Highly stable, environmentally friendly gel balls and their manufacturing method

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 daily detergents, and particularly relates to highly stable, environmentally friendly gel balls and a method for producing the same. [Background technology]

[0002] As the economy develops and consumption levels rise, the product form of textile detergents has also evolved and changed. They evolved from soap to detergent and then to laundry liquid in recent years. By 2015, P&G launched China's first new laundry product, gel balls. Gel balls are a new generation of textile laundry product characterized by their concentration, convenience, strong decontamination power, easy rinsing, and metered-dose packaging. The industry standard QB / T5658 was released in 2021. The gel ball industry standard QB / T5658 and its production, storage, and transportation requirements dictate that gel balls must meet requirements for stress resistance, decontamination power, and solubility, which has led to significant differences between gel balls and regular laundry liquid.

[0003] When it comes to gel balls, consideration must be given not only to the gelling problem caused by surfactant blending, but also to the compatibility of the gel ball inner solution with the aqueous membrane, i.e., the stability of the gel ball product. For typical gel balls, the gelling problem can generally be solved by rationally blending anionic and nonionic surfactants and adding a large amount of solvent to form a uniform and stable gel ball inner solution. However, due to limited compatibility with the aqueous membrane, it is necessary to add a large amount of organic solvent to the gel ball inner solution to prevent gelling, ensure good compatibility with the aqueous membrane, and avoid affecting the stability of the gel ball. This organic solvent not only increases production costs, but also contributes little to the cleaning function. For natural gel balls, there are fewer natural solvents and surfactants to choose from. Many natural anionic surfactants contain a large amount of water, and given the unstable interaction between the water content and the aqueous membrane, these raw materials are not suitable for producing highly natural gel balls. Furthermore, bases made using only naturally derived nonionic surfactants tend to gel easily and undergo large changes in viscosity, making it difficult to close the film, making it impossible to produce stable, highly natural gel balls.

[0004] For example, Patent Publication CN111040894A discloses mini gel balls containing numerous organic solvents and surfactants derived entirely from the petrochemical industry. Patent Publication CN105861193B discloses a natural soda laundry liquid, which uses naturally occurring surfactants, but incorporates many non-natural inorganic salts. The overall product composition is primarily anionic, making it unsuitable for gel ball products. Patent Publication CN109957470A discloses a concentrated baby laundry liquid containing natural amino acid surfactants and a method for producing the same. While the types and range of raw materials included in this publication allow for the production of a relatively natural gel ball base, the absence of organic solvents and the use of many long-carbon-chain aliphatic alcohol surfactants result in poor stability of the resulting base. For these reasons, many of the disclosed inventions fail to mention features related to natural, organic-solvent-free gel ball products.

[0005] For the reasons stated above, a major issue and challenge in this field is how to use natural carbon-derived surfactants with cleaning effects instead of organic solvents and surfactants derived entirely from the petrochemical industry for gel balls that are naturally derived and do not contain added organic solvents.

[0006] Therefore, in order to solve the above problems, the present invention provides technical means relating to a highly stable, environmentally friendly gel ball. Summary of the Invention [Problem to be solved by the invention]

[0007] To overcome the shortcomings of the prior art, 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 the organic solvents and surfactants derived entirely from the petrochemical industry in the prior art. [Means for solving the problem]

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

[0009] The highly stable, environmentally friendly gel ball contains the following components in the following mass fractions: Surfactant A 10% to 60% Surfactant B 10% to 50% Basic neutralizer 0.01%~10% Auxiliary agent 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 the Alkyl Glucoside AG series of products from AkzoNobel.

[0010] Preferably, said 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 the group consisting of sodium ion, potassium ion, and calcium ion.

[0012] Preferably, the surfactant B2 can be selected from the Elfan range of products from AkzoNobel.

[0013] Preferably, said surfactant B2 is selected from Elfan AT84C.

[0014] Furthermore, the surfactant A is one or more selected from fatty acids, cocoyl glycinates, fatty acid methyl ester sulfonates, fatty alcohol alkoxides, and polyoxyethylene oleates.

[0015] Furthermore, the fatty acids include 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 acid is one or more selected from linoleic acid, linolenic acid, and arachidonic acid.

[0017] Furthermore, the structural formula of the cocoyl glycine salt is as follows: [ka] Here, the aliphatic alcohol moiety is selected from natural origin, n is 6 to 18, and R is preferably Na+ or K+.

