CN105385514A - Kitchen and bath detergent and preparation method thereof - Google Patents
Kitchen and bath detergent and preparation method thereof Download PDFInfo
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- CN105385514A CN105385514A CN201510725798.0A CN201510725798A CN105385514A CN 105385514 A CN105385514 A CN 105385514A CN 201510725798 A CN201510725798 A CN 201510725798A CN 105385514 A CN105385514 A CN 105385514A
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Abstract
The invention relates to a kitchen and bath detergent and a preparation method thereof. The kitchen and bath detergent is prepared from, 0.5-5% of titanium dioxide with surface modified with a silica layer, 0.001-0.1% of copper acetate, 0.1-1% of activated carbon, 5-15% of an activating agent, 5-30% of a non-ionic surface active agent and the balance deionized water. The kitchen and bath detergent produced through the formula has the equivalent cleaning effect as other detergents, still keeps the quite high sterilization rate even after six months, has the excellent sterilization and disinfection effect for bacteria remaining on kitchen tableware or other hard surfaces, and is excellent in stability.
Description
Technical field
The present invention relates to a kind of kitchen guarding's sanitising agent, particularly a kind of kitchen guarding's sanitising agent containing photocatalyst and preparation method thereof, belongs to kitchen guarding's cleaning applications.
Background technology
At present, be roughly divided into three kinds about on kitchen guarding's cleaning technique and cleaning product: the first is strong base, this sanitising agent counterweight greasy dirt has good removal ability, but due to alkalescence strong, easily cause user's hand discomfort or damage is produced to tool face, there is certain danger.The second is solvent-borne type, this sanitising agent is mainly come off by the dissolving of organic solvent to grease and the emulsification solublization of tensio-active agent reaches the object of wipe oil, but this product is due to containing more organic solvent, smell own is larger, organic solvent likely causes certain damage to the painted surface of utensils for kitchen & toilet simultaneously, causes damage to user.Kitchen guarding's sanitising agent commercially available at present belongs to first two type mostly.The third is pure surfactant formula, and this formula has given full play to the effect of the infiltration of tensio-active agent, emulsification and solubilising, realizes the removal to greasy dirt.This series products has certain height on formula technique, and general detersive power is poor, and formula is complicated, and cost is higher.But pay close attention to how efficiently decontamination more at present, not enough to the research of other function of sanitising agent.We know, kitchen guarding's article are all have direct or indirect relation with our food as tableware, wall, ground, generally remain the bacterium, malodorant etc. of food raw material or food spoilage generation, are thus necessary the sterilization and the deodorizing effect that improve sanitising agent.
At present in order to produce the effect of sterilization, deodorizing, the general disinfection sanitizer added has cationic active agent, chlorine compound, containing iodine compound, chemical oxidizing agent etc.Wherein cationic active agent can nonionic, bi ion active agent compound, and representative is quaternary compound, but structure is not strong for sterilization effect.Containing iodine sanitising agent, iodine and tensio-active agent complexing are played a role, effective compared with chlorine-containing compound, but these compounds have certain pungency to skin.The representative of chemical oxidizing agent is chloramines and chlorophenols compound, also can with tensio-active agent compound, but these compounds for contact skin or respiratory tract all there is pungency.Thus, the gentle disinfection sanitizer efficiently of development of new is necessary.
The washing composition that with the addition of photocatalyst has been proposed up to now.JP2005-082708A discloses a kind of laundry detergent, it comprises photocatalyst as titanium dioxide, under light illumination, the oxidizing substance that photocatalyst produces such as superoxide anion and hydroxyl radical free radical can play the effect of sterilization and disinfection, but the oxidizing reaction of photocatalyst is slowly carried out, the composition of washing composition itself is decomposed by photocatalyst, and easily precipitates, and namely dispersion stabilization is not high.
CN101565656A discloses a kind of laundry material, comprise nanometer anion powder, 4A zeolite, photocatalyst, anion surface activity material, polymer bonding material, high-molecular-weight glutenin subunits etc., but this is a kind of solid detergent, and unexposed any effect aspect result.
Thus, for prior art defect, the present invention is intended to develop a kind of kitchen guarding's sanitising agent containing photocatalyst, and its green gentleness is not hindered hand, do not hindered crust, stability is high, cleaning capacity is strong, and there is efficient, stable disinfection effect, to meet daily life needs.
