Antibacterial fabric softener as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of daily chemical products, and discloses an antibacterial fabric softener as well as a preparation method and application thereof. The antibacterial fabric softener is prepared from the following raw materials in percentage by mass: 3 to 15 percent of diester gemini quaternary ammonium salt; 1 to 10 weight percent of oleic acid-based imidazoline quaternary ammonium salt; 0.1-3 wt% of an organic counter ion quaternary ammonium salt; 0.1 to 2 weight percent of polycation head group quaternary ammonium salt; 0.1 to 1 wt% of alkyl morpholine quaternary ammonium salt; 5-10 wt% of an emulsifier; 0.5-3 wt% of a viscosity stabilizer; 2-20 wt% of a cosolvent; 0.1 to 1 wt% of an aromatic agent; 0.1 to 0.5 wt% of a pH conditioning agent; 0-0.1 wt% of a pigment; and the balance water. The obtained fabric softener has good stability at low temperature and normal temperature, the treated fabric has excellent fabric softness, antistatic property, smoothness and antibacterial property and is not prone to yellowing, and the rewettability of the fabric is greatly improved.

Description

Technical Field

[0001] The invention relates to the technical field of daily chemical products, and in particular to an antibacterial fabric softener and a preparation method and application thereof. Background Art

[0002] Fabrics that come into direct contact with the skin, such as towels, clothing, and baby clothes, will gradually age and become rough after repeated long-term use and washing, which will cause rough skin feel and poor comfort during use. The current common solution is to use a softener to soften the fabric after washing. During the application process, fabric softener can be evenly attached to the surface of fabric fibers due to its strong hydrophobic properties, reducing the friction coefficient between fibers, restoring the inherent smoothness and extension properties of the fibers, thereby giving the fabric better softness, smoothness, fluffiness and elasticity, and excellent antistatic properties, which are welcomed by more and more consumers.

[0003] Mainstream fabric softeners available on the market usually use di-long-chain alkyl quaternary ammonium salts or ester-based quaternary ammonium salt surfactants as the main softening ingredients, such as: after the fabric is treated with a softener formulated with dioctadecyl dimethyl ammonium chloride as the main ingredient, the softness and fluffiness of the fabric are significantly improved. However, di-long-chain alkyl dimethyl ammonium chloride is easy to make the fabric yellow and has poor compatibility during actual application, especially difficult to biodegrade in the natural environment, and is gradually banned and replaced by more and more countries. In recent years, ester-based quaternary ammonium salts have become the mainstream products in the field of fabric softening by virtue of their good biodegradability and yellowing resistance. For example, the Chinese invention patent application with publication number CN108221374A uses ester-based quaternary ammonium salts as the main ingredient, and prepares a fabric softener product with nonionic surfactants, cosolvents and dispersants. It has excellent softness and antistatic effects in fabric treatment, and has good biodegradability and is green and environmentally friendly. However, the low water solubility of ester-based quaternary ammonium salts themselves makes the prepared fabric softener poor in stability, which is not conducive to giving full play to the softness of the product. In addition, after the fabric is treated with a fabric softener with a main ingredient of a di-long-chain alkyl quaternary ammonium salt or an ester-based quaternary ammonium salt having strong hydrophobic properties, the fabric will remain on the surface of the fabric and will delay the rewetting of the fabric to a certain extent, causing the rewetting effect of the fabric to deteriorate and affecting the sensory experience of the fabric when it is used again.

[0004] Moreover, with the continuous improvement of people's living standards and the pursuit of comfort, higher requirements are placed on the quality and functionality of fabric softeners. The single softening function is far from meeting the life needs of consumers. People are more willing to get a more comfortable and pleasant fabric experience while maintaining the softness of the fabric. Summary of the invention

[0005] The purpose of the present invention is to provide an antibacterial fabric softener and a preparation method and application thereof, so as to solve the problem that the existing fabric softeners cannot meet the multifunctional requirements such as stability, softness and rewetting.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides an antibacterial fabric softener, comprising the following raw materials in mass fractions:

[0008]

[0009] The general structural formula of the diester-based gemini quaternary ammonium salt is shown in Formula I:

[0010]

[0011] In formula I, R is a saturated or unsaturated C 11 ~C 17 An odd-numbered straight-chain alkyl group;

[0012] The diester-based gemini quaternary ammonium salt comprises one or more of formula I;

[0013] The general structural formula of the organic counterion quaternary ammonium salt is shown in Formula II:

[0014]

[0015] In formula II, R1 is a saturated C8~C 18 An even-numbered straight-chain alkyl group; R2 is -CH3 or -CH2CH2OH; X is HCOO, CH3COO or CH3CH2COO;

[0016] The organic counterion quaternary ammonium salt includes one or more of formula II;

[0017] The general structural formula of the oleic acid imidazoline quaternary ammonium salt is shown in Formula III:

[0018]

[0019] In formula III, R3 is -CH3 or -CH2CH3; X1 is CH3SO4 or CH3CH2SO4;

[0020] The oleic acid imidazoline quaternary ammonium salt includes one or more of formula III;

[0021] The general structural formula of the polycationic head group quaternary ammonium salt is shown in Formula IV:

[0022]

[0023] In formula IV, R4 is a saturated C8~C 18An even number of straight chain alkyl groups;

[0024] The polycationic head group quaternary ammonium salt comprises one or more of formula IV;

[0025] The general structural formula of the alkylmorpholine quaternary ammonium salt is shown in Formula V:

[0026]

[0027] In formula V, R5 is a saturated C8-C 18 An even-numbered straight-chain alkyl group; R6 is -CH3 or -CH2CH3; X2 is CH3SO4, CH3CH2SO4 or Cl;

[0028] The alkylmorpholine quaternary ammonium salt includes one or more of formula V.