[0018] Preferably, the cocoyl glycinate can be selected from the cocoyl glycinate series of Korea Miwon Trading Co., Ltd. or Sino Lion Co., Ltd.

[0019] Furthermore, the structural formula of the fatty acid methyl ester sulfonate is as follows: [ka] Here, the fatty acid moiety R is selected from natural origin, M+ is preferably Na+, K+, NH4+, and the fatty acid has 8 to 18 carbon atoms.

[0020] Preferably, the fatty acid methyl ester sulfonate may be selected from HC-based products of Malaysian Petroleum Company, such as HC701 and HC501.

[0021] Furthermore, the general formula of the aliphatic alcohol alkoxide is as follows: [ka] wherein the fatty alcohol moiety is selected from natural sources, n is 8-20, x represents the average degree of ethoxylation and is 1-16, and y is the degree of ethoxylation and is 0-16.

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

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

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

[0025] Preferably, said surfactant A is selected from the following compositions: fatty acids, ECOBrijO10, AEO7, GENAPOLEP2454, NS-669, sodium cocoyl glycinate, HC501.

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

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

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

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

[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 hydroxide, oxide, carbonate, and hydrogen carbonate.

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

[0033] Furthermore, the auxiliary agent includes at least one of an enzyme preparation, a regulator, a chelating agent, a colorant, a color stabilizer, and an essence.

[0034] Another object of the present invention is to provide a method for producing highly stable, environmentally friendly gel balls. This method includes the steps of dissolving a basic neutralizer in deionized water at room temperature, adding surfactants B1 and B2 and stirring uniformly, adding surfactant A and stirring to dissolve, waiting until the temperature drops to 50°C or below, adding auxiliary agents and stirring uniformly until the appearance is uniform to obtain a gel ball inner liquid, and wrapping the gel ball inner liquid in a PVA film to obtain a finished gel ball. [Effects of the Invention]

[0035] The highly stable, environmentally friendly gel ball provided by the present invention has the following beneficial effects:

[0036] 1. The present invention combines a plant-derived, non-ethoxylated, sulfate-free anion with a short-carbon-chain alkyl glucoside to form a composite surfactant, resulting in excellent synergy, good compatibility between the components, enhanced dispersibility, and strong solubilization. The resulting gel ball products have a uniform appearance and good high and low temperature stability. They also avoid the risk of "extra-film precipitation" in gel ball products caused by excessive sulfate content in the system. Surprisingly, the gel balls of the present invention also have significantly improved decontamination performance, with P values ​​of 1.08 for carbon black, 1.28 for protein, and 1.17 for sebum, demonstrating significant advances over the prior art. Furthermore, the gel balls of the present invention are characterized by their high water content, which not only reduces overall product costs but also dissolves some of the auxiliary agents and surfactants, stabilizing the formulation and making them effective substitutes for petrochemical-derived solvents in gel ball products. The highly stable, environmentally friendly gel balls of the present invention have the advantages of high naturalness, high active substance content, high stability, and excellent cleaning effect, and have good application prospects.

[0037] 2. The present invention also uses a surfactant composition instead of an organic solvent, allowing the gel ball filling to have highly concentrated properties. Furthermore, all of the surfactants used in the present invention are naturally derived. Therefore, the PVA-wrapped gel balls also have the advantages of being highly natural, having a high active ingredient content, high stability, and excellent cleaning performance.

[0038] 3. This invention can completely replace organic solvents with different types of surfactant compositions derived from natural sources, and can combine other natural surfactants, auxiliaries, basic neutralizers, and water to prepare a stable and uniform gel ball filling solution. Through the blending and synergistic action of plant-derived anionic and nonionic surfactants, the final gel ball product is stable and uniform, has good cleaning effect, is high in naturalness and active ingredient content, and is environmentally friendly. DETAILED DESCRIPTION OF THE INVENTION

[0039] In order to more clearly explain the technical solution of the present invention, the following examples are given. Unless otherwise specified, the raw materials, reaction and post-treatment means shown in the examples are all common raw materials on the market and technical means well known to those skilled in the art.

[0040] In the present invention, "naturally derived" means that the carbon-containing structure of the carbon-containing raw material used is naturally derived. The natural index (RCI) in the present invention is the renewable carbon index, and the natural index (RCI) of a raw material is the ratio of the number of renewable carbon atoms to the total number of carbon atoms in its structure, and the natural index (RCI) of a product is the ratio of renewable carbon atoms to total organic carbon in the product.

[0041] In the present embodiment, surfactant B1 can be selected from the Alkyl Glucoside AG series of products from AkzoNobel.

