CN102071111A - Laundry liquid and preparation method thereof - Google Patents
Laundry liquid and preparation method thereof Download PDFInfo
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- CN102071111A CN102071111A CN 201110005054 CN201110005054A CN102071111A CN 102071111 A CN102071111 A CN 102071111A CN 201110005054 CN201110005054 CN 201110005054 CN 201110005054 A CN201110005054 A CN 201110005054A CN 102071111 A CN102071111 A CN 102071111A
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Abstract
The invention discloses laundry liquid and a preparation method thereof. The laundry liquid is prepared by the following materials in percentage by mass: 0.1 to 5.0 percent of oleophylic modified polymer, 0.2 to 5.0 percent of carboxylic acid polymer, 1 to 25.0 percent of nonionic surfactant, 1 to 25.0 percent of anionic surfactant, 0.01 to 1.5 percent of enzyme, 0.1 to 15.0 percent of enzyme stabilizer, 0.5 to 8.0 percent of foam control agent, 0.5 to 10 percent of other auxiliary agents and the balance of water. By the preparation method of the laundry liquid, the production time can be reduced by about 30 percent, and the laundry liquid is efficiently produced; and the prepared laundry liquid has high detergency to mud and oil stains and high stain redeposition resistance.
Description
Technical field
The present invention relates to the washing composition technical field, be specifically related to a kind of washing liquid and preparation method thereof.
Background technology
In China, along with the raising of living standards of the people, the human consumer more and more favors in using the good washing liquid of solvability.With respect to washing powder, washing liquid has the characteristics of gentleness, easy dissolving, less energy-consumption.Washing liquid is started late in China, and the shared market share is also very low, but washing liquid market keeps growing at top speed recent years always.The commercially available washing liquid of China is still based on common washing liquid at present, and active matter content generally is no more than 25%.And in American-European, Japanese developed country, mainly be concentrating washing liquid, actives is generally more than 25%, 2 times concentrate, 3 times of concentrated washing liquids like by the human consumer deeply.Concentrated washing liquid can be saved packaging material, the reduction production energy consumption has the environmental protection characteristics, will be the developing direction of following washing liquid.
When producing the concentrated type washing liquid, need take much time surfactant dissolves in water, need simultaneously water is heated to certain temperature.If can increase tensio-active agent such as poly alkyl alcohol ethers nonionic, the dissolution rate of aliphatic alcohol polyether sulfate anion in water, can shorten the production time of washing liquid to a great extent, improve the production capacity of washing liquid factory, reduce production costs.The viscosity of concentrated type washing liquid is bigger in addition, and the human consumer is difficult for using.Need seek a kind of can viscosity reduction and improve the auxiliary agent of the dissolution rate of tensio-active agent.
In the daily life; run into oil loving dirt through regular meeting; sebum dirt as edible oil, machine oil, human secretory; also has the hydrophilic dirt of natural inorganic in addition; except that the dirt that has once in a while in the soil; mostly be buoyant dust in the atmosphere, in office where the district all has more silicon, aluminium, iron, calcium, manganese in any case.Hydrophilic dirt of these natural particles and oleophylic dirt mix and form the W-O emulsification system attached on the clothes, when the human body perspiration is more, change into the O-W system again, and W-O and O-W can transform mutually, but mainly are the W-O types.This class stain is difficult to remove.Traditional washing composition relies on solubilising, the wetting action of tensio-active agent can remove the dirt of a part, but can not reach gratifying effect.When these mixed dirts deposit on the clothing behind the wash-out from the fabric easily once more.So need seek one or more polymkeric substance, can act synergistically with tensio-active agent, reach gratifying removal dirt effect, and can be suspended in the dirt that elutes and prevent in the washing soln that dirt from depositing to the surface of fabric once more.
Polymkeric substance is used in washing composition widely.Disclose the polyamine that contains hydrophobically modified and the laundry detergent composition of nonionogenic tenside as CN 1404525C, said composition provides enhanced to remove hydrophilic dirt, especially the effect of clay.
US 5,858,948 disclose the washing liquid that contains modified polyamine polymers, and this polyamine polymer contains function modified group can improve the clean effect of washing liquid to cotton fabric, and simultaneously composite have the composition and the proteolytic enzyme that can improve non-cotton fabric clean effect.
US 7,331, and 355 disclose floor and the glass cleaner composition that contains co-polymer.This sanitising agent can put in place in a step cleaning, and can improve the gloss of timber floor.US2007/0272277 discloses a kind of meal lotion that contains the multiple polymers component, and this polymkeric substance is formed by hydrophilic, oleophylic monomer copolymerization, can improve the meal lotion smeary is removed ability.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of strong detergency to mud greasy dirt dirt, the anti-soil dirt strong washing liquid of deposition capability again with not enough, and the dissolution rate of the tensio-active agent that this washing liquid contained in water is big.