Summary of the invention
In order to address the aforementioned drawbacks, present inventor has performed and concentrate on studies, after paying a large amount of creative work, thus complete the present invention.
The present invention relates to a kind of kitchen guarding's sanitising agent, particularly a kind of kitchen guarding's sanitising agent containing photocatalyst, and find surprisingly, described kitchen guarding's sanitising agent of the present invention not only has the cleaning effect suitable with other sanitising agent, and under visible light illumination, the bacterium remained for kitchenware or other crust has excellent disinfection effect, and excellent in stability.
In addition, present invention also offers the preparation method of this kitchen guarding's sanitising agent.
Specifically, first aspect, the invention provides a kind of kitchen guarding's sanitising agent, by percentage to the quality, described kitchen guarding's sanitising agent comprises: finishing has the titanium dioxide 0.5-5% of silica layer, neutralized verdigris 0.001-0.1%, gac 0.1-1%, activator 5-15%, nonionogenic tenside 5-30%, the deionized water of surplus.
In described kitchen guarding's sanitising agent of the present invention, described finishing has in the titanium dioxide of silica layer, titanium dioxide is nitrogen-doped anatase-type titanium dioxide, described finishing has the mass percent of the titanium dioxide of silica layer to be 0.5-5%, such as, can be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%.
In described kitchen guarding's sanitising agent of the present invention, described finishing has the titanium dioxide of silica layer to be obtained by the method comprised the steps:
(1) anatase titanium dioxide nanometer powder mixed with urea and stir, then at 400-600 DEG C, 40-60 minute is incubated, obtain nitrogen-doped anatase-type titania powder, wherein the mass ratio of titanic oxide nano powder and urea is 30-80: 1.
(2) by the nitrogen-doped anatase-type titania powder of n-octyl Trimethoxy silane and step (1) gained at mass percent concentration be 95% ethanol in mix and blend 2-10h, then centrifugal, with washing with acetone 3-6 time, then vacuum-drying at 40-60 DEG C, obtains the titanium dioxide that finishing has silica layer.
In above-mentioned steps (1), the granularity of anatase titanium dioxide nanometer powder is 10-30nm, such as, can be 10nm, 15nm, 20nm, 25nm or 30nm.
In above-mentioned steps (1), anatase titanium dioxide nanometer powder mixes with urea and holding temperature after stirring is 400-600 DEG C, such as, be 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C or 600 DEG C;
In above-mentioned steps (1), soaking time is 40-60 minute, such as, can be 40 minutes, 45 minutes, 50 minutes, 55 minutes or 60 minutes.
In above-mentioned steps (1), the mass ratio of anatase titanium dioxide nanometer powder and urea is 30-80: 1, such as, can be 30: 1,40: 1,50: 1,60: 1,70: 1 or 80: 1.
In above-mentioned steps (2), the weight ratio of the nitrogen-doped anatase-type titania powder of n-octyl Trimethoxy silane and step (1) gained is 1: 50-100, such as, can be 1: 50,1: 60,1: 70,1: 80,1: 90 or 1: 100.
In described kitchen guarding's sanitising agent of the present invention, the mass percent of neutralized verdigris is 0.001-0.1%, such as, can be 0.001%, 0.005%, 0.01%, 0.02%, 0.04%, 0.06%, 0.08%% or 0.1%.
In described kitchen guarding's sanitising agent of the present invention, the mass percent of described gac is 0.1-1%, and such as can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%, its specific surface area is preferably 500-700m
2/ g, most preferably is 650m
2/ g.
In described kitchen guarding's sanitising agent of the present invention, described activator be selected from Trisodium Citrate, sodium fumarate, sodium tartrate, sodium maleate, Sodium.alpha.-hydroxypropionate, L-arginine, sodium succinate any one or multiple arbitrarily.
The mass percent of described activator is 5-15%, such as, can be 5%, 7%, 9%, 10%, 12%, 14% or 15%.
In described kitchen guarding's sanitising agent of the present invention, described nonionogenic tenside has following structure: R1-[EO] n-[PO] m-[BO] p-H
Wherein: R1 is C8-C20 alkyl; EO is ethylene oxide; PO is propylene oxide; BO is oxybutylene; M, n, p are the integer of 1-10;
As one citing, m, n and p can be all 1,2,3,4,5,6,7,8,9 or 10 independently.
