Composite thickening agent capable of being used for quaternary ammonium salt system in weak acid environment

Abstract

The invention provides a composite thickening agent capable of being used for a quaternary ammonium salt system in a weak acid environment, and belongs to the field of thickening agents. The formula comprises cationic guar gum, silicone oil, cationic cellulose and a zwitterionic buffer agent. Through charge synergy of the cationic guar gum and the ester quaternary ammonium salt, network strengthening of the cationic cellulose and pH stability of the zwitterionic buffering agent, the problems of thickening of an organic acid pickling agent containing the quaternary ammonium salt in a weak acid system and compatibility of the organic acid pickling agent containing the quaternary ammonium salt and a quaternary ammonium salt bactericide are solved.

Description

Technical Field

[0001] The present invention relates to the technical field of thickeners, in particular to a composite thickener that can be used in a quaternary ammonium salt system under a weakly acidic environment. Background Art

[0002] As the core preparation for industrial cleaning and metal surface treatment, pickling agents are mainly divided into three categories: inorganic acids, organic acids and composite types.

[0003] Inorganic acids (such as hydrochloric acid, sulfuric acid, and nitric acid) can quickly dissolve metal oxides and stubborn scale due to their strong acidity. For example, hydrochloric acid can effectively remove rust, and sulfuric acid accelerates the reaction at high temperatures. However, their strong corrosiveness can easily damage the metal matrix (especially stainless steel and aluminum, which may cause pitting or stress corrosion). In addition, the cleaning waste liquid often contains toxic components such as chloride ions and nitrites, requiring reliance on corrosion inhibitors and strict control of operating conditions.

[0004] In contrast, organic acids (such as citric acid, EDTA, and glycolic acid) are mildly acidic and dissolve metal oxides through chelation, significantly reducing the risk of matrix corrosion. For example, citric acid can achieve mild rust removal by chelating iron ions during boiler cleaning. Aminosulfonic acid is non-corrosive to galvanized metals, making it the only choice for cleaning galvanized materials.

[0005] The core advantages of organic acids lie in their environmental friendliness and material compatibility: their waste liquids are low in toxicity and partially biodegradable (such as glycolic acid), which meets green industrial standards; they are more adaptable to sensitive materials such as stainless steel and copper alloys. For example, citric acid will not damage the passivation layer when cleaning austenitic steel, and EDTA can complete cleaning and passivation in one step, reducing secondary corrosion. In addition, organic acids can be enhanced through compounding (such as mixing glycolic acid and formic acid to enhance scale dissolving ability) and meet the stringent hygiene requirements of food, medical and other fields (such as food-grade CIP cleaning agents). Although organic acids are relatively expensive, their low pollution and high safety characteristics make them more competitive in precision instruments and environmentally sensitive scenarios. In the future, as compound formulation technology advances, it will further balance efficiency and sustainability needs and become the mainstream direction of high-end manufacturing and green cleaning.

[0006] A thickener needs to be added to the pickling agent to increase the viscosity, thereby enhancing the adhesion of the liquid to vertical surfaces and prolonging the contact time between the acid and dirt or rust stains, thereby improving cleaning efficiency; at the same time, it reduces the risk of acid mist splashing and splattering, thereby improving operational safety.

[0007] However, the acidic thickeners currently used in formulas on the market are mainly for thickening strong acids such as hydrochloric acid. To address the problem of reduced sterilization efficiency after replacing strong acids with weak acids, quaternary ammonium salts are commonly used for compounding. However, this compounding scheme raises new issues for formula thickeners:

[0008] 1) Traditional acidic thickeners such as oleylamine polyoxyethylene ether only have a good thickening effect on strong acids. After thickening, the system is stable and is not prone to thinning during storage (the main mechanism is that in a strong acid environment, oleylamine polyoxyethylene ether forms a stable chemical bond with the acid, and the intermolecular force is strong, which can resist the influence of external factors and maintain the viscosity and performance of the system stable; however, in a weak acid system, the thickening effect is very weak because the hydrogen ion concentration of the weak acid is low, and the interaction with oleylamine polyoxyethylene ether is not as strong as that of the strong acid. The micelle structure formed is unstable, resulting in a low degree of thickening and poor stability. With the passage of time or changes in the environment, phenomena such as viscosity reduction and stratification may occur.

[0009] 2) Most of the formulations on the market that use weak acid as the pickling component use hydrophilic colloids for thickening. However, after compounding with quaternary ammonium salt fungicides, most hydrophilic polymer thickeners are incompatible with quaternary ammonium salts because of the anionic functional groups in their structures.

