CN103938444A - Negative-ion type antibacterial glue - Google Patents
Negative-ion type antibacterial glue Download PDFInfo
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- CN103938444A CN103938444A CN201410162811.1A CN201410162811A CN103938444A CN 103938444 A CN103938444 A CN 103938444A CN 201410162811 A CN201410162811 A CN 201410162811A CN 103938444 A CN103938444 A CN 103938444A
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Abstract
The invention relates to negative-ion type antibacterial glue, and in particular relates to negative-ion type antibacterial glue particularly suitable for cloth. 3-20% (in weight ratio) of negative-ion material is added in glue. According to the negative-ion type antibacterial glue particularly suitable for cloth, as negative ions are radioactively screened, the possible injury to a human body caused by radioactive ingredients is avoided; the negative ions of the negative-ion type antibacterial glue can be released stably and sustainably, and the negative-ion type antibacterial glue can release 5000-25000 negative ions per cubic centimeter through detection, and can remarkably achieve the deodorizing and antibacterial effects; the negative-ion type antibacterial glue has more than 97% of antibacterial ratio to escherichia coli, staphylococcus aureus, pseudomonas fluorescens, bacillus megatherium, bacillus subtilis and the like.
Description
Technical field
The present invention relates to the antibacterial glue of a kind of anion, be specifically related to a kind of antibacterial glue of anion that is specially adapted to cloth.
Background technology
In environmental evaluation, anion concentration is an important parameter of Air Quality Evaluation.In air, the anion of debita spissitudo is suspended in airborne dust, toxic gas and anti-bacteria mould to elimination positive effect, can reach the object purifying air.People are longer in indoor office, inhabitation time simultaneously, the reasons such as indoor, spoiled food smooth owing to ventilating cause foul smell, peculiar smell a lot, and large multipair health has harm, some or even carcinogen, its source has: formaldehyde, ammonia, TDI and the benzene discharging in decorating and renovating material or other organic volatiles; H in lavatory, kitchen
2the multiple organic compound such as S and oil smoke; The stink of house refuse and other corrupt substances; The smog stink that smoking is emitted etc.These foul smell, peculiar smell and bacterium, smog etc. are all with positive charge, and anion can neutralize it; Meanwhile, anion also can neutral zone has smog, the pernicious gas of oxygen radical.
Along with the development of material science, people are studying product that can sustained release anion.As the negative ion paint of producing, anion floor, anion tile etc., and this year, the additive that has occurred the production using anion as cloth is directly produced anion cloth, as CN200710196907.X and CN200810146867.2, its drawback is technique relative complex, and the cost of gained cloth is higher.CN200610006734.6 gives a kind of method using crude tourmaline powder epoxy glue as coating material production health-care cloth, but tourmaline is owing to containing a large amount of radioactive compositions, and it is unfavorable to human body on the contrary that it directly uses.CN201110429923.5 has provided a kind of far-infrared negative-ion gluing, but same its used tourmaline powder, tourmaline contains harmful radioactive composition, pure single tourmaline powder is difficult to discharge anion at normal temperatures, is further lowered again by the ability of tourmaline anion releasing after colloid parcel.Moreover tourmaline is water insoluble, and emulsion paint and white glue with vinyl are water-base cement, and therefore the Combination of the two is not good, and uniformity and bonding force to obtained coating have considerable influence.
Summary of the invention
The invention provides one can sustained release anion and far infrared, has deodorizing, the plurality of health care functions such as antibacterial, and the antibacterial glue of the anion that is specially adapted to cloth easy to use, compound ability is good.
In order to achieve the above object, the technical solution adopted in the present invention is as follows:
The antibacterial glue of anion of the present invention adds anion material in rubber cement, and the weight ratio that described anion material accounts for rubber cement is 3% ~ 20%.
As to further restriction of the present invention, anion material of the present invention is water soluble negative ionic material or water-insoluble anion material.