[0029] Preferably, in the antibacterial fabric softener, the emulsifier comprises C 8～14 One or more of fatty alcohol polyoxyethylene ether, alkyl glucosides, oil-based ethoxylates, cocamidopropyl betaine and dodecyl methyl betaine.

[0030] Preferably, in the antibacterial fabric softener, the oil-based ethoxylate comprises coconut oil ethoxylate, soybean oil ethoxylate, palm oil ethoxylate, palm kernel oil ethoxylate, rapeseed oil ethoxylate, corn oil ethoxylate, cottonseed oil ethoxylate or castor oil ethoxylate.

[0031] Preferably, in the antibacterial fabric softener, the viscosity stabilizer comprises carboxymethyl cellulose and / or hydroxyethyl cellulose.

[0032] Preferably, in the antibacterial fabric softener, the co-solvent comprises one or more of ethanol, isopropanol, ethylene glycol, propylene glycol and glycerol.

[0033] Preferably, in the antibacterial fabric softener, the fragrance is an oil-soluble fragrance or a water-soluble fragrance, and the fragrance does not contain anionic components.

[0034] Preferably, in the antibacterial fabric softener, the pH regulator comprises one or more of hydrochloric acid, nitric acid and citric acid.

[0035] The present invention also provides a method for preparing the antibacterial fabric softener, comprising the following steps:

[0036] The cosolvent and water are first mixed to obtain a mixed solution; the mixed solution, diester-based gemini quaternary ammonium salt, oleic acid-based imidazoline quaternary ammonium salt, organic counterion quaternary ammonium salt, polycationic head-based quaternary ammonium salt, alkyl morpholine quaternary ammonium salt, viscosity stabilizer and emulsifier are secondly mixed, and fragrance, pigment and pH regulator are added to the obtained mixed solution to obtain an antibacterial fabric softener.

[0037] Preferably, in the method for preparing the antibacterial fabric softener, the temperature of the first mixing and the second mixing are independently 50-75°C.

[0038] The invention also provides an application of the antibacterial fabric softener in fabric washing and care.

[0039] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:

[0040] (1) The diester-based gemini quaternary ammonium salt used in the present invention is di-N + The head group structure has better water solubility and stability than traditional ester quaternary ammonium salts, and has excellent softness and antistatic properties for fabrics. It is compounded with oleic acid imidazoline quaternary ammonium salts and emulsifiers with good rewetting properties. The resulting fabric softener has good stability at low temperature (-15°C) and room temperature (37°C). The fabric treated with the softener has excellent fabric softness, antistatic properties, smoothness, and is not easy to yellow. The rewetting of the fabric is also greatly improved.

[0041] (2) The organic counterion quaternary ammonium salt antibacterial agent added in the present invention is an improved product of traditional quaternary ammonium salts. Compared with commonly used quaternary ammonium salts such as dodecyl dimethyl benzyl ammonium chloride (1227 bactericide) and didecyl dimethyl ammonium chloride, it shows better bactericidal performance and compound synergistic effect, does not have drug resistance problems, is safe to use and is easily biodegradable. It can also play a synergistic role with polycationic head group quaternary ammonium salts and alkyl morpholine quaternary ammonium salts, and has excellent antibacterial properties. After the antibacterial softener is used to treat fabrics, the antibacterial properties of fabrics against various pathogens can be significantly improved.

[0042] (3) The diester-based gemini quaternary ammonium salt, oleic acid-based cyclic imidazoline quaternary ammonium salt, organic counterion quaternary ammonium salt and nonionic emulsifier used in the present invention are all green and environmentally friendly surfactant products with good biodegradability and safe use. The overall formula embodies the "green" feature.

[0043] (4) The fabric softener of the present invention has softness, antistatic and antibacterial properties, embodies the concept of multifunctionality, and has the advantages of good water solubility, fast dispersion, no yellowing, and good re-wetting properties. It is suitable for home fabric washing, commercial fabric washing such as hotels and hospitals, car care and industrial production. At the same time, the production process of the product of the present invention is simple, which is convenient for further industrialization. DETAILED DESCRIPTION

[0044] The present invention provides an antibacterial fabric softener, comprising the following raw materials in mass fractions:

[0045]

[0046]

[0047] The general structural formula of the diester-based gemini quaternary ammonium salt is shown in Formula I:

[0048]

[0049] In formula I, R is a saturated or unsaturated C 11 ~C 17 An odd-numbered straight-chain alkyl group;

[0050] The diester-based gemini quaternary ammonium salt comprises one or more of formula I;

[0051] The general structural formula of the organic counterion quaternary ammonium salt is shown in Formula II:

[0052]

[0053] In formula II, R1 is a saturated C8~C 18 An even-numbered straight-chain alkyl group; R2 is -CH3 or -CH2CH2OH; X is HCOO, CH3COO or CH3CH2COO;

[0054] The organic counterion quaternary ammonium salt includes one or more of formula II;

[0055] The general structural formula of the oleic acid imidazoline quaternary ammonium salt is shown in Formula III:

[0056]

[0057] In formula III, R3 is -CH3 or -CH2CH3; X1 is CH3SO4 or CH3CH2SO4;

[0058] The oleic acid imidazoline quaternary ammonium salt includes one or more of formula III;

[0059] The general structural formula of the polycationic head group quaternary ammonium salt is shown in Formula IV:

[0060]

[0061] In formula IV, R4 is a saturated C8~C 18 An even number of straight chain alkyl groups;

[0062] The polycationic head group quaternary ammonium salt comprises one or more of formula IV;

[0063] The general structural formula of the alkylmorpholine quaternary ammonium salt is shown in Formula V:

[0064]

[0065] In formula V, R5 is a saturated C8-C 18 An even-numbered straight-chain alkyl group; R6 is -CH3 or -CH2CH3; X2 is CH3SO4, CH3CH2SO4 or Cl;

[0066] The alkylmorpholine quaternary ammonium salt includes one or more of formula V.