The mass percent of described nonionogenic tenside is 5-30%, such as, can be 5%, 10%, 15%, 20%, 25% or 30%.
The alkoxyl group copolyreaction that this nonionogenic tenside can adopt prior art known is synthesized, such as method disclosed in US2677700A, US2674619A.
According to second aspect, the invention provides a kind of method preparing described kitchen guarding's sanitising agent, first activator, gac, finishing there are is the titanium dioxide of silica layer, neutralized verdigris at room temperature grinds pre-mixing according to aforementioned proportion, then the above-mentioned powder that deionized water, nonionogenic tenside and premix get togather is joined successively agitator mixing, 5-24h is stirred at 30-40 DEG C of temperature, leave standstill, obtain described kitchen guarding's sanitising agent.
The present invention is by the organic assembling of photocatalyst, gac, neutralized verdigris and activator, the selection of nonionogenic tenside, the control of each component concentration, thus make final kitchen guarding's sanitising agent not only have suitable soil removability relative to prior art, but also have excellent disinfection effect, and there is very excellent stability.Obtaining of all these effects, depends on enforcement and/or the selection of following technique means:
1. finishing has the nitrogen-doped titanium dioxide of silica layer after excited by visible light, can produce active superoxide anion and hydroxyl radical free radical, thus can play germicidal action in a mild condition.Meanwhile, the modification of surface silicon oxygen layer can strengthen the dispersion stabilization of titanium dioxide nano-particle, and is conducive to the transmission of surface-catalyzed reactions thing.
2. certain surface area activated carbon, can play interception, thus improves the light stability of photocatalyst, and can adsorb the bacterium or other repugnant substance for the treatment of catalyzed degradation, thus makes in limited light application time, improves the efficiency of photo-catalyst.
3. by the activator of select tape carboxyl, titanium dioxide surface can be adsorbed on by ester bond effect, thus improve its dispersion stabilization, also can improve the soil removability of nonionogenic tenside simultaneously as washing assistant.
4. the nonionogenic tenside that the present invention selects is that the art-recognized green gentleness of a class is not hindered hand and do not hindered the compound of crust, and has efficient soil removability.
Embodiment
Below by specific embodiment, the present invention is described in detail, but these exemplary embodiments not form any type of any restriction to real protection scope of the present invention.
Preparation example 1:
(1) be that the anatase titanium dioxide powder of 10nm mixes with urea and stirs by granularity, then at 400 DEG C of temperature, be incubated 40 minutes, obtain nitrogen-doped anatase-type titania powder, wherein the mass ratio of titanium dioxide and urea is 30: 1.
(2) by n-octyl Trimethoxy silane and above-mentioned nitrogen-doped anatase-type titania powder with 1: 50 mass ratio, be mix and blend 2h in the ethanol of 95% at mass percent concentration, then centrifugal, with washing with acetone 3 times, then vacuum-drying at 40 DEG C, obtain the titania powder that finishing has silica layer, called after SiTiN-1.Through transmission electron microscope test, median size is 12nm.
Preparation example 2:
(1) be that the anatase titanium dioxide powder of 15nm mixes with urea and stirs by granularity, then at 480 DEG C of temperature, be incubated 45 minutes, obtain nitrogen-doped anatase-type titania powder, wherein the mass ratio of titanium dioxide and urea is 50: 1.
(2) by n-octyl Trimethoxy silane and above-mentioned nitrogen-doped anatase-type titania powder with mass ratio 1: 75, be mix and blend 5h in the ethanol of 95% at mass percent concentration, then centrifugal, with washing with acetone 4 times, then vacuum-drying at 50 DEG C, obtain the titanium dioxide that finishing has silica layer, called after SiTiN-2.Through transmission electron microscope test, median size is 17nm.
Preparation example 3:
(1) be that 20nm anatase titanium dioxide powder mixes with urea and stirs by granularity, then at 550 DEG C of temperature, be incubated 50 minutes, obtain nitrogen-doped anatase-type titania powder, wherein the mass ratio of titanium dioxide and urea is 65: 1.
