CN115340911B - Micro-water environment-friendly automobile cleaning agent and preparation method thereof - Google Patents
Micro-water environment-friendly automobile cleaning agent and preparation method thereof Download PDFInfo
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- CN115340911B CN115340911B CN202210942022.4A CN202210942022A CN115340911B CN 115340911 B CN115340911 B CN 115340911B CN 202210942022 A CN202210942022 A CN 202210942022A CN 115340911 B CN115340911 B CN 115340911B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims abstract description 22
- JVAZJLFFSJARQM-RMPHRYRLSA-N (2r,3r,4s,5s,6r)-2-hexoxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical group CCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O JVAZJLFFSJARQM-RMPHRYRLSA-N 0.000 claims abstract description 20
- -1 alkyl hydroxyethyl dimethyl ammonium chloride Chemical compound 0.000 claims abstract description 20
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 claims abstract description 15
- 229940079781 sodium cocoyl glutamate Drugs 0.000 claims abstract description 15
- 229940077089 sodium palmitoyl glutamate Drugs 0.000 claims abstract description 15
- KLIFRVSZGDONER-FERBBOLQSA-M sodium;(4s)-4-(hexadecanoylamino)-5-hydroxy-5-oxopentanoate Chemical compound [H+].[Na+].CCCCCCCCCCCCCCCC(=O)N[C@H](C([O-])=O)CCC([O-])=O KLIFRVSZGDONER-FERBBOLQSA-M 0.000 claims abstract description 15
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 14
- 239000004064 cosurfactant Substances 0.000 claims abstract description 13
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 10
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 12
- 239000001509 sodium citrate Substances 0.000 claims description 12
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 12
- 239000000176 sodium gluconate Substances 0.000 claims description 12
- 229940005574 sodium gluconate Drugs 0.000 claims description 12
- 235000012207 sodium gluconate Nutrition 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000001587 sorbitan monostearate Substances 0.000 claims description 6
- 229940035048 sorbitan monostearate Drugs 0.000 claims description 6
- 235000011076 sorbitan monostearate Nutrition 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- FKOKUHFZNIUSLW-UHFFFAOYSA-N 2-Hydroxypropyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(C)O FKOKUHFZNIUSLW-UHFFFAOYSA-N 0.000 claims description 3
- 229940093625 propylene glycol monostearate Drugs 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 abstract description 31
- 230000000052 comparative effect Effects 0.000 description 37
- 230000000694 effects Effects 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 238000005202 decontamination Methods 0.000 description 6
- 230000003588 decontaminative effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000004530 micro-emulsion Substances 0.000 description 5
- 238000011086 high cleaning Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000270666 Testudines Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 235000013923 monosodium glutamate Nutrition 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229940073490 sodium glutamate Drugs 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000011885 synergistic combination Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000008124 floral development Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2068—Ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/221—Mono, di- or trisaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/667—Neutral esters, e.g. sorbitan esters
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Molecular Biology (AREA)
- Detergent Compositions (AREA)
Abstract
The invention provides a micro-water environment-friendly automobile cleaning agent and a preparation method thereof, wherein the micro-water environment-friendly automobile cleaning agent comprises the following components in parts by weight: 0.4-1 part of cationic surfactant, 24-30 parts of anionic surfactant, 10-15 parts of nonionic surfactant, 6-10 parts of complexing agent, 10-20 parts of cosurfactant, 10-15 parts of diethylene glycol diethyl ether, 10-20 parts of triglyceride, 5-10 parts of light white oil and 40-60 parts of deionized water; the cationic surfactant is alkyl hydroxyethyl dimethyl ammonium chloride, the anionic surfactant is a mixture of sodium cocoyl glutamate and sodium palmitoyl glutamate, and the nonionic surfactant is hexyl glucoside. The cleaning agent does not need a large amount of water during cleaning, has strong detergency, is environment-friendly and is easy to degrade.