[0010] At present, there are no thickeners with completely similar formula scenarios on the market. For example, if an organic acid system is used, anionic colloids such as xanthan gum are basically used as thickeners, but the applied formula cannot contain cationic components such as quaternary ammonium salts. Because weak acids themselves have weak bactericidal ability, their bactericidal and sterilization effects in bathrooms and other places are limited. Compound quaternary ammonium salts can greatly compensate for this effect, but they are incompatible with anionic colloids such as xanthan gum. Therefore, organic acid pickling agents can only be compounded quaternary ammonium salts but have no viscosity; or have higher viscosity but cannot be compounded with quaternary ammonium salts. There is currently no solution that can have the best of both worlds. Summary of the Invention

[0011] The present invention provides a composite thickener that can be used in a quaternary ammonium salt system in a weakly acidic environment, so as to fill the current related market gap.

[0012] In a first aspect, the present invention provides a composite thickener comprising the following components calculated by mass percentage:

[0013] 36-48% cationic guar gum

[0014] 24-35% silicone oil

[0015] 3.6-5% cationic cellulose

[0016] 0.18-0.45% zwitterionic buffer;

[0017] The thickener is dissolved in the alcohol solvent.

[0018] The silicone oil is cationic silicone oil or non-ionic silicone oil.

[0019] Preferably, the silicone oil is a cationic silicone oil

[0020] More preferably, the silicone oil is a non-terminated cationic silicone oil.

[0021] More preferably, the silicone oil is amino silicone oil.

[0022] Preferably, the alcohol solvent is a C2-C9 alcohol.

[0023] More preferably, the alcohol solvent is a C7-C9 long-chain alcohol.

[0024] Preferably, the zwitterionic buffer is 2-morpholineethanesulfonic acid and / or 3-morpholinepropanesulfonic acid.

[0025] In a second aspect, the present invention further provides the use of the aforementioned composite thickener in an organic acid pickling agent containing a quaternary ammonium salt disinfectant.

[0026] Preferably, the acid is added to the organic acid pickling agent in the form of being pre-dissolved in an alcohol solvent.

[0027] Preferably, the addition amount of the present invention is 0.1-1.5% of the total mass of the pickling agent to adjust the viscosity to be within 100-2000 mPa·s.

[0028] The present invention adopts cationic guar gum and ester-based quaternary ammonium salt (both of which are cationic or non-ionic structures) as core thickening components, avoiding the charge conflict problem between traditional anionic thickeners and quaternary ammonium salts, achieving efficient compounding of quaternary ammonium salt bactericides in weak acid systems, and solving the pain point of "thickening and bactericidal cannot coexist".

[0029] Cationic guar gum uses the positive charge of its quaternary ammonium groups to bind to negatively charged fibers or particles (such as quaternary ammonium fungicides), forming a stable hydrogen bond and electrostatic adsorption network. The mannose-galactose structure in its backbone provides physical crosslinking points, enhancing system viscosity. Its charge is compatible with quaternary ammonium fungicides, avoiding the precipitation issues associated with traditional anionic thickeners (such as xanthan gum). The quaternary ammonium groups in the pickling agent synergize with the cationic guar gum to form a cationic network, improving viscosity stability. The hydrogen bonds between the quaternary ammonium groups and the guar gum complement each other, forming a three-dimensional network. The hydroxyethyl group enhances water solubility and improves low-temperature stability.

[0030] Cationic silicone oil can remain stable under acidic conditions of pH 4-6, and the positive charge adsorbs on the metal surface to form a dense membrane structure, thereby improving thickening efficiency and durability.

[0031] The advantages of non-ionic silicone oils are wide pH adaptability, no charge restrictions, and can be compounded with anionic / cationic systems without charge repulsion issues, making them suitable for complex formulations. Different silicone oils can be selected according to the specific pH and concentration of the pickling agent.

[0032] The active groups at the end of the non-terminated silicone oil molecular chain (such as hydroxyl and amino) can cross-link quickly, and a small amount of addition can significantly increase the viscosity; and after thickening, the fluidity and anti-splashing properties are better.

[0033] Zwitterionic buffers maintain charge balance through the buffering effect of sulfonic acid groups and morpholine rings, preventing cationic components from aggregating due to pH fluctuations and ensuring the charge stability of cationic components under weak acid conditions.

[0034] Alcohols are used as solvents to pre-dissolve the various components, ensuring that the thickener dissolves quickly in the acidic medium and avoiding local agglomeration or uneven viscosity. At the same time, if long-chain alcohols are used, they also have a defoaming effect, destroying the foam film by reducing surface tension and reducing the negative impact on viscosity.

