 1 to 5, characterized by comprising the steps of dissolving a basic neutralizing agent in deionized water, adding surfactant B1 and surfactant B2, stirring uniformly, adding surfactant A and stirring to dissolve, adding an auxiliary agent, and wrapping with a PVA film to obtain a finished gel ball.

7. A method for producing a highly stable, environmentally friendly gel ball according to claim 6, characterized in that the temperature is lowered to 50°C or below before adding the aforementioned auxiliary agent.

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