[0067] In the present invention, R in Formula I is preferably a saturated C 11 ~C 17 An odd-numbered straight-chain alkyl group, preferably a saturated C 13 ~C 15 An odd-numbered straight-chain alkyl group, more preferably a saturated C 15 of a straight chain alkyl group.

[0068] In the present invention, the preparation method of the diester-based gemini quaternary ammonium salt is preferably obtained by referring to the Chinese patent application with publication number CN115724754A and titled "A diester-based gemini quaternary ammonium salt and its preparation method and application".

[0069] In the present invention, the mass fraction of the diester-based gemini quaternary ammonium salt is preferably 4 to 12 wt %, more preferably 6 to 10 wt %, and more preferably 8 wt %.

[0070] In the present invention, the diester-based gemini quaternary ammonium salt is used as the main component of the fabric softener, which has good fabric softening and antistatic effects, and the treated fabric has excellent anti-yellowing performance; at the same time, the diester-based gemini quaternary ammonium salt is the latest generation of quaternary ammonium salt products, because it has two N + The head group and two hydrophobic chains have better water solubility than traditional ester-based quaternary ammonium salts, which is crucial to improving the hydrophilicity of fabric softeners in actual applications and their stability at low and normal temperatures.

[0071] In the present invention, R3 in the formula III is preferably -CH2CH3.

[0072] In the present invention, X1 in the formula III is preferably CH3CH2SO4.

[0073] In the present invention, the mass fraction of the oleic acid imidazoline quaternary ammonium salt is preferably 3 to 8 wt %, more preferably 4 to 6 wt %, and more preferably 5 wt %.

[0074] In the present invention, the preparation method of the oleic acid imidazoline quaternary ammonium salt preferably comprises the following steps: using oleic acid and diethylenetriamine as raw materials, synthesizing a cyclic imidazoline intermediate by a dehydration reaction, and then adding dimethyl sulfate or diethyl sulfate for a quaternization reaction to obtain an oleic acid imidazoline quaternary ammonium salt.

[0075] In the present invention, the oleic acid preferably comprises one or more of palmitic acid, soybean oleic acid, linoleic acid, arachidic acid and ricinoleic acid, further preferably comprises one or more of soybean oleic acid, linoleic acid and ricinoleic acid, more preferably comprises soybean oleic acid, linoleic acid or ricinoleic acid.

[0076] In the present invention, the parameter conditions in the preparation method of the oleic acid imidazoline quaternary ammonium salt are not limited, and the schemes well known to those skilled in the art can be adopted.

[0077] In the present invention, R1 in Formula II is preferably C8~C 14 An even-numbered straight-chain alkyl group, more preferably C 10 ~C 12 An even number of straight chain alkyl groups, more preferably C 12 An even numbered straight chain alkyl group.

[0078] In the present invention, R2 in the formula II is preferably -CH2CH2OH.

[0079] In the present invention, X in the formula II is preferably HCOO or CH3CH2COO, and more preferably HCOO.

[0080] In the present invention, the mass fraction of the organic counter ion quaternary ammonium salt is preferably 0.5 to 3 wt %, more preferably 1 to 2 wt %, and more preferably 1 wt %.

[0081] In an embodiment of the present invention, the manufacturer of the organic counter-ion quaternary ammonium salt is preferably China Daily Chemical Research Institute Co., Ltd.

[0082] In the present invention, the organic counterion quaternary ammonium salt does not contain halogen ions, and compared with the traditional dodecyl dimethyl benzyl ammonium chloride and didecyl dimethyl ammonium chloride quaternary ammonium salts, it has more efficient killing / inhibiting performance, good compounding performance, low toxicity and low irritation, and is a type of ecologically safe surfactant. The application of such organic counterion quaternary ammonium salts in fabric softeners can give the product excellent antibacterial effect and certain antistatic properties, and can avoid the drug resistance problem of traditional quaternary ammonium salts.

[0083] In the present invention, R4 in the formula IV is preferably a saturated C8-C 14 An even-numbered straight-chain alkyl group, preferably a saturated C 10 ~C 14 An even number of straight chain alkyl groups, more preferably a saturated C 12 of a straight chain alkyl group.

[0084] In the present invention, the preparation method of the polycationic head group quaternary ammonium salt is preferably obtained by referring to the Chinese patent application with publication number CN115197077A and titled "A cationic oligomeric surfactant containing polyquaternary ammonium head groups and its preparation method".

[0085] In the present invention, the mass fraction of the polycationic head group quaternary ammonium salt is preferably 0.2 to 1.5 wt %, more preferably 0.4 to 1.0 wt %, and more preferably 0.5 wt %.

[0086] In the present invention, R5 in the formula V is preferably a saturated C 10 ~C 16 An even-numbered straight-chain alkyl group, preferably a saturated C 12 ~C 14 An even number of straight chain alkyl groups, more preferably a saturated C 12 of a straight chain alkyl group.

[0087] In the present invention, R6 in the formula V is preferably -CH2CH3.

[0088] In the present invention, X2 in the formula V is preferably CH3SO4 or CH3CH2SO4, and more preferably CH3CH2SO4.