Another object of the present invention is to provide the preparation method of above-mentioned washing liquid.
Purpose of the present invention is achieved through the following technical solutions:
A kind of washing liquid is prepared by the composition of following mass percent:
Oleophylic is polymer-modified: 0.1～5.0%
Carboxylic acid polyalcohol: 0.2～5.0%
Nonionogenic tenside: 1.0～25.0%
Anion surfactant: 1.0～25.0%
Enzyme: 0.01～1.5%
Enzyme stabilizers: 0.1～15.0%
Foam Control: 0.5～8.0%
Other auxiliary agents: 0.5～10%
Water: surplus
A kind of washing liquid also can be prepared by the composition of following mass percent:
Oleophylic is polymer-modified: 0.5～4.0%
Carboxylic acid polyalcohol: 0.5～4.0%
Nonionogenic tenside: 5～23.0%
Anion surfactant: 5～23.0%
Enzyme: 0.05～1.0%
Enzyme stabilizers: 2.0～15.0%
Foam Control: 1.0～8.0%
Other auxiliary agents: 1.0～8.0%
Water: surplus
A kind of washing liquid can also be prepared by the composition of following mass percent:
Oleophylic is polymer-modified: 1.0～3.0%
Carboxylic acid polyalcohol: 1.0～2.0%
Nonionogenic tenside: 15.0～20.0%
Anion surfactant: 10.0～20.0%
Enzyme: 0.3～0.8%
Enzyme stabilizers: 7.0～13.0%
Foam Control: 2.0～7.0%
Other auxiliary agents: 3.0～6.0%
Water: surplus
The present invention adopts oleophylic polymer-modified, is used for improving the dissolution rate of washing liquid production process tensio-active agent, and the detergency ability of raising washing liquid and anti-soil dirt be deposition properties again.
Described oleophylic is polymer-modified to be formed by monomer that has hydrophilic-structure more than and the monomer polymerization that has the oleophylic structure more than one; Monomer with hydrophilic-structure is 1: 8～99: 1 with the monomeric mol ratio with oleophylic structure, preferred 1: 2～8: 1; This oleophylic modified polymer molecule amount is 800～10000, and is preferred 1000～9000, more preferably 2000～8000.
Described monomer with hydrophilic-structure is the monomer that contains carboxylate radical, as vinylformic acid, toxilic acid, Uregit, α-Lv Bingxisuan, α-itrile group vinylformic acid, butenoic acid, α-Ben Jibingxisuan, Sorbic Acid, methylene-succinic acid;
Described monomer with oleophylic structure is vinylbenzene, alpha-methyl styrene, methyl methacrylate, 2-ethylacrylic acid, octyl group vinylformic acid.
Be fit to that oleophylic of the present invention is polymer-modified selects business-like product, as the Alcosperse series oleophylic modified product of Akzo Nobel N.V..
Described carboxylic acid polyalcohol is polymerized by in vinylformic acid, toxilic acid, Uregit, α-Lv Bingxisuan, α-itrile group vinylformic acid, butenoic acid, Sorbic Acid or the methylene-succinic acid more than one, its molecular weight is 1000～10000, preferred 2000～6000, preferred especially 3000～5000.
The synthetic method of described carboxylic acid polyalcohol can be with reference to existing publication, as U.S. Pat 5,328, and 972, US 11,459,233.
Be fit to carboxylic acid polyalcohol of the present invention and can select commerical prod for use, as the Dow Chemical Company the Acusol series product.
Described nonionogenic tenside can for:
1) fatty alcohol-polyoxyethylene ether of C12-C14, its oxyethyl group adduct number can be 9 or 7, preferred 7.Can select the nonionogenic tenside of TERGITOLTM26-L series of the Dow Chemical Company or the NEODOL nonionogenic tenside of Shell Co. Ltd.
2) C12-C14 alkyl glycoside nonionogenic tenside.Can select the nonionogenic tenside of the Glucopon series of Kening Co.,Ltd for use.
3) condenses of C12-C18 Fatty Alcohol(C12-C14 and C12-C18) and ethylene oxide/propylene oxide segmented copolymer can be selected the nonionogenic tenside of the ECOSURFTM EH of the Dow Chemical Company series for use.