[0035] The invention solves the problem of compatibility between thickening and quaternary ammonium salt fungicide in a weak acid system by utilizing the charge synergy of cationic guar gum and ester-based quaternary ammonium salt, network strengthening of cationic cellulose, and pH stabilization of a zwitterionic buffer. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is the effect of the composite thickener provided in Example 1 of the present invention when added to an organic acid pickling agent.

[0037] Figure 2 This is the effect of the composite thickener provided in Example 7 of the present invention when added to an organic acid pickling agent.

[0038] Figure 3 This is the effect of the composite thickener provided in Example 8 of the present invention when added to an organic acid pickling agent. DETAILED DESCRIPTION

[0039] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making any creative efforts shall fall within the scope of protection of the present invention.

[0040] Unless otherwise specified, the experimental methods used in the specific embodiments are all conventional methods, and the materials, reagents, etc. used are all commercially available unless otherwise specified.

[0041] In the present invention, unless otherwise specified, “%” represents mass percentage; the raw materials, reagents, etc. used are all conventional commercially available products.

[0042] The guar gum used in the present invention is guar gum hydroxypropyltrimonium chloride (cationic type) and carboxymethyl guar gum (anionic type).

[0043] The silicone oils used in the present invention are hydroxy silicone oil (non-ionic), amino silicone oil (cationic), and polydimethylsiloxane alcohol (anionic).

[0044] The alcohols used in the present invention are ethanol (C2), n-heptanol (C7), isohexanediol (C8), 1-nonanol (C9), n-undecanol (C10), 11 ).

[0045] The cellulose used in the present invention is cationic cellulose and carboxymethyl cellulose.

[0046] The organic acid pickling agent used in the present invention comprises the following components:

[0047] Citric acid 15%

[0048] Succinic acid 3%

[0049] Oxalic acid 2%

[0050] Didecyldimethylammonium chloride 0.4%

[0051] Water balance.

[0052] Example 1

[0053] A method for preparing a composite thickener comprises the following steps:

[0054] S1 Weighing: Weigh each component according to the following mass parts:

[0055] 36 parts guar hydroxypropyltrimonium chloride

[0056] 24 parts amino silicone oil

[0057] 3.6 parts cationic cellulose

[0058] 0.18 parts of 2-morpholineethanesulfonic acid

[0059] S2 Mixing: Take isohexanediol and add the above components while stirring slowly until a uniform emulsion is formed; the mass ratio of isohexanediol to other components is 1:1; after mixing, seal and set aside.

[0060] Example 2

[0061] A method for preparing a composite thickener comprises the following steps:

[0062] S1 Weighing: Weigh each component according to the following mass parts:

[0063] 42 parts guar hydroxypropyltrimonium chloride

[0064] 30 parts amino silicone oil

[0065] 4.2 parts cationic cellulose

[0066] 0.32 parts of 3-morpholinepropanesulfonic acid

[0067] S2 Mixing: Take n-heptanol and add the above components while stirring slowly until a uniform emulsion is formed; the mass ratio of iso-n-heptanol to other components is 1:1; after mixing, seal and set aside.

[0068] Example 3

[0069] A method for preparing a composite thickener comprises the following steps:

[0070] S1 Weighing: Weigh each component according to the following mass parts:

[0071] 48 parts guar hydroxypropyltrimonium chloride

[0072] 35 parts amino silicone oil

[0073] 5.0 parts cationic cellulose

[0074] 0.45 parts of 3-morpholinepropanesulfonic acid

[0075] S2 Mixing: Take 1-nonanol and add the above components while stirring slowly until a uniform emulsion is formed; the mass ratio of 1-nonanol to other components is 1:1; after mixing, seal and set aside.

[0076] Example 4

[0077] A method for preparing a composite thickener comprises the following steps:

[0078] S1 Weighing: Weigh each component according to the following mass parts:

[0079] 36 parts guar hydroxypropyltrimonium chloride

[0080] 24 parts hydroxy silicone oil

[0081] 3.6 parts cationic cellulose

[0082] 0.18 parts of 2-morpholineethanesulfonic acid

[0083] S2 Mixing: Take isohexanediol and add the above components while stirring slowly until a uniform emulsion is formed; the mass ratio of isohexanediol to other components is 1:1; after mixing, seal and set aside.