(2) by n-octyl Trimethoxy silane and above-mentioned nitrogen-doped anatase-type titania powder with mass ratio 1: 100, be mix and blend 10h in the ethanol of 95% at mass percent concentration, then centrifugal, with washing with acetone 5 times, then vacuum-drying at 55 DEG C, obtain the titanium dioxide that finishing has silica layer, called after SiTiN-3.Through transmission electron microscope test, median size is 23nm.
Preparation example 4:
(1) be that the anatase titanium dioxide powder of 25nm mixes with urea and stirs by granularity, then at 600 DEG C of temperature, be incubated 60 minutes, obtain nitrogen-doped anatase-type titania powder, wherein the mass ratio of titanium dioxide and urea is 80: 1.
(2) by n-octyl Trimethoxy silane and above-mentioned nitrogen-doped anatase-type titania powder with mass ratio 1: 55, be mix and blend 4h in the ethanol of 95% at mass percent concentration, then centrifugal, with washing with acetone 4 times, then vacuum-drying at 60 DEG C, obtain the titanium dioxide that finishing has silica layer, called after SiTiN-4.Through transmission electron microscope test, median size is 28nm.
Embodiment 1:
First by activator, gac, the SiTiN-1 of preparation example 1, neutralized verdigris at room temperature grinds pre-mixing, then by deionized water, the above-mentioned powder that n-C12H25-[EO] 5-[PO] 3-[BO] 2-H and premix get togather joins agitator mixing successively, wherein each raw material mixes according to following required mass percentage: the SiTiN-1 of 1%, 0.01% neutralized verdigris, the gac (specific surface area that adsorptiometry records is 650m2/g) of 0.5%, 10% Trisodium Citrate, n-C12H25-[EO] 5-[PO] 3-[BO] 2-H of 30%, all the other are deionized water, 24h is stirred at 30 DEG C of temperature, leave standstill, without demixing phenomenon, obtain described kitchen guarding's sanitising agent.
Embodiment 2:
Except the L-arginine of the SiTiN-1 in the SiTiN-2 alternative embodiment 1 of the preparation example 2 by equivalent and use equivalent is replaced except Trisodium Citrate, to implement the present embodiment with the same way of embodiment 1, obtain described kitchen guarding's sanitising agent.
Embodiment 3:
Except the sodium maleate of the SiTiN-1 in the SiTiN-3 alternative embodiment 1 of the preparation example 3 by equivalent and use equivalent is replaced except Trisodium Citrate, to implement the present embodiment with the same way of embodiment 1, obtain described kitchen guarding's sanitising agent.
Embodiment 4:
Except by except the SiTiN-1 in the SiTiN-4 alternative embodiment 1 of preparation example 4, to implement the present embodiment with the same way of embodiment 1, obtain described kitchen guarding's sanitising agent.
Embodiment 5:
Except the content of SiTiN-1 in embodiment 1 is replaced with 5% and use 15% Sodium.alpha.-hydroxypropionate replace except 10% Trisodium Citrate, to implement the present embodiment with the same way of embodiment 1, obtain described kitchen guarding's sanitising agent.
Embodiment 6:
Except by except the content of SiTiN-1 replaces with 0.5% in embodiment 1, to implement the present embodiment with the same way of embodiment 1, obtain described kitchen guarding's sanitising agent.
Embodiment 7:
Except 0.01% neutralized verdigris in embodiment 1 being replaced with 0.08% neutralized verdigris and replacing with except the sodium tartrate of 5% by the Trisodium Citrate of 10%, to implement the present embodiment with the same way of embodiment 1, obtain described kitchen guarding's sanitising agent.
Embodiment 8:
Except by embodiment 1 0.5% gac replace with except the gac of 1%, to implement the present embodiment with the same way of embodiment 1, obtain described kitchen guarding's sanitising agent.
Sanitising agent prepared by embodiment 1-8 does not show any to be appreciablely separated after room temperature places three months, demonstrates special satisfactory stability.
Comparative example 1-4:
Except not containing in embodiment 1 except SiTiN-1, neutralized verdigris, gac, activator respectively, implement this comparative example 1-4 respectively with the same way with embodiment 1, wherein there is obvious demixing phenomenon in kitchen guarding's sanitising agent of comparative example 4.
Comparative example 5-6:
Except respectively the content of SiTiN-1 in enforcement 1 being replaced with except 0.1% or 10%, to implement comparative example 5-6 respectively with the same way of embodiment 1.