[0089] In the present invention, the mass fraction of the alkylmorpholine quaternary ammonium salt is preferably 0.2 to 0.8 wt %, more preferably 0.4 to 0.6 wt %, and more preferably 0.5 wt %.

[0090] In the present invention, the emulsifier preferably comprises C 8～14 One or more of fatty alcohol polyoxyethylene ether, alkyl glucosides, oil-based ethoxylates, cocamidopropyl betaine and dodecyl methyl betaine, preferably C 8～14Fatty alcohol polyoxyethylene ether, alkyl glycoside, oil-based ethoxylate or cocamidopropyl betaine, more preferably oil-based ethoxylate.

[0091] In the present invention, the alkyl glycoside preferably comprises C8 to C 14 Straight chain or isomeric alkyl glycosides, preferably C8 to C 12 Straight chain alkyl glycosides, more preferably comprising C8~C 10 Straight chain alkyl glycosides.

[0092] In the present invention, the oil-based ethoxylate preferably comprises coconut oil ethoxylate, soybean oil ethoxylate, palm oil ethoxylate, palm kernel oil ethoxylate, rapeseed oil ethoxylate, corn oil ethoxylate, cottonseed oil ethoxylate or castor oil ethoxylate, further preferably comprises coconut oil ethoxylate, soybean oil ethoxylate, palm kernel oil ethoxylate, corn oil ethoxylate or castor oil ethoxylate, more preferably soybean oil ethoxylate.

[0093] In the present invention, the preparation method of the oil-based ethoxylate is preferably obtained by referring to the Chinese patent application with publication number CN1730145A and titled "An ethoxylate of oil and fat and its preparation method".

[0094] In the present invention, the mass fraction of the emulsifier is preferably 5 to 8 wt %, more preferably 5 to 7 wt %, and more preferably 6 wt %.

[0095] In an embodiment of the present invention, the manufacturer of the alkyl glycoside and the oil-based ethoxylated compound is preferably China Daily Chemical Research Institute Co., Ltd.

[0096] In the present invention, the viscosity stabilizer preferably comprises carboxymethyl cellulose and / or hydroxyethyl cellulose, more preferably comprises carboxymethyl cellulose or hydroxyethyl cellulose, and more preferably comprises carboxymethyl cellulose.

[0097] In the present invention, the mass fraction of the viscosity stabilizer is preferably 0.5 to 2 wt %, more preferably 1 to 2 wt %, and more preferably 1 wt %.

[0098] In the present invention, the co-solvent preferably comprises one or more of ethanol, isopropanol, ethylene glycol, propylene glycol and glycerol, further preferably comprises one or more of ethanol, isopropanol and propylene glycol, and more preferably is propylene glycol.

[0099] In the present invention, the mass fraction of the co-solvent is preferably 5 to 15 wt %, more preferably 8 to 10 wt %, and more preferably 10 wt %.

[0100] In the present invention, the fragrance is preferably an oil-soluble fragrance or a water-soluble fragrance, and the fragrance does not contain an anionic component.

[0101] In the present invention, the specific type of the fragrance is not limited, and substances well known to those skilled in the art can be used. Specifically in the embodiment of the present invention, the fragrance preferably includes one or more of jasmine essence, rose essence, lavender essence and lily essence.

[0102] In the present invention, the mass fraction of the aromatic agent is preferably 0.2-1 wt %, more preferably 0.2-0.5 wt %, and more preferably 0.3 wt %.

[0103] In the present invention, the pH adjuster preferably comprises one or more of hydrochloric acid, nitric acid and citric acid, more preferably comprises hydrochloric acid, nitric acid or citric acid, and more preferably is citric acid.

[0104] In the present invention, the mass fraction of the pH adjuster is preferably 0.1 to 0.3 wt %, more preferably 0.1 to 0.2 wt %, and more preferably 0.2 wt %.

[0105] In the present invention, the specific type of the pigment is not limited, and substances well known to those skilled in the art can be used. Specifically in the embodiment of the present invention, the pigment preferably includes one or more of lemon yellow pigment, lake blue pigment, bright blue pigment, light green pigment, light pink pigment and purple pigment.

[0106] In the present invention, the mass fraction of the pigment is preferably 0.02 to 0.1 wt %, more preferably 0.05 to 0.1 wt %, and more preferably 0.1 wt %.

[0107] In the present invention, when the diester-based gemini quaternary ammonium salt, the oleic acid imidazoline quaternary ammonium salt, the organic counterion quaternary ammonium salt, the polycationic head group quaternary ammonium salt, the alkyl morpholine quaternary ammonium salt, the emulsifier, the viscosity stabilizer, the cosolvent, the fragrance, the pH adjuster or the pigment is preferably a plurality of types, the ratio between the various substances is not limited and can be adjusted according to needs.

[0108] The present invention also provides a method for preparing the antibacterial fabric softener, comprising the following steps:

[0109] The cosolvent and water are first mixed to obtain a mixed solution; the mixed solution, diester-based gemini quaternary ammonium salt, oleic acid-based imidazoline quaternary ammonium salt, organic counterion quaternary ammonium salt, polycationic head-based quaternary ammonium salt, alkyl morpholine quaternary ammonium salt, viscosity stabilizer and emulsifier are secondly mixed, and fragrance, pigment and pH regulator are added to the obtained mixed solution to obtain an antibacterial fabric softener.

[0110] In the present invention, the temperature of the first mixing is preferably 50-75°C, more preferably 55-65°C, and more preferably 60°C; the time is preferably 5-10 min, more preferably 8-10 min, and more preferably 10 min.