[0084] Example 5

[0085] A method for preparing a composite thickener comprises the following steps:

[0086] S1 Weighing: Weigh each component according to the following mass parts:

[0087] 36 parts guar hydroxypropyltrimonium chloride

[0088] 24 parts amino silicone oil

[0089] 3.6 parts cationic cellulose

[0090] 0.18 parts of 2-morpholineethanesulfonic acid

[0091] S2 Mixing: Take ethanol and add the above components while stirring slowly until a uniform emulsion is formed; the mass ratio of ethanol to other components is 1:1; after mixing, seal and set aside.

[0092] Example 6

[0093] A method for preparing a composite thickener comprises the following steps:

[0094] S1 Weighing: Weigh each component according to the following mass parts:

[0095] 36 parts guar hydroxypropyltrimonium chloride

[0096] 24 parts amino silicone oil

[0097] 3.6 parts cationic cellulose

[0098] 0.18 parts of 2-morpholineethanesulfonic acid

[0099] S2 Mixing: Take n-undecanol and add the above components while stirring slowly until a uniform emulsion is formed; the mass ratio of n-undecanol to other components is 1:1; after mixing, seal and set aside.

[0100] Example 7

[0101] A method for preparing a composite thickener comprises the following steps:

[0102] S1 Weighing: Weigh each component according to the following mass parts:

[0103] 36 parts guar hydroxypropyltrimonium chloride

[0104] 24 parts amino silicone oil

[0105] 3.6 parts carboxymethyl cellulose

[0106] 0.18 parts of 2-morpholineethanesulfonic acid

[0107] S2 Mixing: Take isohexanediol and add the above components while stirring slowly until a uniform emulsion is formed; the mass ratio of isohexanediol to other components is 1:1; after mixing, seal and set aside.

[0108] Example 8

[0109] A method for preparing a composite thickener comprises the following steps:

[0110] S1 Weighing: Weigh each component according to the following mass parts:

[0111] 36 parts guar hydroxypropyltrimonium chloride

[0112] 24 parts dimethicone

[0113] 3.6 parts cationic cellulose

[0114] 0.18 parts of 2-morpholineethanesulfonic acid

[0115] S2 Mixing: Take isohexanediol and add the above components while stirring slowly until a uniform emulsion is formed; the mass ratio of isohexanediol to other components is 1:1; after mixing, seal and set aside.

[0116] Example 9

[0117] A method for preparing a composite thickener comprises the following steps:

[0118] S1 Weighing: Weigh each component according to the following mass parts:

[0119] 36 parts carboxymethyl guar gum

[0120] 24 parts amino silicone oil

[0121] 3.6 parts cationic cellulose

[0122] 0.18 parts of 2-morpholineethanesulfonic acid

[0123] S2 Mixing: Take isohexanediol and add the above components while stirring slowly until a uniform emulsion is formed; the mass ratio of isohexanediol to other components is 1:1; after mixing, seal and set aside.

[0124] Example 10

[0125] A method for preparing a composite thickener comprises the following steps:

[0126] S1 Weighing: Weigh each component according to the following mass parts:

[0127] 24 parts amino silicone oil

[0128] 3.6 parts cationic cellulose

[0129] 0.18 parts of 2-morpholineethanesulfonic acid

[0130] S2 Mixing: Take isohexanediol and add the above components while stirring slowly until a uniform emulsion is formed; the mass ratio of isohexanediol to other components is 1:1; after mixing, seal and set aside.

[0131] Example 11

[0132] A method for preparing a composite thickener comprises the following steps:

[0133] S1 Weighing: Weigh each component according to the following mass parts:

[0134] 36 parts guar hydroxypropyltrimonium chloride

[0135] 3.6 parts cationic cellulose

[0136] 0.18 parts of 2-morpholineethanesulfonic acid

[0137] S2 Mixing: Take isohexanediol and add the above components while stirring slowly until a uniform emulsion is formed; the mass ratio of isohexanediol to other components is 1:1; after mixing, seal and set aside.

[0138] Example 12

[0139] A method for preparing a composite thickener comprises the following steps:

[0140] S1 Weighing: Weigh each component according to the following mass parts:

[0141] 36 parts guar hydroxypropyltrimonium chloride

[0142] 24 parts amino silicone oil

[0143] 0.18 parts of 2-morpholineethanesulfonic acid

[0144] S2 Mixing: Take isohexanediol and add the above components while stirring slowly until a uniform emulsion is formed; the mass ratio of isohexanediol to other components is 1:1; after mixing, seal and set aside.

