A water-swellable material based on natural sources, a sheet laundry product and a method for preparing the same

Abstract

The application belongs to the field of daily chemicals, and discloses a water-swellable material based on natural sources for sheet-shaped washing products, which comprises an anionic film-forming agent and a non-ionic film-forming agent; the anionic film-forming agent is composed of carboxymethyl chitosan and carboxymethyl starch sodium; the non-ionic film-forming agent is guar gum; and the weight ratio of the anionic film-forming agent to the non-ionic film-forming agent is 40-60:0.2-1. The material adopts the anionic film-forming agent to form a main body, adopts the non-ionic film-forming agent and the anionic film-forming agent to form a water absorption network, so that a polymer film can be quickly swelled to release surfactants, and the shortcomings of slow water absorption and slow collapse of a traditional film product prepared from natural source raw materials are effectively overcome, and the loading capacity of surfactants can reach 30% or more. Meanwhile, the application also discloses a sheet-shaped washing product and a preparation method thereof.

Description

Technical Field

[0001] This invention relates to the field of daily chemical products, and more particularly to a water-swellable material based on natural sources, a sheet detergent product, and a method for preparing the same. Background Technology

[0002] Dishwashing sheets and laundry sheets, as a new type of detergent product, are a commercially promising new product following laundry pods; the following literature discloses the scheme of sheet-type detergent products:

[0003] Publication No. 202311593105.8, the subject of which is a soft stain-removing laundry composition and its preparation method and laundry sheets;

[0004] Publication No. 202211492081.2, the subject of which is a three-dimensional composition detergent tablet and its preparation method;

[0005] The water-soluble membranes used in the aforementioned sheet detergent products are all polymers such as polyvinyl alcohol and polyvinylpyrrolidone;

[0006] Currently, there is no mature dishwashing sheet on the domestic market; while the demand from overseas customers is that the raw materials for sheet-type dishwashing products should be as natural as possible or mostly natural or modified natural products to improve the environmental friendliness of the products.

[0007] As is well known, plant-derived water-soluble polymers such as starch and polysaccharides have significant performance differences from polyvinyl alcohol and polyvinylpyrrolidone. The former absorbs water slowly, disintegrates slowly, and has poor surfactant loading capacity.

[0008] Therefore, the technical problem solved by this invention is: how to prepare a water-swellable thin film material that can effectively load surfactants and is prepared from naturally sourced raw materials. Summary of the Invention

[0009] The purpose of this invention is to provide a water-swellable material based on natural sources for sheet detergent products. This material uses an anionic film-forming agent as the main body and a water-absorbing network composed of a nonionic film-forming agent and anionic film-forming agent, which enables the polymer film to swell rapidly to release surfactants. This effectively overcomes the shortcomings of traditional film products made from natural raw materials, such as slow water absorption and slow disintegration. At the same time, the surfactant loading can reach 30% or more.

[0010] Meanwhile, the present invention also discloses a sheet-like detergent product and its preparation method.

[0011] To achieve the above objectives, this application discloses:

[0012] A water-swellable material based on natural sources for use in sheet detergent products, comprising anionic and nonionic film-forming agents;

[0013] The anionic film-forming agent is composed of carboxymethyl chitosan and sodium carboxymethyl starch; the nonionic film-forming agent is guar gum.

[0014] The weight ratio of the anionic film-forming agent to the nonionic film-forming agent is 40-60:0.2-1.

[0015] In the research process of this invention, carboxymethyl chitosan was first used to prepare a film. It was found that the film dissolved very slowly after being loaded with surfactant, which could not meet the working requirements of the dishwasher.

[0016] In subsequent research, we found that by combining carboxymethyl chitosan and sodium carboxymethyl starch, the water absorption and disintegration rates increased significantly, but this was only limited when the surfactant content was less than 20%. When the surfactant content exceeded 20%, the water absorption and disintegration rates decreased significantly. The reason why it performed better than carboxymethyl chitosan alone is that sodium carboxymethyl starch swells but does not dissolve after absorbing water, and its swelling rate is significantly better than that of carboxymethyl chitosan. It can quickly support the polymer network of the film based on electrostatic repulsion.