[0042] In the present embodiment, surfactant B1 is preferably AG6206 or AG6202.

[0043] Surfactant B2 in this embodiment of the invention can be selected from the Elfan range of products from AkzoNobel.

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

[0045] The cocoyl glycinate in the embodiment of the present invention can be selected from the cocoyl glycinate series of Korea Miwon Trading Co., Ltd. or Sino Lion Co., Ltd.

[0046] In the embodiment of the present invention, the fatty acid methyl ester sulfonate may be selected from HC-based products of Malaysian Petroleum Company, such as HC701 and HC501.

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

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

[0049] [Table 1]

[0050] The method for producing the gel balls of Examples 1 to 3 includes the following steps.

[0051] The method for producing the above gel balls involves dissolving the basic neutralizer in deionized water at room temperature, adding surfactant B1 and surfactant B2 according to their mass fractions, stirring uniformly, then adding surfactant A according to their mass fractions and stirring to dissolve, waiting until the temperature drops to 50°C or below, adding the auxiliary agents according to their mass fractions, stirring uniformly until the appearance is uniform, to obtain a gel ball inner liquid, which is then wrapped in PVA film to obtain the finished gel balls.

[0052] Comparative Examples 1 to 5 were set 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: in comparative example 1, an organic solvent and an excess of inorganic base were added and the content of surfactant B was reduced; in comparative example 2, an organic solvent was added and the ratio of surfactant B1 to surfactant B2 was adjusted; in comparative example 3, an organic solvent was added but no surfactant B1 was added; in comparative example 4, a large amount of organic solvent was added; and in comparative example 5, a large amount of solubilization raw material was added.

[0055] Test Example 1

[0056] A stability test was conducted on the appearance of the gel balls of Examples 1 to 3 and Comparative Examples 1 to 5 during storage, and the specific test method and evaluation criteria were as follows.

[0057] High-temperature stability: Place the gel balls in the designated packaging and place them in an environment of 45°C ± 1°C. After leaving them at a constant temperature for one month, they are allowed to return to room temperature of 25°C ± 5°C. If there is no significant change in the appearance of the gel balls, no breakage or leakage, and no phase separation, cloudiness, gelation, or precipitation in the liquid inside the gel balls, they pass the high-temperature stability test.

[0058] Low-temperature stability: The gel balls are placed in their designated packaging and placed in an environment of -5°C ± 2°C. After leaving them at this constant temperature for one month, they are removed and immediately observed. If there is no significant change in the appearance of the gel balls, no breakage or leakage, and no phase separation, cloudiness, gelation, or precipitation in the liquid inside the gel balls, they pass the low-temperature stability test.

[0059] Freeze-thaw cycle stability: Gel balls were placed in their designated packaging and placed in an environment between -15°C and -20°C. After 24 hours at constant temperature, they were removed and placed in a room temperature environment of 25°C ± 5°C for 24 hours. This cycle was repeated five times, and the composition was observed after each cycle. This experiment was a freeze-thaw cycle test. If there was no significant change in the appearance of the gel ball, no breakage or leakage, and no phase separation, cloudiness, gelation, or precipitation in the liquid inside the gel ball, it was deemed to have passed the low-temperature stability test.

[0060] Room temperature stability: Place the gel balls in the designated packaging and place them in a room temperature environment (20℃~30℃). After leaving them for one month, 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, they pass the room temperature stability test.

[0061] The results of measuring the stability and uniformity of the gel balls in the examples of the present invention and the comparative examples are shown in Table 3. The naturalness of the composition was measured as follows: Renewable Carbon Index (RCI) of product composition = number of renewable carbons in the composition / number of total organic carbons × 100%.

[0062] [Table 3]

[0063] As is clear from Table 3, Examples 1 to 3 use many naturally derived ingredients and therefore have a high degree of naturalness (RCI > 60%). The stability test results for Examples 1 to 3 demonstrate that the gel balls of Examples 1 to 3 ensure sample stability at each test temperature. Furthermore, the inventors discovered the following during their experiments: Although Examples 1 to 3 incorporate a large amount of free water into their compositions, resulting in an overall water content of 15% or greater, the long-term weight loss rate of the gel ball products wrapped in PVA film during storage was ultimately 15% or less, thereby meeting the weight stability requirements for gel balls in QB / T5658.