[0111] In the present invention, the temperature of the second mixing is preferably 50 to 75°C, more preferably 55 to 65°C, and even more preferably 60°C.

[0112] In the present invention, after mixing the mixed solution, diester-based gemini quaternary ammonium salt, oleic acid imidazoline quaternary ammonium salt, organic counterion quaternary ammonium salt, polycationic head-based quaternary ammonium salt, alkyl morpholine quaternary ammonium salt, viscosity stabilizer and emulsifier, the step of preferably further comprising: cooling to 25-50°C, more preferably to 30-40°C, and more preferably to 35°C.

[0113] The invention also provides an application of the antibacterial fabric softener in fabric washing and care.

[0114] In the present invention, the application method is not limited, and any method known to those skilled in the art may be used.

[0115] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments 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 ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0116] Example 1

[0117] This embodiment provides a method for preparing an antibacterial fabric softener, comprising the following steps:

[0118] (1) Prepare the required raw materials according to the following raw material ratios: diester-based gemini quaternary ammonium salt 1,4-di(palmitoylethyl dimethyl ammonium bromide) butane: 40.0 g, soybean oleic acid imidazoline ethyl sulfate quaternary ammonium salt (R3 is -CH2CH3): 100.0 g, antibacterial agent dioctyl dimethyl ammonium formate: 5.0 g, C10 alkyl polycationic head group quaternary ammonium salt: 10.0 g, n-decyl morpholine methyl methyl sulfate ammonium: 5.0 g, emulsifier alkyl polyglycoside APG0810: 50.0 g, viscosity stabilizer carboxymethyl cellulose: 10.0 g, cosolvent ethanol: 100.0 g, jasmine essence: 2.0 g, citric acid: 3.0 g, brilliant blue pigment: 0.5 g, and deionized water: 674.5 g;

[0119] (2) Add the co-solvent and deionized water into the mixing container, heat and stir at 50°C for 5 to 10 minutes until uniform;

[0120] (3) adding measured amounts of diester-based gemini quaternary ammonium salt, imidazoline quaternary ammonium salt, organic counterion quaternary ammonium salt, polycationic head group quaternary ammonium salt, alkyl morpholine quaternary ammonium salt, viscosity stabilizer and emulsifier in sequence, mixing and stirring at 50° C., and cooling to 35° C. after the mixture becomes clear and bright;

[0121] (4) Add fragrance, pigment and pH adjuster into a mixing container and stir evenly to obtain an antibacterial fabric softener.

[0122] Example 2

[0123] The present embodiment provides a method for preparing an antibacterial fabric softener, which is different from the embodiment 1 in that the raw material ratio of step (1) is replaced by: diester-based gemini quaternary ammonium salt 1,4-di(oleylethyl dimethyl ammonium bromide) butane: 100.0 g, palmitoleic acid imidazoline methyl sulfate quaternary ammonium salt (R3 is -CH3): 50.0 g, antibacterial agent didecyl hydroxyethyl methyl ammonium formate: 10.0 g, C8 alkyl polycationic head group quaternary ammonium salt: 15.0 g, dodecyl morpholine ethyl sulfate ethyl ammonium: 1.0 g, emulsifier C 12 Fatty alcohol polyoxyethylene ether (09) (molecular formula C 12 H 25 O(CH2CH2O)9H): 70.0g, viscosity stabilizer hydroxyethyl cellulose: 20.0g, co-solvent ethanol: 150.0g, rose essence: 5.0g, nitric acid: 1.0g, light green pigment: 1.0g, deionized water: 577.0g, the heating temperature of step (2) and the mixing and stirring temperature of step (3) are replaced with 60°C, and the other parameter conditions are the same as those in Example 1.

[0124] Example 3

[0125] The present embodiment provides a method for preparing an antibacterial fabric softener, which is different from the embodiment 1 in that the raw material ratio of step (1) is replaced by: diester-based gemini quaternary ammonium salt 1,4-di(palmitic acid ethyl ester dimethyl ammonium bromide) butane: 120.0 g, linolenic acid imidazoline ethyl sulfate quaternary ammonium salt (R3 is -CH2CH3): 30.0 g, antibacterial agent didecyl dimethyl ammonium propionate: 30.0 g, C12 alkyl polycationic head group quaternary ammonium salt: 5.0 g, Octylmorpholinemethylammonium methylsulfate: 10.0 g, emulsifier cocamidopropyl betaine: 100.0 g, viscosity stabilizer hydroxyethyl cellulose: 5.0 g, cosolvent isopropyl alcohol: 200.0 g, rose essence: 10.0 g, citric acid: 5.0 g, lake blue pigment: 0.2 g, deionized water: 484.8 g, the heating temperature of step (2) and the mixing and stirring temperature of step (3) are replaced with 65° C., and the other parameter conditions are the same as those in Example 1.

[0126] Example 4

[0127] The present embodiment provides a method for preparing an antibacterial fabric softener, which is different from the embodiment 1 in that the raw material ratio of step (1) is replaced by: diester-based gemini quaternary ammonium salt 1,4-di(stearate ethyl dimethyl ammonium bromide) butane: 60.0 g, ricinoleic acid imidazoline methyl sulfate quaternary ammonium salt (R3 is -CH3): 80.0 g, antibacterial agent monododecyl hydroxyethyl dimethyl ammonium acetate: 20.0 g, C16 alkyl polycationic head group quaternary ammonium salt: 20.0 g, hexadecane Ammonium ethyl morpholine sulfate: 10.0 g, emulsifier soybean oil ethoxylate (EO addition number 30): 60.0 g, viscosity stabilizer carboxymethyl cellulose: 30.0 g, cosolvent propylene glycol: 50.0 g, jasmine essence: 1.0 g, hydrochloric acid: 2.0 g, lemon yellow pigment: 1.0 g, deionized water: 666.0 g, the heating temperature of step (2) and the mixing and stirring temperature of step (3) are replaced with 75° C., and the other parameter conditions are the same as those in Example 1.