[0017] To address the shortcomings of current research on water-swellable materials, such as slow disintegration, slow swelling, and low surfactant loading, we further optimized the above formulation. By using a nonionic film-forming agent, the negative repulsion of the anionic film-forming agent supports the swelling network. Combined with the long-chain structure of the nonionic film-forming agent, the negative repulsion thickening network is reinforced. Another characteristic of the nonionic film-forming agent is its extremely rapid swelling and solubility, which can initially support the thickening network of the film, allowing water to enter the network, promoting the ionization of the anionic film-forming agent, increasing the swelling and disintegration rate of the film, and effectively leveraging the rapid disintegration characteristics of sodium carboxymethyl starch. This effectively suppresses the influence of surfactants on the performance of sodium carboxymethyl starch and increases the surfactant loading.

[0018] Through the above optimizations, the goal of using all naturally sourced raw materials was achieved, resulting in higher surfactant loading and faster surfactant release.

[0019] In the above-mentioned water-swellable material, the weight ratio of carboxymethyl chitosan to sodium carboxymethyl starch is 4 to 6:2.

[0020] The water-swellable material mentioned above also includes glycerin, and the weight ratio of the anionic film-forming agent to glycerin is 40-60:4-6.

[0021] Glycerin plays two roles in water-swellable materials: a softener and a plasticizer. By using glycerin, films can be made softer and more resilient, improving the yield rate of film production and reducing losses during storage, transportation, and use.

[0022] The water-swellable material mentioned above is composed of carboxymethyl chitosan, sodium carboxymethyl starch, nonionic film-forming agent, and glycerin.

[0023] The weight ratio of the anionic film-forming agent, the nonionic film-forming agent, and glycerin is 45-60:0.2-1:4-6.

[0024] In the above-mentioned water-swellable material, the weight ratio of carboxymethyl chitosan, sodium carboxymethyl starch, nonionic film-forming agent, and glycerin is 45-55:0.4-0.8:4.5-5.5.

[0025] Meanwhile, the present invention also discloses a sheet-like detergent product, comprising the water-swellable material as described above and a surfactant; the surfactant is free of cationic surfactants;

[0026] The water-swellable material forms a sheet carrier for the sheet-like detergent product; the surfactant is loaded onto the sheet carrier;

[0027] The weight ratio of the water-swellable material to the surfactant is 46.2–67:25–35.

[0028] In the above-mentioned sheet detergent products, the surfactant is an anionic surfactant, or a combination of anionic and nonionic surfactants;

[0029] The anionic surfactant is one or more of the following: sodium α-olefin sulfonate, sodium dodecyl sulfate, sodium fatty acid methyl ester sulfonate, sodium stearate, sodium dodecyl polyether sulfate, and sodium fatty acid methyl ester ethoxysulfonate.

[0030] The nonionic surfactant is one or more of fatty alcohol polyoxyethylene ether, cocoamide, and alkyl glycoside.

[0031] In the above-mentioned sheet detergent products, the anionic surfactant accounts for 80-100 wt% of the surfactant;

[0032] The sheet-shaped detergent product is a dishwashing sheet.

[0033] Finally, the present invention also discloses a method for preparing a sheet-like detergent product as described in any of the above, comprising the following steps:

[0034] Step 1: Add the anionic film-forming agent and the nonionic film-forming agent to the acetic acid solution and dissolve them at 40-60°C;

[0035] Step 2: Add the surfactant to the solution from Step 1 to dissolve and disperse it;

[0036] Step 3: Pour and dry the product obtained in Step 2 to obtain a sheet-like detergent product.