As to further restriction of the present invention, water-insoluble anion material of the present invention obtains as follows:
Step 1: tourmaline and rare earth grind step by step respectively, screen acquisition granularity and be not less than 500 order ~ 10000 object powder;
Step 2: be mixed to get composition by following parts by weight:
Tourmaline powder: 10 ~ 40 weight portions,
Rare earth: 60 ~ 90 weight portions;
Step 3: step 2 resulting composition is carried out to high-frequency electrical and intensify;
Step 4: the composition that the composition after step 3 gained high-frequency electrical is intensified and step 2 gained intensify without high-frequency electrical is taking weight as 1:(3 ~ 6) ratio be mixed to get composite negative ion material.
As to further restriction of the present invention, tourmaline of the present invention and rare earth through radioactivity prospecting instrument screening dispels radioactive material.
As to further restriction of the present invention, the frequency that high-frequency electrical of the present invention intensifies is 800 ~ 1200 megahertzes.
As to further restriction of the present invention, rubber cement of the present invention is selected from latex rubber cement, mucilago amyli, polyvinyl alcohol chemistry rubber cement or ternary and closes cloth slurry.
Simultaneously, it is a kind of easy and simple to handle that the present invention also provides, the preparation method of the eco-friendly antibacterial glue of anion that is applicable to cloth, the antibacterial glue of its prepared anion can sustained release anion and far infrared, there is deodorizing, the plurality of health care functions such as antibacterial, and easy to use, compound ability good.
In order to achieve the above object, the technical solution adopted in the present invention is as follows:
The antibacterial glue of anion of the present invention is prepared by following method:
Step 1: the water-soluble negative ion powder of getting 1 weight portion adds in the water of 0.8 ~ 1.5 weight portion,
Drip while stirring alkali lye anion is dissolved completely, regulator solution pH to 7.0 ~ 11.0;
Step 2: get the rubber cement of 5 ~ 33 weight portions, add while stirring step 1 gained negative solution, continue to stir 5 ~ 30min after interpolation.
As to further restriction of the present invention, water preheat described in step 1 of the present invention is to 50-70 DEG C, and the alkali described in step 1 is KOH or NaOH.
The antibacterial glue of anion of the present invention is prepared by following method:
Step 1: water-insoluble anion material and water are poured in ball grinder, and wherein the weight ratio of water-insoluble anion material and water is 1:0.6 ~ 0.8, regulates pH to identical with the pH of described rubber cement, and ball milling 8-24 hour makes the aqueous dispersion of anion;
Step 2: the rubber cement of 5 ~ 33 weight portions is poured in the charging basket of high speed dispersor, slowly added the aqueous dispersion of above-mentioned anion in the rubber cement of high-speed stirred, after interpolation, then stir 5 ~ 30 minutes.
Moreover, the invention provides the purposes of the antibacterial glue of described anion in cloth is bonding.
In order to achieve the above object, the technical solution adopted in the present invention is as follows:
The antibacterial glue of anion of the present invention is the application in bonding and cloth coating at cloth.
Rubber cement of the present invention is selected from latex rubber cement, mucilago amyli, polyvinyl alcohol chemistry rubber cement or ternary and closes cloth slurry.Wherein ternary is closed the cloth slurry that cloth slurry is polyacrylamide, polyvinyl alcohol and natural serum blend.
Anion material of the present invention is selected from water soluble negative ion or water-insoluble anion, can use commercially available anion material, also can use and make as provided by the present invention anion material by oneself, while using self-control anion material, the anion quantity that the unit interval discharges and the time of sustainable anion releasing are significantly higher than commercially available negative ion powder.
The preparation method of anion material of the present invention, prepared is a kind of water-insoluble anion, and wherein tourmaline and rare earth composition are screened to 500 ~ 10000 orders through grinding, and order number is larger, the more tiny surface area of particle is just larger, better in the effect of the top layer of glue institute anion releasing.Can select before grinding is sieved or grind after sieving material carried out to radioactivity screening, dispel radioactive material wherein, significantly reduced the radioactivity of finished product, prevent the radioactivity injury that human body is produced.
Beneficial effect of the present invention comprises:
The invention provides a kind of antibacterial glue of anion that is specially adapted to cloth, because anion has passed through radioactivity screening, therefore stopped the damage that radioactive composition may cause human body.And the release of the antibacterial glue anion of anion provided by the present invention is continual and steady, after testing, the amount of this product release natural negative ion per second can reach 5000 ~ 25000/cm
3, can reach significantly deodorizing, antibacterial effect, wherein Escherichia coli, staphylococcus aureus, Pseudomonas fluorescence, Bacillus megatherium, hay bacillus antibiotic rate are greater than to 97%.