[0128] Example 5

[0129] The present embodiment provides a method for preparing an antibacterial fabric softener, which is different from the embodiment 1 in that the raw material ratio of step (1) is replaced by: diester-based gemini quaternary ammonium salt 1,4-di(oleylethyl dimethyl ammonium bromide) butane: 30.0 g, arachidonic acid imidazoline ethyl sulfate quaternary ammonium salt (R3 is -CH2CH3): 100.0 g, antibacterial agent dioctyl hydroxyethyl methyl ammonium formate: 5.0 g, C12 alkyl polycationic head group quaternary ammonium salt: 10.0 g, ten Dialkylmorpholinemethylammonium chloride: 3.0 g, emulsifier coconut oil ethoxylate (EO addition number 20): 50.0 g, viscosity stabilizer carboxymethyl cellulose: 20.0 g, co-solvent isopropanol: 20.0 g, rose essence: 2.0 g, nitric acid: 1.0 g, purple pigment: 1.0 g, deionized water: 758.0 g, the heating temperature of step (2) and the mixing and stirring temperature of step (3) are replaced with 60° C., and the other parameter conditions are the same as those in Example 1.

[0130] Example 6

[0131] The present embodiment provides a method for preparing an antibacterial fabric softener, which is different from the embodiment 1 in that the raw material ratio of step (1) is replaced by: diester-based gemini quaternary ammonium salt 1,4-di(myristyl ethyl ester dimethyl ammonium bromide) butane: 150.0 g, soybean oil acid imidazoline methyl sulfate quaternary ammonium salt (R3 is -CH3): 50.0 g, antibacterial agent didecyl hydroxyethyl methyl ammonium acetate: 1.0 g, C14 alkyl polycationic head group quaternary ammonium salt: 15.0 g, dodecyl morphine Ammonium methyl sulfate: 1.0 g, emulsifier palm kernel oil ethoxylate (EO addition number 25): 100.0 g, viscosity stabilizer hydroxyethyl cellulose: 5.0 g, cosolvent propylene glycol: 100.0 g, lavender essence: 2.0 g, hydrochloric acid: 2.0 g, brilliant blue pigment: 1.0 g, deionized water: 573.0 g, the heating temperature of step (2) and the mixing and stirring temperature of step (3) are replaced with 55° C., and the other parameter conditions are the same as those in Example 1.

[0132] Example 7

[0133] The present embodiment provides a method for preparing an antibacterial fabric softener, which is different from the embodiment 1 in that the raw material ratio of step (1) is replaced by: diester-based gemini quaternary ammonium salt 1,4-di(palmitoylethyl dimethylammonium bromide) butane: 80.0 g, linoleic acid imidazoline methyl sulfate quaternary ammonium salt (R3 is -CH3): 60.0 g, antibacterial agent didodecyl hydroxyethyl methyl ammonium formate: 10.0 g, C10 alkyl polycationic head group quaternary ammonium salt: 5.0 g, n-decyl morpholine ethyl ethyl sulfate ammonium: 4.0 g, emulsifier corn oil ethoxylate (EO addition number 40): 50.0 g, viscosity stabilizer carboxymethyl cellulose: 10.0 g, cosolvent ethanol: 80.0 g, jasmine essence: 3.0 g, citric acid: 3.0 g, light pink pigment: 1.0 g, deionized water: 694.0 g, and other parameter conditions are the same as those in the embodiment 1.

[0134] Example 8

[0135] The present embodiment provides a method for preparing an antibacterial fabric softener, which is different from the embodiment 1 in that the raw material ratio of step (1) is replaced by: diester-based gemini quaternary ammonium salt 1,4-di(oleic acid ethyl ester dimethyl ammonium bromide) butane: 120.0 g, ricinoleic acid imidazoline ethyl sulfate quaternary ammonium salt (R3 is -CH2CH3): 40.0 g, antibacterial agent didecyl hydroxyethyl methyl propionic acid ammonium: 20.0 g, C16 alkyl polycationic head group quaternary ammonium salt: 20.0 g, tetradecane Ammonium ethyl morpholine sulfate: 8.0 g, emulsifier castor oil ethoxylate (EO addition number 60): 80.0 g, viscosity stabilizer hydroxyethyl cellulose: 10.0 g, cosolvent propylene glycol: 150.0 g, lily essence: 1.0 g, nitric acid: 1.0 g, light green pigment: 1.0 g, deionized water: 549.0 g, the heating temperature of step (2) and the mixing and stirring temperature of step (3) are replaced with 55° C., and the other parameter conditions are the same as those in Example 1.

[0136] Comparative Example 1

[0137] The difference between this comparative example and Example 1 is that the diester-based gemini quaternary ammonium salt 1,4-di(palmitoylethyl ester dimethyl ammonium bromide) butane in step (1) is replaced by the mainstream ester-based quaternary ammonium salt - dipalmitoylethyl ester hydroxyethyl methyl ammonium methyl sulfate, and the other parameter conditions are the same as those in Example 1.