[0037] In the above preparation method, the acetic acid concentration in the acetic acid solution is 2 wt%; the acetic acid solution accounts for 70-80 wt% of the total weight of the water-swellable material, surfactant, and acetic acid solution.

[0038] This application has at least the following beneficial effects:

[0039] This invention uses an anionic film-forming agent as the main body and a nonionic and anionic film-forming agent to form a water-absorbing network, enabling the polymer film to swell rapidly to release surfactants. This effectively overcomes the shortcomings of traditional films made from naturally sourced raw materials, such as slow water absorption and slow disintegration. At the same time, the surfactant loading can reach 30% or more. Attached Figure Description

[0040] Figure 1 This is a still photograph of the dishwashing disc of the present invention;

[0041] Figures 2 to 4 The state of the ceramic dish, stainless steel bowl, and glass container before the test;

[0042] Figures 5 to 7 The photo shows the test results of Example 3;

[0043] Figures 8 to 10 The image shows the test results of Example 6;

[0044] Figures 11 to 13 Photographs showing the test results for Comparative Example 1;

[0045] Figures 14 to 16 Photographs showing the test results for Comparative Example 2;

[0046] Figures 17 to 19 Photographs showing the test results for Comparative Example 3;

[0047] Figures 20 to 22 Photographs showing the test results for Comparative Example 4;

[0048] Figures 23 to 25 This is a photograph of the test results for Comparative Example 5.

[0049] Specific implementation methods

[0050] The present invention will now be clearly and completely described in conjunction with embodiments thereof. It should be noted that, unless otherwise specified in the embodiments, conditions are performed under conventional conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products. Unless otherwise specified, all parts used in the embodiments of the present invention are parts by weight.

[0051] Examples and Comparative Examples

[0052] A method for preparing dishwashing tablets includes the following steps:

[0053] Step 1: Add the anionic film-forming agent and the nonionic film-forming agent to the acetic acid solution and dissolve them at 50°C; the acetic acid concentration in the acetic acid solution is 2wt%; the amount of acetic acid solution used is 80wt% of the total weight of the acetic acid solution, anionic film-forming agent, nonionic film-forming agent, glycerin, and surfactant.

[0054] After the film-forming agent is evenly dispersed, add glycerin and continue stirring. After stirring evenly, proceed to step 2.

[0055] Step 2: Add the surfactant to the solution from Step 1 to dissolve and disperse it;

[0056] Step 3: Pour and dry the product obtained in Step 2 to obtain a sheet-like detergent product.

[0057] The specifications of the sheet detergent product are: thickness 1mm; length * width 100mm * 40mm.

[0058] The relevant formulas can be found in Table 1;

[0059] Table 1 Formula Table (Unit: g)

[0060]

[0061] Product appearance reference in Example 3 Figure 1 .

[0062] Comparative Example 6

[0063] It is largely the same as Example 3, except that sodium carboxymethyl cellulose is used to replace carboxymethyl chitosan by weight.

[0064] Performance testing

[0065] The test consists of three parts: static swelling rate test; dynamic swelling rate test; and washing performance test.

[0066] The test method for static swelling rate is as follows: place one dishwashing tablet in 1L of tap water and observe the time required for it to completely swell until the film shape is no longer clearly visible to the naked eye; in the static swelling test, more than 30 seconds is counted as 1 minute, and less than 30 seconds is counted as 0 minutes.

[0067] The test method for dynamic swelling rate is as follows: Place one dishwashing tablet in a 1L container containing 1L of tap water, and continuously add tap water from an external source to the container at a rate of 0.5L / min. Observe the time required for it to completely swell until the film morphology is no longer clearly visible to the naked eye; the timing for dynamic swelling test is accurate to the second.