Description
Technical Field
The invention relates to the technical field of preparation of automobile cleaning agents, in particular to a micro-water environment-friendly automobile cleaning agent and a preparation method thereof.
Background
With the improvement of the living standard of people, automobile products become an indispensable transportation means for people to travel, and the keeping amount of private cars is increased year by year, so that the automobile cleaning and maintenance demands are also increasing. Generally, the automobile surface is cleaned and maintained by adopting an automobile cleaning agent, and the automobile cleaning agent can remove stains such as greasy dirt, dust and viscose on the automobile body surface, but some strong acid and strong alkali cleaning solution can damage a rubber sealing part of an automobile cleaning machine, and can bring great damage to the automobile body, such as color loss of automobile paint, flower development of windshield glass, reduced perspective, hardening and color loss of a rubber sealing adhesive tape, accelerated aging, and can cause plastic to become color loss and brittle.
At present, a large amount of water is needed for cleaning an automobile, the basic process mainly comprises the steps of firstly flushing the surface of the automobile body with a large amount of water, then spraying a cleaning agent, wiping with a rag, removing stains, then flushing the cleaning agent with a large amount of water, the whole process is time-consuming and waste water, the flushed water is often directly discharged into a ground water network, the components of the cleaning agent after the cleaning agent are not easy to degrade, and great pollution hidden dangers exist.
Disclosure of Invention
Aiming at the defects of water consumption, environmental protection, decontamination and the like of the automobile cleaning agent in the prior art, the invention provides a micro-water environment-friendly automobile cleaning agent and a preparation method thereof. The micro water provided by the invention is used for cleaning and rinsing by using a small amount of water in the cleaning process, so that the effects of high cleaning efficiency and low residue can be achieved.
In order to achieve the above purpose, the present application adopts the following technical scheme:
The micro-water environment-friendly automobile cleaning agent comprises the following components in parts by weight: 0.4-1 part of cationic surfactant, 24-30 parts of anionic surfactant, 10-15 parts of nonionic surfactant, 6-10 parts of complexing agent, 10-20 parts of cosurfactant, 10-15 parts of diethylene glycol diethyl ether, 10-20 parts of triglyceride, 5-10 parts of light white oil and 40-60 parts of deionized water; the cationic surfactant is alkyl hydroxyethyl dimethyl ammonium chloride, the anionic surfactant is a mixture of sodium cocoyl glutamate and sodium palmitoyl glutamate, and the nonionic surfactant is hexyl glucoside.
Preferably, the cationic surfactant is C12-18 alkyl hydroxyethyl dimethyl ammonium chloride. As a trade name, clariant PRAEPAGEN HY.
Preferably, the anionic surfactant is a mixture of sodium cocoyl glutamate and sodium palmitoyl glutamate according to a mass ratio of 1:5.
Preferably, the complexing agent is a composition of sodium citrate and sodium gluconate, and the mass ratio of the sodium citrate to the sodium gluconate is 1:2-4.
Preferably, the cosurfactant is one of sorbitan monostearate or propylene glycol monostearate.
Preferably, 0.6 part of cationic surfactant, 27.5 parts of anionic surfactant, 12 parts of nonionic surfactant, 8 parts of complexing agent, 13 parts of cosurfactant, 15 parts of diethylene glycol diethyl ether, 16 parts of triglyceride, 10 parts of light white oil and 60 parts of deionized water.
The preparation method of the micro-water environment-friendly automobile cleaning agent comprises the following steps:
s1: weighing the components according to weight fractions; uniformly stirring a cationic surfactant, an anionic surfactant and a nonionic surfactant at 35-45 ℃ to obtain a compound surfactant;
S2: adding sodium citrate and sodium gluconate into the step S1, mixing and stirring, and continuously stirring to obtain a mixed solution A;
s3: mixing triglyceride and light white oil, and stirring at 55-65deg.C; and then adding the mixed solution A obtained in the step S2, diethylene glycol diethyl ether, a cosurfactant and deionized water, and continuing stirring for reaction to obtain the micro-water environment-friendly automobile cleaning agent.