Comparative example 7-8:
The gac being 630m2/g except the specific surface area recorded by adsorptiometry in enforcement 1 replaces with 300m
2/ g or 1000m
2outside the gac of/g, to implement comparative example 7-8 respectively with the same way of embodiment 1.
Comparative example 9-11:
Except not adding in enforcement 1 except gac, SiTiN-1, neutralized verdigris respectively, and correspondingly add respectively outside Cocoalkyl benzyl dimethyl ammonium, Iodophor, Whitfield's ointment, to implement comparative example 9-11 respectively with the same way of embodiment 1, namely do not add gac in comparative example 9, but add Cocoalkyl benzyl dimethyl ammonium; Do not add SiTiN-1 in comparative example 10, but add Iodophor; Do not add neutralized verdigris in comparative example 11, but add Whitfield's ointment.
Performance test and stability test
The clean-up performance of the material in kitchen guarding's sanitising agent of the present invention that each embodiment obtains by following measuring and comparative example and sterilization and disinfection performance.
1, the present invention's qualitative decontamination testing method used is: from the oil box of normal domestic use lampblack absorber, collect 4-6 greasy dirt sample and mix, then mix with the ratio of n-propyl alcohol in 3: 1 (mass ratioes), after mixing by gained mixed solution even application on the surface of No. 45 steel discs, and at room temperature place 3 hours, then scratch into the lattice of 5 × 4 after continuing at room temperature aging 24-36 hour, the coating weight of each lattice is about 0.3g.
The test specimens aqueous solution (mass percent concentration is 5%) of equal in quality percentage concentration is dripped in each and every one grid spaces every, leave standstill after 2 days according to the testing method in standard " JB/T4323.1-1999 water base metal cleaning agent ", general crust pendulum is used to wash the quantitative assay that machine carries out detersive power, record pendulum washes rear dirt amount with pendulum before washing, and calculates detersive efficiency.
Wherein commercial samples 1,2 is respectively " brave and fierce Mr. ", " goldfish liquid detergent ", and result is shown in Table 1;
Table 1
| Numbering | Soil removal efficiency (%) |
| Embodiment 1 | 94.5 |
| Embodiment 2 | 94.8 |
| Embodiment 3 | 95.5 |
| Embodiment 4 | 94.2 |
| Embodiment 5 | 93.6 |
| Embodiment 6 | 94.2 |
| Embodiment 7 | 94.5 |
| Embodiment 8 | 93.8 |
| Commercial samples 1 | 94.4 |
| Commercial samples 2 | 90.1 |
| Comparative example 1 | 92.5 |
| Comparative example 2 | 93.4 |
| Comparative example 3 | 91.1 |
| Comparative example 4 | 92.3 |
As seen from the above table: kitchen guarding's sanitising agent of the present invention has the clean-up performance suitable with commercial detergent, this illustrates that adding photocatalyst does not affect the performance that the ingredient exerts such as nonionogenic tenside clean decontamination.
Get each embodiment of equal quality and the sample of comparative example, then dilute 100 times with Sterile Hard Water.Bactericidal assay test temperature is 25 DEG C, and adopt the luminescent lamp (F8T5DL, YoungwhaLampCo.) of 10W to provide the visible ray photograph of 400-720nm, illumination sterilizing time is 1 hour.Detect according to being ministry of Health of China " disinfection technology standard " (the 2002nd edition), 2.1.1.5.5 joint and 2.1.1.7.4 joint, adopt Suspension quantitative bactericidal test method, bactericidal assay the results are shown in table 2.
Table 2
As seen from the above table: kitchen guarding's sanitising agent of the present invention has excellent sterilization and disinfection performance, and when not comprising SiTiN-1, almost without bactericidal property, and when not containing neutralized verdigris or gac or activator, its bactericidal property all can sharply reduce.Meanwhile, sanitising agent of the present invention, compared with other sanitising agents containing conventional sterilization compound, has more excellent sterilizing rate under the same conditions.
In addition, as can be seen from the above table, the content of the titanium dioxide that siloxanes of the present invention is modified has significant impact to its bactericidal property, and when for 0.5-5%, bactericidal property is best, outside this scope, then has significant reduction.Meanwhile, the specific surface area of gac also has significant impact to its bactericidal property, when being 500-700m
2during/g, bactericidal property is best, outside this scope, then has significant reduction.