[0068] Washing performance test: set up blank group, meat, egg and grease stain group, Maillard reaction stain group, sugar and oil mixture stain group; each group is equipped with ceramic plate, stainless steel bowl and glass container;

[0069] The formula for the meat, egg, and grease stain group is: 1g egg liquid, 1g cooking oil, and 0.2g cornstarch;

[0070] The Maillard reaction staining kit is formulated as follows: 2g cooking oil, 0.2g cornstarch, and 1g soy sauce;

[0071] The recipe for the sugar-oil mixture stain group is: 2g chocolate, 1g butter, 1.5g cornstarch, and 1.5g milk;

[0072] The washing program is as follows: the dishwasher is set to the heavy-duty wash mode, and the washing time is 48 minutes.

[0073] The dishwasher tablets used in the washing performance test were derived from Examples 3, 6, Comparative Examples 1 to 4 and Comparative Example 6, with a size of 1mm*100mm*40mm and a weight of approximately 2.15±0.15g.

[0074] The test results are shown in Table 2 below and attached. Figure 2 To be continued Figure 25 ;

[0075] Figures 2 to 4 The ceramic dish, stainless steel bowl, and glass container are shown in their state before the test. To save space, only one set of tests is shown in their state before the test; the other tests are similar.

[0076] Figures 5 to 7 The photo shows the test results of Example 3;

[0077] Figures 8 to 10 The image shows the test results of Example 6;

[0078] Figures 11 to 13 Photographs showing the test results for Comparative Example 1;

[0079] Figures 14 to 16Photographs showing the test results for Comparative Example 2;

[0080] Figures 17 to 19 Photographs showing the test results for Comparative Example 3;

[0081] Figures 20 to 22 Photographs showing the test results for Comparative Example 4;

[0082] Figures 23 to 25 Photographs showing the test results for Comparative Example 6;

[0083] Table 2 Results of swelling rate test

[0084] Example 1 16 3min42s Example 2 20 3min50s Example 3 18 3min35s Example 4 18 3min40s Example 5 19 4min10s Example 6 18 3min38s Example 7 15 3min17s Example 8 21 5min01s Comparative Example 1 37min 12min19s Comparative Example 2 27min 8min27s Comparative Example 3 28min 8min11s Comparative Example 4 35min 11min22s Comparative Example 5 - - Comparative Example 6 41min 13min53s

[0085] Results analysis:

[0086] 1. Through the appendix Figure 2 To be continued Figure 25 As can be seen, the dishwashing sheets of Examples 3 and 6 of the present invention can effectively remove stains from the meat and egg grease stain group, the Maillard reaction stain group, and the sugar and oil mixture stain group. The effect of Example 3 is slightly better than that of Example 6. Water droplets are present in the stainless steel bowl of Example 6, which is more obvious in the meat and egg grease stain group and the sugar and oil mixture stain group. However, both Example 3 and Example 6 have significantly better washing effects compared with other comparative cases. The swelling time data of Examples 3 and 6 show that they can swell and disintegrate quickly to release surfactants, which is an important factor in their good cleaning effect.

[0087] 2. Through the appendix Figure 2 To be continued Figure 25It is evident that the washing effects of Comparative Examples 1 to 4 and Comparative Example 6 are all somewhat inadequate. Comparative Example 5, which did not undergo washing or swelling tests, showed poor flexibility and exhibited significant flaking during use, thus qualifying as a substandard sample. The swelling experiments of Comparative Examples 1 to 4 and Comparative Example 6 revealed that neither Comparative Example 1, using only carboxymethyl chitosan, nor Comparative Example 4, using a mixture of carboxymethyl chitosan and guar gum, showed a significant improvement in swelling speed. This indicates that sodium carboxymethyl starch is crucial for disintegration, exhibiting more rapid water absorption, swelling, and disintegration. However, using only sodium carboxymethyl starch, as in Comparative Example 4, results in poor sheet flexibility. Comparative Example 2 used sodium carboxymethyl starch to replace carboxymethyl chitosan, which effectively shortened the swelling time. Comparative Example 3 used xanthan gum, which has similar properties to guar gum. Since xanthan gum has a certain amount of carboxyl groups, it belongs to plant polysaccharide gum with a small amount of anionic groups. Although both are plant polysaccharide gums, the replacement of guar gum with xanthan gum did not show a substantial improvement in swelling performance compared to Comparative Example 2. Comparative Example 6 used sodium carboxymethyl cellulose, which is also an anionic film-forming agent, to replace carboxymethyl chitosan. Even in the presence of sodium carboxymethyl starch and guar gum, its swelling performance was worse. The possible reason is that sodium carboxymethyl cellulose has too strong a film-forming property, and its water absorption and swelling rate is much slower than that of carboxymethyl chitosan.