Preferably, step S1 specifically includes: stirring at a speed of 600-800r/min for 20-30min at 35-45deg.C.
Preferably, step S2 specifically includes: stirring is continued for 10-20min at the speed of 500-700 r/min.
Preferably, the step S3 specifically includes: mixing triglyceride and light white oil, and stirring at 55-65deg.C and 600-800r/min for 10-20min; and then adding the mixed solution A obtained in the step S2, diethylene glycol diethyl ether, a cosurfactant and deionized water, and continuing stirring and reacting for 40-60min.
The beneficial effects are that:
1. The invention adopts alkyl hydroxyethyl dimethyl ammonium chloride, cocoyl sodium glutamate and palm sodium glutamate mixture and hexyl glucoside as a compound surfactant; the synergistic combination of the alkyl hydroxyethyl dimethyl ammonium chloride and the hexyl glucoside obviously improves the wettability and compatibility of the solution, and can effectively and cooperatively remove oil stains and insoluble particle dirt on the surface of a vehicle body; the synergistic combination of the mixture of the hexyl glucoside, the sodium cocoyl glutamate and the sodium palmitoyl glutamate greatly improves degreasing property and detergency; and meanwhile, the alkyl hydroxyethyl dimethyl ammonium chloride can also eliminate static electricity generated by vehicle body friction.
2. In order to further enhance the decontamination effect, the invention adopts sodium citrate and sodium gluconate as complexing agents, can have extremely strong complexing capacity with calcium ions, magnesium ions and iron ions in stains on the surface of a vehicle body, and simultaneously avoids the formation of indissolvable substances by combining metal ions with an anionic surfactant so as to maintain the decontamination activity of the anionic surfactant.
3. The presence of the triglyceride and the light white oil can better increase the decontamination effect; the micro-emulsified liquid is formed by the triglyceride and the light white oil under the action of the surfactant, the cosurfactant and the deionized water, so that the dissolving force on stains is further increased, the droplet size of the micro-emulsified liquid is smaller, the stains in gaps can be better dissolved, the removing effect is better, and the water consumption can be reduced to a greater extent. The addition of the diethylene glycol diethyl ether can greatly improve the detergency of the cleaning agent, and compared with other alcohol ether solvents, the solvent diethylene glycol diethyl ether can be better fused with the microemulsion system to improve the detergency of the cleaning agent.
4. The automobile cleaning agent prepared by the invention has the advantages of strong antistatic and decontamination capability, good cleaning effect, small water consumption during cleaning, biodegradability, health and environmental friendliness, no pollution, compared with similar products on the market, a large amount of water is not needed during use, the cleaning agent is sprayed and used for cleaning dirt by using a towel after being static for a plurality of times, the residual liquid is cleaned by using a water-soaking towel, the cleaning effect is realized, the purpose of low residue is achieved, the purpose of cleaning can be achieved by using micro water, and the water consumption is obviously reduced when the same cleaning effect is achieved.
Detailed Description
The invention will be further described with reference to the following embodiments, which are provided to illustrate the invention, not to limit the invention. Among them, the alkyl hydroxyethyl dimethyl ammonium chloride used in the examples and comparative examples of the present invention was clariant PRAEPAGEN HY.
Example 1
S1: weighing 0.4g of alkyl hydroxyethyl dimethyl ammonium chloride, 4g of sodium cocoyl glutamate, 20g of sodium palmitoyl glutamate and 10g of hexyl glucoside, and stirring at the temperature of 35 ℃ for 20min at the speed of 600r/min to obtain a compound surfactant;
S2: adding 2g of sodium citrate and 4g of sodium gluconate to the step S1, mixing, and continuously stirring for 10min to obtain a mixed solution A;
S3: mixing 10g of triglyceride and 5g of light white oil, and stirring at a speed of 600r/min for 10min at a temperature of 55 ℃; and then adding the mixed solution A obtained in the step S2, 10g of diethylene glycol diethyl ether, 10g of sorbitan monostearate and 40g of deionized water, and continuing to stir and react for 40min to obtain the micro-water environment-friendly automobile cleaning agent.