[0138] Comparative Example 2

[0139] The difference between this comparative example and Example 1 is that the soybean oil imidazoline sulfate ethyl ester quaternary ammonium salt (R3 is -CH2CH3) in step (1) is replaced by the diester-based gemini quaternary ammonium salt 1,4-di(palmitoylethyl dimethylammonium bromide) butane, and the other parameter conditions are the same as those in Example 1.

[0140] Comparative Example 3

[0141] The difference between this comparative example and Example 2 is that the antibacterial agent didecylhydroxyethylmethylammonium propionate in step (1) is replaced by conventional quaternary ammonium salt didecyldimethylammonium chloride, and the other parameter conditions are the same as those in Example 2.

[0142] Comparative Example 4

[0143] The difference between this comparative example and Example 1 is that the diester quaternary ammonium salt, oleic acid imidazoline quaternary ammonium salt, organic counterion quaternary ammonium salt, polycationic head group quaternary ammonium salt and alkyl morpholine quaternary ammonium salt in step (1) are replaced by deionized water, and the other parameter conditions are the same as those in Example 1.

[0144] Test Example 1: Stability Test

[0145] The stability of Examples 1 to 4 and Comparative Example 1 was tested under the following conditions: (1) Low temperature test: Freeze in a refrigerator at -15°C ± 1°C for 2 months, then take out and restore to 25°C to observe the change in the softener product state; if there is no stratification, no suspended matter, and the transparent liquid is not turbid, the product has good low temperature performance. (2) Normal temperature test: Place in a constant temperature box at 37°C for 3 months; if there is no change in the product appearance, no precipitation and no suspension, it means that the product has good normal temperature stability. The stability test results are shown in Table 1.

[0146] Table 1. Stability test results of Examples 1 to 4 and Comparative Example 1

[0147] Test conditions Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Low temperature (-15℃) No abnormality No abnormality No abnormality No abnormality More suspended matter Normal temperature (37℃) No abnormality No abnormality No abnormality No abnormality No abnormality

[0148] The stability test results show that Examples 1 to 4 have good low temperature stability and room temperature stability. Comparing Example 1 with Comparative Example 1, more suspended insoluble matter will appear in Comparative Example 1 under low temperature conditions, while Example 1 has obvious advantages in low temperature stability, which is mainly due to the fact that the double N + The diester-based gemini quaternary ammonium salts with head group structure have better water solubility and hydrophilicity than traditional ester-based quaternary ammonium salts.

[0149] Test Example 2: Fabric Softness and Rewetting Test

[0150] The fabric softness and rewetting properties of Examples 1 to 3, Comparative Examples 1 to 2 and Comparative Example 4 were tested.

[0151] Softness test method: Select JB-00 cotton white cloth, cut the cotton white cloth into 100mm×100mm square pieces, use 5 pieces of cloth for each solution, and set up a blank control group. Add 1.0g / L sample solution prepared with 250mg / L hard water to each cylinder of the RHLQ-Ⅲ type decontamination machine, and use the DRK119R type softness tester to measure its lateral softness (softness tester slit width 10mm). The softness of the cotton white cloth after washing represents the softness performance of the softener. The smaller the value, the better the softness performance of the softener. The test results of fabric softness are shown in Table 2.

[0152] Rewetting property determination method: According to QB / T4309-2012 "Determination of rewetting property of fabric softener", the rewetting property of fabric softener products was determined. Four test pieces were measured in parallel for each sample, and the average value of the measurement results was taken. The shorter the time, the better the rewetting property. The test results of fabric rewetting property are shown in Table 2.

[0153] Table 2. Softness and rewetting test results of Examples 1 to 3, Comparative Examples 1 to 2 and Comparative Example 4

[0154] Technical indicators Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 4 Softness / mN 186 175 182 188 185 251 Rewetting / s 236 251 256 232 350 126

[0155] In terms of softness, Examples 1 to 3 and Comparative Examples 1 to 2 have a significant effect of improving the softness of the fabric compared to Comparative Example 4, and Example 2 has the best softening effect. Example 1 and Comparative Example 1 have similar softness on the fabric, which shows that the diester-based gemini quaternary ammonium salt and the commercially available ester-based quaternary ammonium salt are basically equivalent in terms of fabric softness.

[0156] In terms of rewetting, after the fabrics were treated with the softener products prepared in Examples 1 to 3 and Comparative Examples 1 to 2, the rewetting of the fabrics was significantly worse than that of Comparative Example 4. This was mainly because the quaternary ammonium salts with longer hydrophobic chains were adsorbed on the fabric surface and formed a hydrophobic molecular layer, which hindered the rewetting effect of the fabrics. It should be noted that the rewetting of Examples 1 to 3 was significantly better than that of Comparative Example 2, which indicates that the oleic acid imidazoline quaternary ammonium salt has better rewetting performance than the diester-based gemini quaternary ammonium salt, and can effectively improve the rewetting of the fabric softener.

[0157] Test Example 3: Antibacterial Test

[0158] The softener products prepared in Examples 1 to 4 and Comparative Example 3 were tested for antibacterial effect using the suspension quantitative method according to 7.2 of "Evaluation Method for Antibacterial and Antimicrobial Effect of Daily Chemical Products" (QB / T 2738-2023). The test results are shown in Table 3.