Described anion surfactant can for:
1) C11～C18 alkylbenzene sulfonate (LAS)
2) C12～C18 alkyl alkoxy sulfate (AES)
Described enzyme can be proteolytic enzyme, amylase, lipase, cellulase, peroxidase, mannase; Preferred protease.
Enzyme used in the present invention can be selected the commerical prod on the market for use, as Novozymes Company
The proteolytic enzyme of series, company of outstanding person's energy section
The proteolytic enzyme of series.
In order to make the enzyme among the present invention stable in prescription, need in prescription, add enzyme stabilizers.Enzyme stabilizers can be that any enzyme that can make is stable and with the good material of formula system compatibleness, it can be more than one mixtures of following material:
A) calcium ion or magnesium ion; Preferred calcium ion.Calcium ion rises important important to the stability of zymin, its can with the protease activities center in conjunction with suppressing its activity.
B) derivative of borate or boric acid.
C) carboxylate salt of C1～C4 is preferentially selected formate.
D) alcohol is as propylene glycol, ethanol, sorbyl alcohol.Preferential propylene glycol and the ethanol selected.
For the foam that makes washing liquid of the present invention enriches extent control in suitable scope, need add Foam Control in the present invention.Foam Control can be selected C12～C18 soap, organosilicon.
Described other auxiliary agents are meant white dyes, sequestrant, sanitas, essence or the pigment that can add as required.
The preparation method of above-mentioned washing liquid may further comprise the steps:
(1) whole anion surfactant in the prescription is mixed with 0.5～1.5% oleophylic is polymer-modified, stir;
(2) polymer-modified, the whole carboxylic acid polyalcohol of nonionogenic tensides whole in the prescription and remaining oleophylic is mixed, stir;
(3) in agitator kettle, add entry, be heated to 40 ℃～60 ℃, add the mixture of step (1) and step (2), stir;
(4) in agitator kettle, add enzyme stabilizers, soap and sequestrant, stir;
(5) the pH value of reaction system is 7～9 in the adjusting agitator kettle;
(6) add enzyme, organosilicon, whitening agent, sanitas and essence again, stirred discharging 5～15 minutes.
The present composition contains polymeric system, can reduce the dissolution time of tensio-active agent when producing washing liquid, improves the production efficiency of washing liquid.The polymkeric substance compound system can act synergistically with surfactant system in decontamination process, significantly improves the detersive power of washing liquid to mud greasy dirt dirt.When more mud greasy dirt dirt was arranged in the laundry processes by wash-out, polymkeric substance can be brought into play the effect of antiredeposition.
The present invention has following advantage and effect with respect to prior art:
(1) it is about 30% that the preparation method of washing liquid of the present invention can reduce the production time, realized the High-efficient Production of washing liquid.
(2) deposition capability is strong again to strong detergency, the anti-soil dirt of mud greasy dirt dirt for washing liquid of the present invention, and the dissolution rate of the tensio-active agent that it contained in water is big.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
Present embodiment is a Comparative Examples, and what adopted is prior art, and the composition of its washing liquid is as shown in table 1, and the preparation process of washing liquid is as follows:
(1) in agitator kettle, feeds deionized water, open and stir, be heated to 40 ℃～60 ℃;
(2) in agitator kettle, add alkyl benzene sulphonate (ABS) salt anionic surfactant, AES to dissolving fully;
(3) drop into the fatty alcohol-polyoxyethylene ether nonionogenic tenside to dissolving fully toward agitator kettle;
(4) drop into soap, Trisodium Citrate, Sodium Tetraborate, calcium chloride, sodium formiate, propylene glycol toward agitator kettle;
(5) regulate pH value to 7～9;
(6) drop into proteolytic enzyme, amylase, cellulase, lipase, mannase, essence, silicone antifoam agent, whitening agent, sanitas toward agitator kettle, stirred 5 minutes, sample examination, qualified can discharging the packing.
The composition of table 1: embodiment 1 washing liquid
Material name addition (%)
C
11～C
13Alkylbenzene sulfonate 4.0
C
12～C
18Alkyl alkoxy (3EO) 16.0
Vitriol (AES)
C
12～C
14Fatty alcohol-polyoxyethylene ether 15.0
(EO＝7)
Trisodium Citrate 4.0
C12～C18 soap 4.0
(organosilicon disappears 2.0 to the organosilicon suds suppressor
Infusion is DOW
Proteinase-10 .5
Amylase 0.07
Cellulase 0.2
Lipase 0.05
Mannase 0.01
Propylene glycol 5
Sodium Tetraborate 2
Calcium chloride 0.02
Whitening agent CBS-X 0.1
Sodium formiate 3
Essence 0.4
Sanitas (CMIT/MIT) 0.2
The deionized water surplus
This embodiment production time probably is 90 minutes.