[0088] The experimental results above show that by using anionic film-forming agents as the main body and nonionic and anionic film-forming agents to form a water-absorbing network, the polymer film can swell rapidly to release surfactants. This effectively overcomes the shortcomings of traditional films made from natural raw materials, such as slow water absorption and slow disintegration. At the same time, the surfactant loading can reach 30% or more.

[0089] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description; thus, all changes falling within the meaning and scope of the claims are intended to be embraced within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

Claims

1. A sheet-like detergent product, characterized in that, The product includes a water-swellable material and a surfactant; the surfactant is free of cationic surfactants; the water-swellable material forms a sheet carrier for the sheet-like detergent product; the surfactant is loaded onto the sheet carrier; the weight ratio of the water-swellable material to the surfactant is 46.2–67:25–35. The water-swellable material includes anionic and nonionic film-forming agents; the anionic film-forming agent is composed of carboxymethyl chitosan and sodium carboxymethyl starch; the nonionic film-forming agent is guar gum; the weight ratio of the anionic and nonionic film-forming agents is 40-60. 0.2–1, wherein the weight ratio of carboxymethyl chitosan to sodium carboxymethyl starch is 4–6:2; the surfactant is anionic surfactant, or a combination of anionic and nonionic surfactant; the anionic surfactant is one or more of sodium α-olefin sulfonate, sodium dodecyl sulfate, sodium fatty acid methyl ester sulfonate, sodium stearate, sodium dodecyl polyether sulfate, and sodium fatty acid methyl ester ethoxysulfonate; the nonionic surfactant is one or more of fatty alcohol polyoxyethylene ether, cocoamide, and alkyl glycoside.

2. The sheet-like detergent product according to claim 1, characterized in that, The water-swellable material also includes glycerin, and the weight ratio of the anionic film-forming agent to glycerin is 40-60:4-6.

3. The sheet-like detergent product according to claim 2, characterized in that, The water-swellable material is composed of carboxymethyl chitosan, sodium carboxymethyl starch, a nonionic film-forming agent, and glycerin; the weight ratio of the anionic film-forming agent, the nonionic film-forming agent, and glycerin is 45-60. 0.2～1：4～6。 4. The sheet-like detergent product according to claim 3, characterized in that, The weight ratio of carboxymethyl chitosan, sodium carboxymethyl starch, nonionic film-forming agent, and glycerin is 45-55:0.4-0.8:4.5-5.

5.

5. The sheet-like detergent product according to claim 1, characterized in that, The surfactant comprises 80-100 wt% anionic surfactant; the sheet detergent product is a dishwashing sheet.

6. A method for preparing a sheet-like detergent product as described in claim 1 or 2, characterized in that, The process includes the following steps: Step 1: Add anionic and nonionic film-forming agents to an acetic acid solution and dissolve them at 40-60°C; Step 2: Add surfactants to the solution in Step 1 and dissolve and disperse them; Step 3: Cast and dry the product obtained in Step 2 to obtain a sheet-like detergent product.

7. The preparation method according to claim 6, characterized in that, The acetic acid concentration in the acetic acid solution is 2 wt%; the acetic acid solution accounts for 70-80 wt% of the total weight of the water-swellable material, surfactant, and acetic acid solution.

Images