[0159] Table 3. Antibacterial effect test results of Examples 1 to 4 and Comparative Example 3

[0160]

[0161]

[0162] The test results of antibacterial effect show that when the action time is 10min, the softeners prepared in Examples 1 to 4 have killing logarithmic values ​​of Staphylococcus aureus, Escherichia coli and Candida albicans (fungus) at dilutions of 1:100 and 1:200, which are all greater than 5, showing excellent antibacterial effect. The antibacterial properties of Comparative Example 3 and Example 2 are compared. The killing effect of Comparative Example 3 on Candida albicans fungi at a dilution of 1:100 and the killing effect of Comparative Example 3 on Staphylococcus aureus, Escherichia coli and Candida albicans fungi at a dilution of 1:200 are significantly worse than those of Example 3. This is because the organic counterion quaternary ammonium salt selected in the present invention is an improved product of traditional quaternary ammonium salts, and has higher antibacterial efficiency than traditional quaternary ammonium salt antibacterial agents, and has better synergistic effect with raw materials such as polycationic head group quaternary ammonium salts and alkyl morpholine quaternary ammonium salts, and there is no drug resistance problem. After the antibacterial fabric softener prepared by the invention is used to treat fabric, the antibacterial performance of the fabric against various pathogens can be significantly improved.

[0163] Test Example 4: Safety Test

[0164] According to the relevant requirements of the second part 2.3.1 and 2.3.3 of the "Technical Specifications for Disinfection" (2002 Edition), a single skin irritation test and an acute oral toxicity test were conducted on Example 1 and Example 2. The results of the single skin irritation test show that the softener products configured in Example 1 and Example 2 are non-irritating to the single intact skin test results of New Zealand rabbits. The results of the acute oral toxicity test show that during the test of the softener products configured in Example 1 and Example 2, no obvious symptoms of poisoning or death were observed in all the tested animals during the 14-day observation period; the softener product has an acute oral toxicity LD50>5000mg / kgBW for SPF-level KM mice, which is actually non-toxic.

[0165] The above test results show that the fabric softener product prepared by the embodiment of the present invention has good stability and is safe to use, and can well achieve the effects of good fabric softening performance, good rewetting performance and significant antibacterial performance.

[0166] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An antibacterial fabric softener, characterized in that: Contains the following raw materials by mass fraction: The general structural formula of the diester-based gemini quaternary ammonium salt is shown in Formula I: In formula I, R is a saturated or unsaturated C 11 ~C 17 An odd-numbered straight-chain alkyl group; The diester-based gemini quaternary ammonium salt comprises one or more of formula I; The general structural formula of the organic counterion quaternary ammonium salt is shown in Formula II: In formula II, R1 is a saturated C8~C 18 An even-numbered straight-chain alkyl group; R2 is -CH3 or -CH2CH2OH; X is HCOO, CH3COO or CH3CH2COO; The organic counterion quaternary ammonium salt includes one or more of formula II; The general structural formula of the oleic acid imidazoline quaternary ammonium salt is shown in Formula III: In formula III, R3 is -CH3 or -CH2CH3; X1 is CH3SO4 or CH3CH2SO4; The oleic acid imidazoline quaternary ammonium salt includes one or more of formula III; The general structural formula of the polycationic head group quaternary ammonium salt is shown in Formula IV: In formula IV, R4 is a saturated C8~C 18 An even number of straight chain alkyl groups; The polycationic head group quaternary ammonium salt comprises one or more of formula IV; The general structural formula of the alkylmorpholine quaternary ammonium salt is shown in Formula V: In formula V, R5 is a saturated C8-C 18 An even-numbered straight-chain alkyl group; R6 is -CH3 or -CH2CH3; X2 is CH3SO4, CH3CH2SO4 or Cl; The alkylmorpholine quaternary ammonium salt includes one or more of formula V.

2. The antibacterial fabric softener according to claim 1, characterized in that: The emulsifier comprises C 8～14 One or more of fatty alcohol polyoxyethylene ether, alkyl glucosides, oil-based ethoxylates, cocamidopropyl betaine and dodecyl methyl betaine.

3. An antibacterial fabric softener according to claim 2, characterized in that: The oil-based ethoxylate comprises coconut oil ethoxylate, soybean oil ethoxylate, palm oil ethoxylate, palm kernel oil ethoxylate, rapeseed oil ethoxylate, corn oil ethoxylate, cottonseed oil ethoxylate or castor oil ethoxylate.

4. The antibacterial fabric softener according to claim 2, characterized in that: The viscosity stabilizer comprises carboxymethyl cellulose and / or hydroxyethyl cellulose.

5. An antibacterial fabric softener according to claim 1 or 4, characterized in that: The co-solvent comprises one or more of ethanol, isopropanol, ethylene glycol, propylene glycol and glycerol.

6. The antibacterial fabric softener according to claim 5, characterized in that: The fragrance is an oil-soluble fragrance or a water-soluble fragrance, and the fragrance does not contain an anionic component.

7. An antibacterial fabric softener according to claim 1 or 6, characterized in that: The pH adjuster includes one or more of hydrochloric acid, nitric acid and citric acid.

8. The method for preparing an antibacterial fabric softener according to any one of claims 1 to 7, characterized in that: The following steps are involved: The cosolvent and water are first mixed to obtain a mixed solution; the mixed solution, diester-based gemini quaternary ammonium salt, oleic acid-based imidazoline quaternary ammonium salt, organic counterion quaternary ammonium salt, polycationic head-based quaternary ammonium salt, alkyl morpholine quaternary ammonium salt, viscosity stabilizer and emulsifier are secondly mixed, and fragrance, pigment and pH regulator are added to the obtained mixed solution to obtain an antibacterial fabric softener.

9. The method for preparing an antibacterial fabric softener according to claim 8, characterized in that: The temperatures of the first mixing and the second mixing are independently 50 to 75°C.

10. Use of the antibacterial fabric softener according to any one of claims 1 to 7 or the antibacterial fabric softener prepared by the preparation method according to any one of claims 8 to 9 in fabric washing and care.

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