Embodiment 2～4
Embodiment 2～4 is an object lesson of the present invention, and the composition of washing liquid is added with polymeric system, and has adopted preparation method provided by the present invention, has reduced the production time, has improved production efficiency.
The composition of embodiment 2～4 washing liquids is as shown in table 2, and the preparation process of washing liquid is as follows:
(1) in agitator kettle, feeds deionized water, open and stir, be heated to 40 ℃;
(2) add AES at pre-molten pot A, the oleophylic of adding 1.5% is polymer-modified, stirs;
(3) in pre-molten pot B, add the fatty alcohol-polyoxyethylene ether nonionogenic tenside, add then that remaining oleophylic is polymer-modified, carboxylic acid polyalcohol stirs;
(4) add AES and fatty alcohol-polyoxyethylene ether nonionogenic tenside in the pre-molten pot in the agitator kettle, stir;
(5) drop into soap, Trisodium Citrate, Sodium Tetraborate, calcium chloride, sodium formiate, propylene glycol toward agitator kettle;
(6) regulate pH value to 7;
(7) drop into proteolytic enzyme, amylase, cellulase, mannase, essence, silicone antifoam agent, whitening agent, sanitas toward agitator kettle, stirred 15 minutes, sample examination, qualified can discharging the packing.
The composition of table 2: embodiment 2～4 washing liquids
The time that embodiment 2～4 produces one pot of (about 2 tons) washing liquid to be needed is about 60 minutes, has saved for about 33% time than embodiment 1
Embodiment 5～7
Embodiment 5～7 is an object lesson of the present invention, and the composition of embodiment 5～7 washing liquids is as shown in table 3, and the preparation process of washing liquid is as follows:
(1) in agitator kettle, feeds deionized water, open and stir, be heated to 60 ℃;
(2) add AES at pre-molten pot A, add 0.5% polymer-modified the stirring of oleophylic;
(3) add fatty alcohol-polyoxyethylene ether and APG nonionogenic tenside in pre-molten pot B, polymer-modified remaining oleophylic then, carboxylic acid polyalcohol input stirs;
(4) add the anion surfactant and the nonionogenic tenside of pre-molten pot in the agitator kettle, stir;
(5) drop into soap, Trisodium Citrate, Sodium Tetraborate, calcium chloride, sodium formiate, propylene glycol toward agitator kettle;
(6) regulate pH value to 9;
(7) drop into proteolytic enzyme, amylase, cellulase, mannase, essence, sanitas toward agitator kettle, stirred 5 minutes, sample examination, qualified can discharging the packing.
The composition of table 3: embodiment 5～7 washing liquids
The time that embodiment 5～7 produces one pot of (about 2 tons) washing liquid to be needed is about 65 minutes, has saved for about 27.7% time than embodiment 1.
The performance evaluation of the obtained washing liquid of embodiment
Detersive power is estimated
In order to verify the detersive power of washing liquid of the present invention, carry out detergency test.Adopt GB carbon black JB-01, GB albumen JB-02, GB sebum JB-03, mud greasy dirt cloth, EMPA117 soiled cotton.Carrying out specimen is embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6, implementation column 7 preparation-obtained washing liquids.
Experiment condition is: adopting 250ppm hard water, wash concentration is that 3g/L, washing time 20 minutes, temperature are 30 ℃, to adopt the vertical spotter of RQHL type, the rotating speed of GB regulation be 60 to change
Experimental result is as follows:
Following table is the difference after washing before soiled cotton is washed.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| The GB carbon black | 17.03 | 18.56 | 18.34 | 18.21 | 18.32 | 19.02 | 19.12 |
| Mud greasy dirt cloth | 12.22 | 15.63 | 15.77 | 15.31 | 15.84 | 15.69 | 15.19 |
| The GB sebum | 22.6 | 24.33 | 23.38 | 24.02 | 23.89 | 24.06 | 24.36 |
| GB albumen | 20.33 | 20.41 | 20.44 | 20.22 | 20.51 | 20.44 | 20.24 |
| EMPA-117 | 11.3 | 11.12 | 12.09 | 12.08 | 12.33 | 12.31 | 12.35 |
From top data as can be seen, relative embodiment 1, embodiment 2～7 has tangible lifting in the performance of GB carbon black, mud greasy dirt cloth, GB sebum detersive power, and the detersive power performance of GB albumen, EMPA-117 soiled cotton is kept identical level.