Example 2
S1: 1g of alkyl hydroxyethyl dimethyl ammonium chloride, 5g of sodium cocoyl glutamate, 25g of sodium palmitoyl glutamate and 15g of hexyl glucoside are weighed and stirred for 30min at the temperature of 45 ℃ at the speed of 800r/min to obtain a compound surfactant;
S2: adding 2g of sodium citrate and 8g of sodium gluconate into the step S1, mixing, and continuously stirring for 20min to obtain a mixed solution A;
S3: mixing 20g of triglyceride and 10g of light white oil, and stirring at a speed of 800r/min for 20min at a temperature of 65 ℃; and then adding the mixed solution A obtained in the step S2, 15g of diethylene glycol diethyl ether, 20g of propylene glycol monostearate and 60g of deionized water, and continuing to stir and react for 60 minutes to obtain the micro-water environment-friendly automobile cleaning agent.
Example 3
S1: weighing 0.6g of alkyl hydroxyethyl dimethyl ammonium chloride, 4g of sodium cocoyl glutamate, 25g of sodium palmitoyl glutamate and 12g of hexyl glucoside, and stirring at the temperature of 40 ℃ for 25min at the speed of 800r/min to obtain a compound surfactant;
S2: adding 2g of sodium citrate and 5g of sodium gluconate into the step S1, mixing, and continuously stirring for 20min to obtain a mixed solution A;
S3: mixing 20g of triglyceride and 6g of light white oil, and stirring at a speed of 750r/min for 15min at a temperature of 55 ℃; and then adding the mixed solution A obtained in the step S2, 12g of diethylene glycol diethyl ether, 18g of sorbitan monostearate and 50g of deionized water, and continuing to stir and react for 45min to obtain the micro-water environment-friendly automobile cleaning agent.
Example 4
S1: weighing 0.8g of alkyl hydroxyethyl dimethyl ammonium chloride, 5g of sodium cocoyl glutamate, 20g of sodium palmitoyl glutamate and 14g of hexyl glucoside, and stirring at the temperature of 45 ℃ for 30min at the speed of 700r/min to obtain a compound surfactant;
s2: adding 2g of sodium citrate and 7g of sodium gluconate into the step S1, mixing, and continuously stirring for 15min to obtain a mixed solution A;
S3: mixing 15g of triglyceride and 8g of light white oil, and stirring at a speed of 700r/min for 20min at a temperature of 60 ℃; and then adding the mixed solution A obtained in the step S2, 15g of diethylene glycol diethyl ether, 20g of sorbitan monostearate and 55g of deionized water, and continuing to stir and react for 55min to obtain the micro-water environment-friendly automobile cleaning agent.
Example 5
S1: weighing 0.6g of alkyl hydroxyethyl dimethyl ammonium chloride, 4.5g of sodium cocoyl glutamate, 23g of sodium palmitoyl glutamate and 12g of hexyl glucoside, and stirring at the temperature of 40 ℃ for 26min at the speed of 800r/min to obtain a compound surfactant;
S2: adding 2g of sodium citrate and 6g of sodium gluconate into the step S1, mixing, and continuously stirring for 18min to obtain a mixed solution A;
S3: mixing 16g of triglyceride and 10g of light white oil, and stirring at a speed of 800r/min for 15min at a temperature of 62 ℃; and then adding the mixed solution A obtained in the step S2, 15g of diethylene glycol diethyl ether, 13g of sorbitan monostearate and 60g of deionized water, and continuing to stir and react for 55min to obtain the micro-water environment-friendly automobile cleaning agent.
Comparative example 1: the difference from example 1 is that the preparation does not contain alkyl hydroxyethyl dimethyl ammonium chloride, whereas the amount of hexyl glucoside is 10.4g; the others are unchanged.