After kitchen guarding's sanitising agent in above-described embodiment and comparative example is placed 6 months in masking foil, again measure it to bactericidal property, thus investigate its stability.The results are shown in Table 3.
Table 3
As seen from the above table, kitchen guarding's sanitising agent of the present invention has satisfactory stability, even if after six months, still maintains very high sterilizing rate.And when not comprising gac or promoting agent, bactericidal property significantly reduces.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can to the present invention do various change, amendment and or modification, these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. kitchen guarding's sanitising agent, by percentage to the quality, described kitchen guarding's sanitising agent comprises: finishing has the titanium dioxide 0.5-5% of silica layer, neutralized verdigris 0.001-0.1%, gac 0.1-1%, activator 5-15%, nonionogenic tenside 5-30%, the deionized water of surplus.
2. kitchen guarding's sanitising agent as claimed in claim 1, it is characterized in that: described finishing has in the titanium dioxide of silica layer, titanium dioxide is nitrogen-doped anatase-type titanium dioxide.
3. kitchen guarding's sanitising agent as claimed in claim 2, is characterized in that: described finishing has the titanium dioxide of silica layer to be obtained by the method comprised the steps:
(1) anatase titanium dioxide nanometer powder mixed with urea and stir, then at 400-600 DEG C, 40-60 minute is incubated, obtain nitrogen-doped anatase-type titania powder, wherein the mass ratio of titanic oxide nano powder and urea is 30-80: 1.
(2) by the nitrogen-doped anatase-type titania powder of n-octyl Trimethoxy silane and step (1) gained at mass percent concentration be 95% ethanol in mix and blend 2-10h, then centrifugal, with washing with acetone 3-6 time, then vacuum-drying at 40-60 DEG C, obtains the titanium dioxide that finishing has silica layer.
4. kitchen guarding's sanitising agent as claimed in claim 3, it is characterized in that: in described step (1), the granularity of anatase titanium dioxide nanometer powder is 10-30nm.
5. the kitchen guarding's sanitising agent as described in claim 3 or 4, is characterized in that: in described step (2), and the weight ratio of the nitrogen-doped anatase-type titania powder of n-octyl Trimethoxy silane and step (1) gained is 1: 50-100.
6. the kitchen guarding's sanitising agent as described in any one of claim 1-5, is characterized in that: described nonionogenic tenside has following structure:
R1-[EO]n-[PO]m-[BO]p-H
Wherein:
R1 is C8-C20 alkyl; EO is ethylene oxide; PO is propylene oxide; BO is oxybutylene; M, n, p are the integer of 1-10.
7. the kitchen guarding's sanitising agent as described in any one of claim 1-6, is characterized in that: the specific surface area of described gac is 500-700m
2/ g.
8. kitchen guarding's sanitising agent as claimed in claim 7, is characterized in that: the specific surface area of described gac is 650m
2/ g.
9. the kitchen guarding's sanitising agent as described in any one of claim 1-8, is characterized in that: described activator be selected from Trisodium Citrate, sodium fumarate, sodium tartrate, sodium maleate, Sodium.alpha.-hydroxypropionate, L-arginine, sodium succinate any one or multiple arbitrarily.
10. prepare the method for kitchen guarding's sanitising agent described in claim 1 for one kind, concrete steps are: first activator, gac, finishing are had the titanium dioxide of silica layer, neutralized verdigris at room temperature grinds pre-mixing according to aforementioned proportion, then the above-mentioned powder that deionized water, nonionogenic tenside and premix get togather is joined successively agitator mixing, 5-24h is stirred at 30-40 DEG C of temperature, leave standstill, obtain described kitchen guarding's sanitising agent.
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| CN201510725798.0A CN105385514A (en) | 2015-10-23 | 2015-10-23 | Kitchen and bath detergent and preparation method thereof |
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|---|---|---|---|---|
| CN107746757A (en) * | 2017-10-30 | 2018-03-02 | 平湖市中天卫厨设备厂 | A kind of kitchen and bath's cleaning agent |
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| CN107746757A (en) * | 2017-10-30 | 2018-03-02 | 平湖市中天卫厨设备厂 | A kind of kitchen and bath's cleaning agent |
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Application publication date: 20160309 |