[0064] In Comparative Example 1, sample precipitation occurred due to excessive addition of inorganic base and insufficient addition of surfactant B (including AG6202, AG6206, and Elfan AT84C). In Comparative Example 2, the gel balls were soft and crumbled, and stress resistance was poor due to an issue with the blending ratio of surfactant B1 (AG6202, AG6206) and surfactant B2 (Elfan AT84C). In Comparative Example 3, gelation occurred in the sample due to an issue with the blending of each surfactant component and the absence of surfactant B1 (including AG6202 and AG6206). On the other hand, in Comparative Examples 4 and 5, a common surfactant was used and a certain amount of organic solvent was added, resulting in a high surfactant content in the gel balls themselves. Although the overall clarity decreased to some extent, the results were basically acceptable. Furthermore, the naturalness of the overall composition was low due to the type of surfactant selected.

[0065] Test Example 2

[0066] The decontamination ability of Examples 1-3 and Comparative Examples 4-5 was tested in accordance with GB / T 13174 2008, "Measurement of Decontamination Ability and Circulation Washing Performance of Laundry Detergents." The amount of sample added during the decontamination test conformed to the requirements of QB / T 5658 Gel Ball. The results 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 liquid is used as the 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 liquid. A higher P value indicates better detergency. The stability of Comparative Examples 1-2 all failed the test, exhibiting obvious softening, crumbling, phase separation, gelation, or cloudiness, making this test unnecessary. The test results are shown in Table 4.

[0067] [Table 4]

[0068] As can be seen from Table 4, the gel balls of the examples were significantly better at decontaminating carbon black, protein, and sebum than the standard laundry detergent and comparative examples 4 and 5. Comparative examples 4 and 5 had low naturalness and some reduction in clarity, but had a high total surfactant content and strong decontamination power. The gel balls of the examples of the present invention had high decontamination power and significantly better overall washing performance than the standard laundry detergent and comparative examples.

[0069] It will be apparent to those skilled in the art that the present invention is not limited to the details of the illustrative embodiments set forth above, and that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. Therefore, in all respects, the embodiments are to be considered illustrative and not restrictive. The scope of the present invention is limited by the appended claims, rather than the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are intended to be embraced therein.

[0070] Although this specification is described according to the embodiments, each embodiment does not necessarily include only one independent technical means. This description in this specification is for the purpose of clarity, and those skilled in the art should understand the specification as a whole, and the technical means in each embodiment may be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A highly stable, environmentally friendly gel ball, The highly stable, environmentally friendly gel ball contains the following components in the following mass fractions: Surfactant A 10% to 60% Surfactant B 10% to 50% Basic neutralizer 0.01% to 10% Auxiliary agent 0.1% to 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, 【Chemical 1】 【Chemistry 2】 The surfactant B2 is represented by the general formula of Structural Formula III: 【Chemistry 3】 Here, R is selected from the group consisting of sodium ions, potassium ions, and calcium ions, making this a highly stable, environmentally friendly gel ball.

2. 2. The highly stable, environmentally friendly gel ball according to claim 1, wherein the surfactant A is one or more selected from the group consisting of fatty acids, cocoyl glycinates, fatty acid methyl ester sulfonates, fatty alcohol alkoxides, and polyoxyethylene oleate esters.

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

4. 2. The highly stable, environmentally friendly gel ball according to claim 1, wherein the weight ratio of surfactant B1 to surfactant B2 is 1 to 10:

1.

5. 2. The highly stable, environmentally friendly gel ball according to claim 1, wherein the basic neutralizing agent is an inorganic basic neutralizing agent.

6. 6. The highly stable, environmentally friendly gel ball according to claim 5, wherein the cation of the inorganic neutralizing agent is at least one selected from the group consisting of sodium ions, potassium ions, calcium ions, and magnesium ions, and the anion of the inorganic neutralizing agent is at least one selected from the group consisting of hydroxides, oxides, carbonates, and bicarbonates.

7. 2. The highly stable, environmentally friendly gel ball according to claim 1, wherein the auxiliary agent comprises at least one of an enzyme preparation, a regulator, a chelating agent, a colorant, a color stabilizer, and an essence.

8. 2. The highly stable, environmentally friendly gel ball according to claim 1, wherein the water content is ≥ 15 wt%.

9. The method for producing highly stable, environmentally friendly gel balls according to any one of claims 1 to 8, 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 the resulting mixture in a PVA film to obtain a finished gel ball product.

10. 10. The method for producing a highly stable, environmentally friendly gel ball according to claim 9, wherein the temperature must be lowered to 50°C or less before the auxiliary agent is added.

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