Comparative example 2: the difference from example 1 is that the preparation does not contain hexyl glucoside, but the alkyl hydroxyethyl dimethyl ammonium chloride is used in an amount of 10.4g; the others are unchanged.
Comparative example 3: the difference from example 1 is that the preparation does not contain sodium palmitoyl glutamate, but the dosage of sodium cocoyl glutamate is 24g and the dosage of hexyl glucoside is 10g; the others are unchanged.
Comparative example 4: the difference from example 1 is that the preparation does not contain sodium cocoyl glutamate, but sodium palmitoyl glutamate is 20g and hexyl glucoside is 14g; the others are unchanged.
Comparative example 5: the difference from example 1 is that the preparation does not contain hexyl glucoside, but sodium cocoyl glutamate is 4g and sodium palmitoyl glutamate is 30g; the others are unchanged.
Comparative example 6: the difference from example 1 is that the preparation does not contain triglyceride and light white oil, and the deionized water is used in an amount of 55g; the others are unchanged.
Comparative example 7: the difference from example 1 is that diethylene glycol diethyl ether was not present in the preparation, but was present in an amount of 50g of deionized water; the others are unchanged.
Comparative example 8: the difference from example 1 is that propylene glycol monomethyl ether is used instead of diethylene glycol diethyl ether in step S3; the others are unchanged.
Comparative example 9: the difference from example 1 is that ethylene glycol diethyl ether is used instead of diethylene glycol diethyl ether in step S3; the others are unchanged.
Comparative example 10: commercial Turtle shell, turtle Wax Turtle G-4008R1 hard shell high-foam car washing liquid.
Performance test of examples and comparative examples: a whole piece of the metal plate coated with the heavy-duty automotive paint was taken, and then dried at 60℃for 1 hour to allow the heavy-duty to adhere to the metal plate, and the dried metal plate was cut into 55 pieces of 330mm X100 mm small pieces. Randomly dividing the 55 small blocks into 11 groups of 5 small blocks each; then, cleaning solutions of the cleaning agents of examples and comparative examples (the cleaning agents of examples and comparative examples were diluted with water to a mass concentration of 10%) were sprayed onto the 14 groups of small pieces, sprayed onto the surfaces of the small pieces to be covered with the cleaning agent, then left standing for five minutes, wiped with a dry towel to remove dirt, and then the remaining impurities on the small pieces were wiped with a towel stained with water, and dried at 100 ℃ for 2 hours, and then the cleaning rate and glossiness were tested. Wherein the washing rate was calculated according to a weightless method, wherein the washing rate=100% × (W Metal plate coated with heavy scale and dried -W Washed and dried metal plate )/W Metal plate coated with heavy scale and dried . Gloss: 75 ° measurement (%) using a TOYOSEIKI (glossmeter UD): the test results of each of the above groups were the results of the 5-piece test to calculate the average value.
The results of each example and comparative example are specifically shown in the following table:
| Test | Gloss level | Cleaning rate (%) |
| Example 1 | 115 | 96.5 |
| Comparative example 1 | 101 | 87.8 |
| Comparative example 2 | 100 | 86.3 |
| Comparative example 3 | 103 | 88.6 |
| Comparative example 4 | 105 | 89.7 |
| Comparative example 5 | 102 | 88.1 |
| Comparative example 6 | 98 | 85.0 |
| Comparative example 7 | 96 | 84.2 |
| Comparative example 8 | 106 | 89.9 |
| Comparative example 9 | 107 | 90.6 |
| Comparative example 10 | 101 | 87.6 |
As is clear from comparison of example 1 and comparative examples 1 and 2, when the amount of alkyl hydroxyethyl dimethyl ammonium chloride and hexyl glucoside is unchanged, one of alkyl hydroxyethyl dimethyl ammonium chloride and hexyl glucoside is omitted, the cleaning rate of the obtained cleaning agent and the surface glossiness of the cleaned object are lower than those of example 1, so that the collocation of the alkyl hydroxyethyl dimethyl ammonium chloride and the hexyl glucoside generates synergistic compounding, and the cleaning effect of the product and the glossiness of the cleaned object can be greatly improved. The main reason for analysis is that the combination of the two obviously improves the dirt wetting effect and compatibility of the system, thereby jointly improving the dirt removing effect of the system and the glossiness of the cleaned object.