Antiredeposition performance evaluation
Washing liquid of the present invention is after adding polymeric system, and the antiredeposition performance is greatly improved.With reference to the bioassay standard of GB/T 13174-2008 dress material, embodiment has been carried out antiredeposition performance evaluation with washing composition detersive power and circulation cleaning performance.
Experiment condition: adopting 250ppm hard water, wash concentration is that 3g/L, temperature are 30 ℃, to adopt the vertical spotter of RQHL type, the rotating speed of GB regulation be 60 to change.
Experimentation: stipulate according to GB/T 13174-2008, add the washing composition sample, carry out the GB decontamination of JB-01, JB-02, JB-03, after washing is finished soiled cotton is pulled out, add loess, animal oil, vegetables oil, put into calico and carry out circulation cleaning, wash one and as a child took out calico, dry, use the whiteness instrument to measure calico blu-ray reflection value, the maintenance situation of observing calico.
Below be the antiredeposition result of experiment of each embodiment:
Following numerical value is the whiteness value behind the calico circulation cleaning
From test data as can be seen, embodiment 2, embodiment 3, embodiment 5, embodiment 6 are greatly improved at relative embodiment 1 aspect the calico maintenance, and the sedimentary again performance of anti-soil dirt has had bigger lifting.Prescription is after adding hydrophobically modified polymers, and the antiredeposition performance of washing liquid is greatly improved.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. washing liquid is characterized in that: be that composition by following mass percent prepares:
Oleophylic is polymer-modified: 0.1～5.0%
Carboxylic acid polyalcohol: 0.2～5.0%
Nonionogenic tenside: 1.0～25.0%
Anion surfactant: 1.0～25.0%
Enzyme: 0.01～1.5%
Enzyme stabilizers: 0.1～15.0%
Foam Control: 0.5～8.0%
Other auxiliary agents: 0.5～10.0%
Water: surplus;
Foam Control is C12～C18 soap, organosilicon;
Described other auxiliary agents are white dyes, sequestrant, sanitas, essence or pigment.
2. washing liquid according to claim 1 is characterized in that: be that composition by following mass percent prepares:
Oleophylic is polymer-modified: 0.5～4.0%
Carboxylic acid polyalcohol: 0.5～4.0%
Nonionogenic tenside: 5.0～23.0%
Anion surfactant: 5.0～23.0%
Enzyme: 0.05～1.0%
Enzyme stabilizers: 2.0～15.0%
Foam Control: 1.0～8.0%
Other auxiliary agents: 1.0～8.0%
Water: surplus.
3. washing liquid according to claim 1 is characterized in that: be that composition by following mass percent prepares:
Oleophylic is polymer-modified: 1.0～3.0%
Carboxylic acid polyalcohol: 1.0～2.0%
Nonionogenic tenside: 15.0～20.0%
Anion surfactant: 10.0～20.0%
Enzyme: 0.3～0.8%
Enzyme stabilizers: 7.0～13.0%
Foam Control: 2.0～7.0%
Other auxiliary agents: 3.0～6.0%
Water: surplus.
4. according to each described washing liquid of claim 1-3, it is characterized in that: described nonionogenic tenside is:
1) fatty alcohol-polyoxyethylene ether of C12-C14, its oxyethyl group adduct number is 9 or 7;
2) C12-C14 alkyl glycoside.
5. according to each described washing liquid of claim 1-3, it is characterized in that: described anion surfactant is: C12～C18 alkyl alkoxy sulfate.
6. according to each described washing liquid of claim 1-3, it is characterized in that: described enzyme is proteolytic enzyme, amylase, lipase, cellulase, peroxidase, mannase.
7. washing liquid according to claim 6 is characterized in that: described enzyme is a proteolytic enzyme.
8. according to each described washing liquid of claim 1-3, it is characterized in that: described enzyme stabilizers is calcium ion, borate, formate, propylene glycol, ethanol, sorbyl alcohol.
9. the preparation method of each described washing liquid of claim 1-3 is characterized in that may further comprise the steps:
(1) whole anion surfactant in the prescription is mixed with 0.5～1.5% oleophylic is polymer-modified, stir;
(2) polymer-modified, the whole carboxylic acid polyalcohol of nonionogenic tensides whole in the prescription and remaining oleophylic is mixed, stir;
(3) in agitator kettle, add entry, be heated to 40 ℃～60 ℃, add the mixture of step (1) and step (2), stir;
(4) in agitator kettle, add enzyme stabilizers, soap and sequestrant, stir;
(5) the pH value of reaction system is 7～9 in the adjusting agitator kettle;
(6) add enzyme, organosilicon, whitening agent, sanitas and essence again, stirred discharging 5～15 minutes.
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