[0145] Example 13

[0146] A method for preparing a composite thickener comprises the following steps:

[0147] S1 Weighing: Weigh each component according to the following mass parts:

[0148] 36 parts guar hydroxypropyltrimonium chloride

[0149] 24 parts amino silicone oil

[0150] 3.6 parts cationic cellulose

[0151] S2 Mixing: Take isohexanediol and add the above components while stirring slowly until a uniform emulsion is formed; the mass ratio of isohexanediol to other components is 1:1; after mixing, seal and set aside.

[0152] The above examples were added to the pickling agent and the corresponding viscosity test was performed. The test method is as follows:

[0153] Test standard: GB / T 15357-2014 Surfactants and detergents - Determination of viscosity and flow properties of liquid products by rotational viscometer

[0154] Test environment: standard atmospheric pressure, 25°C

[0155] Test sample: Add a certain amount of Example to the aforementioned pickling agent, stir for 1 minute, and then let it stand for 30 minutes.

[0156] The results are shown in Table 1.

[0157] Table 1

[0158]

[0159]

[0160] The results in Table 1 show that when the addition amount of the embodiments of the present invention is 0.2-3% (half of which is solvent), the system viscosity is within 300-1000 (Examples 1, 2, and 3), which meets the normal use requirements of the pickling agent. However, when the addition amount reaches 3%, the viscosity is too high, which is a special requirement in specific scenarios. Generally speaking, there is currently no use scenario for organic acid pickling agents with a viscosity above 1800. Figure 1 This is the experimental result of Example 1 when the addition amount is 3%. It can be seen that at this addition amount, the organic acid detergent remains transparent and has a wall hanging phenomenon (a phenomenon at a certain viscosity).

[0161] Example 4 uses hydroxy silicone oil, Example 5 uses ethanol, a short-chain alcohol, and Example 6 uses n-11-ol, an alcohol with the longest carbon chain that is liquid at room temperature; the viscosity data are significantly different but still within the appropriate viscosity range, demonstrating that the present invention has a wide adaptability.

[0162] Example 7 uses carboxymethyl cellulose, which is an anionic compound. Electrostatic attraction between anions and cations occurs in the system, forming a white insoluble complex precipitate (such as Figure 2 As shown in Figure 2, the viscosity is significantly reduced and the thickening effect cannot be achieved.

[0163] In Example 8, polydimethylsiloxane (anionic silicone oil) was used to form a three-dimensional physical cross-linked network with cationic guar gum, forming a gel-like substance that caused a sharp increase in viscosity (e.g. Figure 3 shown).

[0164] Example 9 uses carboxymethyl guar gum, and the same phenomenon as Example 8 occurs.

[0165] Examples 10, 11, 12, and 13 are the experimental results of omitting guar gum, silicone oil, cellulose, and 2-morpholineethanesulfonic acid from the system, respectively. It can be seen that the absence of any one component will lead to a slight decrease in viscosity.

[0166] In summary, according to the experimental data in Table 1, since the embodiments 1-13 are all dissolved in the same mass of alcohol, the actual concentration is half of that in Table 1. Therefore, when the present invention is actually applied, the addition amount is within a reasonable range of 0.1-1.5%.

[0167] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A composite thickener, characterized in that Contains the following components by mass percentage: 36-48% cationic guar gum 24-35% silicone oil 3.6-5% cationic cellulose 0.18-0.45% zwitterionic buffer; The silicone oil is cationic silicone oil or nonionic silicone oil The thickener is dissolved in the alcohol solvent.

2. The composite thickener according to claim 1, characterized in that The silicone oil is cationic silicone oil.

3. The composite thickener according to claim 2, characterized in that The silicone oil is a non-terminated cationic silicone oil.

4. The composite thickener according to claim 3, characterized in that The silicone oil is amino silicone oil.

5. The composite thickener according to claim 1, characterized in that The alcohol solvent is a C2-C9 alcohol.

6. The composite thickener according to claim 5, characterized in that The long-chain alcohol is a C7-C9 long carbon chain alcohol.

7. The composite thickener according to claim 1, characterized in that The zwitterionic buffer is 2-morpholineethanesulfonic acid and / or 3-morpholinepropanesulfonic acid.

8. Use of the composite thickener according to claim 1-7 in an organic acid pickling agent containing a quaternary ammonium salt disinfectant.

9. The use of the composite thickener according to claim 8 in an organic acid pickling agent containing a quaternary ammonium salt disinfectant, wherein It is added to the organic acid pickling agent in the form of pre-dissolved in alcohol solvent.

10. The use of the composite thickener according to claim 8 in an organic acid pickling agent containing a quaternary ammonium salt disinfectant, wherein: The composite thickener is added in an amount of at least 0.1 wt % in the organic acid pickling agent containing the quaternary ammonium salt disinfectant.

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