As can be seen from the comparison of comparative examples 3-5 and example 1, the combination of the mixture of hexyl glucoside, sodium cocoyl glutamate and sodium palmitoyl glutamate also produces a synergistic effect to a certain extent and greatly improves the cleaning effect of the system and the glossiness of the cleaned object. As can be seen from the examples 1 and 6, the presence of the triglyceride and the light white oil of the present invention can better increase the decontamination effect; the reason for this may be that the triglyceride and the light white oil form a micro emulsion liquid under the action of the surfactant, the cosurfactant and the deionized water, so that the micro emulsion system increases the dissolution strength of the cleaning agent to the stains to a certain extent, and the micro emulsion liquid has smaller droplet size, can better infiltrate into the gaps and coat and emulsify the stubborn stains in the gaps, thereby achieving better dirt removal effect. As can be seen from the comparison between the example 1 and the comparative example 7, the addition of diethylene glycol diethyl ether can greatly improve the detergency of the cleaning agent, and the main reason is that the unique polarity and nonpolar solubility of diethylene glycol diethyl ether molecules are fused into different phases, so that the surface tension of the system is reduced, pollutants are permeated and softened, and the detergency of the cleaning agent is further improved. As can be seen from a comparison of example 1 and comparative examples 8-9, the use of diethylene glycol diethyl ether in the present invention is better compatible with the microemulsion system of the present invention than other alcohol ether solvents to enhance the cleaning and detergency of the cleaning agent and to increase the gloss of the surface of the article being cleaned. As can be seen by comparing examples with comparative example 10, the system of the present invention has unexpected effects of decontaminating and increasing the gloss of the surface of the object to be cleaned as compared to the prior art products.
The cleaning agent is sprayed on the surfaces of the small blocks so that the metal blocks are covered by the cleaning solution, then the small blocks are kept stand for five minutes, the dirt is removed by wiping with a dry towel, the residual impurities on the small blocks can be wiped with the towel stained with water, and then the small blocks are dried. When the cleaning rate test is carried out, the cleaning solution of the cleaning agent of the embodiment 1 cleans the metal block and dries the metal block, so that the surface of the metal block is clean and has no trace; therefore, the cleaning agent in the embodiment 1 of the invention has little residue on the surface of the metal block under the condition of small water consumption, and has high cleaning efficiency without residue when the cleaning agent is cleaned by a small amount of water. The metal surfaces of comparative examples 1 to 10, which were dried after washing with the washing solution, exhibited marks and figures, and trace amounts of the washing solution components remained on the surfaces of the above-mentioned washed metal pieces, and particularly, the marks and figures on the metal surfaces of comparative example 7 and comparative example 10 were more serious than those on the other metal surfaces. As is clear from the above, the cleaning solutions of comparative examples 1 to 10 were used in the cleaning method of the present invention, that is, the cleaning was performed with a small amount of water, and a trace amount of the cleaning agent remained on the surface of the metal piece after the cleaning. From the above analysis, the technical solution described in embodiment 1 of the present invention can achieve cleaning with high cleaning rate under the condition of using very small amount of water, and the cleaning agent has no residue on the cleaned object; in contrast, in comparative examples 1 to 10, the cleaning agent would remain on the object to be cleaned with a small amount of cleaning water, i.e., comparative examples 1 to 10, particularly comparative examples 7 and 10, cannot be cleaned with a small amount of water, thereby achieving both the advantages of high cleaning rate and small amount of water.
Compared with similar products in the market, the automobile cleaning agent is used without a large amount of water, the cleaning agent is sprayed and kept still for a plurality of times, the dirt is removed by wiping with a towel, and a small amount of purified water is used for wiping residual liquid by wiping with the towel, so that the automobile cleaning agent which can achieve the purpose of cleaning with micro water is realized, and the water consumption is obviously reduced when the same cleaning effect is achieved.
The above description is merely of preferred embodiments of the present invention, and the scope of the present invention is not limited to the above embodiments, but all equivalent modifications or variations according to the present disclosure will be within the scope of the claims.
Claims (9)
1. The micro-water environment-friendly automobile cleaning agent is characterized by comprising the following components in parts by weight: 0.4-1 part of cationic surfactant, 24-30 parts of anionic surfactant, 10-15 parts of nonionic surfactant, 6-10 parts of complexing agent, 10-20 parts of cosurfactant, 10-15 parts of diethylene glycol diethyl ether, 10-20 parts of triglyceride, 5-10 parts of light white oil and 40-60 parts of deionized water; the cationic surfactant is alkyl hydroxyethyl dimethyl ammonium chloride, the anionic surfactant is a mixture of sodium cocoyl glutamate and sodium palmitoyl glutamate, and the nonionic surfactant is hexyl glucoside;
the complexing agent is a composition of sodium citrate and sodium gluconate;
the cosurfactant is one of sorbitan monostearate or propylene glycol monostearate.
2. The micro-water environment-friendly automobile cleaning agent according to claim 1, wherein the cationic surfactant is C12-18 alkyl hydroxyethyl dimethyl ammonium chloride.
3. The micro-water environment-friendly automobile cleaning agent according to claim 1, wherein the anionic surfactant is a mixture of sodium cocoyl glutamate and sodium palmitoyl glutamate according to a mass ratio of 1:5.
4. The micro-water environment-friendly automobile cleaning agent according to claim 1, wherein the mass ratio of the sodium citrate to the sodium gluconate is 1:2-4.
5. The micro-water environment-friendly automobile cleaning agent according to claim 1, wherein the cationic surfactant is 0.6 part, the anionic surfactant is 27.5 parts, the nonionic surfactant is 12 parts, the complexing agent is 8 parts, the cosurfactant is 13 parts, the diethylene glycol diethyl ether is 15 parts, the triglyceride is 16 parts, the light white oil is 10 parts, and the deionized water is 60 parts.
6. A method for preparing the micro-water environment-friendly automobile cleaning agent according to any one of claims 1 to 5, which is characterized by comprising the following steps:
s1: weighing the components according to weight fractions; uniformly stirring a cationic surfactant, an anionic surfactant and a nonionic surfactant at 35-45 ℃ to obtain a compound surfactant;
S2: adding sodium citrate and sodium gluconate into the step S1, mixing and stirring, and continuously stirring to obtain a mixed solution A;
s3: mixing triglyceride and light white oil, and stirring at 55-65deg.C; and then adding the mixed solution A obtained in the step S2, diethylene glycol diethyl ether, a cosurfactant and deionized water, and continuing stirring for reaction to obtain the micro-water environment-friendly automobile cleaning agent.
7. The preparation method according to claim 6, wherein step S1 specifically comprises: stirring at a speed of 600-800r/min for 20-30min at 35-45deg.C.
8. The preparation method according to claim 6, wherein step S2 specifically comprises: stirring is continued for 10-20min at the speed of 500-700 r/min.
9. The preparation method according to claim 6, wherein step S3 specifically comprises: mixing triglyceride and light white oil, and stirring at 55-65deg.C and 600-800r/min for 10-20min; and then adding the mixed solution A obtained in the step S2, diethylene glycol diethyl ether, a cosurfactant and deionized water, and continuing stirring and reacting for 40-60min.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI900847A0 (en) * | 1989-02-21 | 1990-02-20 | Colgate Palmolive Co | A light liquid detergent composition in the form of a microemulsion and a process for its preparation |
| CN1278717A (en) * | 1997-09-17 | 2001-01-03 | 宝洁公司 | Hair care compositions comprising optical brighteners and hair conditioning agents |
| AU2005282429A1 (en) * | 2004-09-07 | 2006-03-16 | Pure Bioscience | Silver dihydrogen citrate compositions |
| CN103710167A (en) * | 2013-12-27 | 2014-04-09 | 威莱(广州)日用品有限公司 | Liquid laundry detergent for infants and preparation method thereof |
| JP2016008206A (en) * | 2014-06-26 | 2016-01-18 | ロート製薬株式会社 | Detergent composition |
| WO2018045924A1 (en) * | 2016-09-08 | 2018-03-15 | 南京联创慧驾汽车服务有限公司 | Efficient environmentally friendly water-free car-wash cleaning solution and preparation method thereof |
| WO2018204812A1 (en) * | 2017-05-04 | 2018-11-08 | Lubrizol Advanced Materials, Inc. | Dual activated microgel |
| CN110373279A (en) * | 2019-07-25 | 2019-10-25 | 上海旗致环保新材料有限公司 | A kind of environmentally friendly vehicle interior trim cleaning solution and preparation method thereof and application method |
| CN111194207A (en) * | 2017-10-10 | 2020-05-22 | 宝洁公司 | Compact shampoo composition comprising sulfate-free surfactant |
-
2022
- 2022-08-08 CN CN202210942022.4A patent/CN115340911B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI900847A0 (en) * | 1989-02-21 | 1990-02-20 | Colgate Palmolive Co | A light liquid detergent composition in the form of a microemulsion and a process for its preparation |
| CN1278717A (en) * | 1997-09-17 | 2001-01-03 | 宝洁公司 | Hair care compositions comprising optical brighteners and hair conditioning agents |
| AU2005282429A1 (en) * | 2004-09-07 | 2006-03-16 | Pure Bioscience | Silver dihydrogen citrate compositions |
| CN103710167A (en) * | 2013-12-27 | 2014-04-09 | 威莱(广州)日用品有限公司 | Liquid laundry detergent for infants and preparation method thereof |
| JP2016008206A (en) * | 2014-06-26 | 2016-01-18 | ロート製薬株式会社 | Detergent composition |
| WO2018045924A1 (en) * | 2016-09-08 | 2018-03-15 | 南京联创慧驾汽车服务有限公司 | Efficient environmentally friendly water-free car-wash cleaning solution and preparation method thereof |
| WO2018204812A1 (en) * | 2017-05-04 | 2018-11-08 | Lubrizol Advanced Materials, Inc. | Dual activated microgel |
| CN111194207A (en) * | 2017-10-10 | 2020-05-22 | 宝洁公司 | Compact shampoo composition comprising sulfate-free surfactant |
| CN110373279A (en) * | 2019-07-25 | 2019-10-25 | 上海旗致环保新材料有限公司 | A kind of environmentally friendly vehicle interior trim cleaning solution and preparation method thereof and application method |
Non-Patent Citations (5)
| Title |
|---|
| Application of dodecyldimethylbenzylammonium chloride in bacteriostatic laundry detergent;X Liujian;China Detergent ＆ Cosmetics;20161031;第46卷(第10期);576-590 * |
| 环境友好洗涤产品创新之路;王泽云;刘心建;;中国洗涤用品工业;20180215(第02期);全文 * |
| 胡砚韬 ; 胡瑾环 ; 朱沛华 ; 熊慧敏.一种列车环保高效清洗剂及其制备方法.科技成果.2016,1-2. * |
| 阳离子表面活性剂复配体系研究进展;肖勰阳;闫国伦;陈亚萍;穆怡佳;;山东化工;20191208(第23期);全文 * |
| 龚毓曦.《汽车美护产品配方与工艺》.长春：吉林大学出版社,2021,66. * |
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