The antibacterial glue of anion of the present invention, can use commercially available anion material, also can use and make as provided by the present invention anion material by oneself, while using self-control anion material, the anion quantity that the unit interval discharges and sustainable anion releasing time are significantly higher than commercially available negative ion powder.
The antibacterial glue of anion of the present invention can use the preparation of water soluble negative ionic material, first prepare in the preparation anion water solution slow and peptization solution again, the concentration of negative solution used in the present invention is larger, owing to reducing the addition of water, therefore very easily there is in the preparation precipitation or form gel, and method provided by the invention can avoid this phenomenon to occur, yield rate is high, and in colloid, the homogeneity of anion is greatly improved.
The antibacterial glue of anion of the present invention can use water-insoluble anion material preparation, first prepare in the preparation the aqueous dispersion of anion, slow and peptization solution again, the concentration of the aqueous dispersion of anion used in the present invention is larger, owing to reducing the addition of water, therefore very easily occur in the preparation precipitation or form gel, and method provided by the invention can avoid this phenomenon to occur, yield rate is high, and in colloid, the homogeneity of anion is greatly improved.
Brief description of the drawings
Fig. 1 is the structural representation of the anion environmental protection cloth prepared of embodiment 1.
Fig. 2 is the structural representation of the anion environmental protection cloth prepared of embodiment 6.
In the accompanying drawings, 1 bed of cloth, the antibacterial gel coating of 2 anion, 3 linings, 4 fabrics, the antibacterial glue-line of 5 anion.
Detailed description of the invention
embodiment 1
One. the preparation of anion material:
Select Renhe, Beijing to contain more than 90% tourmaline of tourmaline content that scientific & trading Co., Ltd. produces, the lanthanide series rare earth that tourmaline factory produces is converged in Lingshou County, the rutile type titanium white (TiO that Langfang City span Chemical Co., Ltd. produces
2), the latex rubber cement that Dong Qiao chemical plant, Guangdong produces.
Wherein TiO
2effect be to hide look, make the color of the mixture of final gained level off to white or faint yellow, TiO
2addition be generally 20 ~ 40 weight portions, TiO
2addition more, the color of the compound finally obtaining is more shallow.
Rare Earth Mine particle is put on small-sized conveyer belt, used JB4060A gamma meter to carry out radioactivity screening.
Tourmaline after screening is ground step by step through ball mill, and sieve through vibrating screen, obtain 500 ~ 1000 object tourmaline powders.
Rare earth after screening is ground step by step through ball mill, and sieve through reciprocating sieve, obtain 500 ~ 1000 object rare earth powders.
Take respectively the tourmaline powder of 30 weight portions of above-mentioned preparation, the rare earth powder of 70 weight portions, the TiO of 30 weight portions
2powder.
In ball mill, 12 hours mixing and ball milling of ball milling evenly obtain composition A.
The above-mentioned composition A that gets 1 weight portion intensifies and obtains the composition B that high-frequency electrical intensifies through 916 megahertz high-frequency electrical.Getting the composition B of 1 weight portion and the composition A of 5 weight portions mixes and makes composite negative ion material.
Two. the preparation of the antibacterial glue of anion
Get the composite negative ion material of the above-mentioned preparation of 1 weight portion and the pure water of 0.7 weight portion, add ball grinder, regulate pH to 11.0, ball milling makes the aqueous dispersion of anion for 12 hours; The genuine milk rubber cement of 10 weight portions is poured in the charging basket of high speed dispersor, in the rubber cement of high-speed stirred, slowly added the aqueous dispersion of above-mentioned anion, after interpolation, then stir 10 minutes.
As shown in Figure 1, the antibacterial glue of anion that the present embodiment makes, through being coated on textiles bed of cloth 1 surface (scraping slurry), obtains the environmental protection cloth with sustained release anion function with the antibacterial gel coating 2 of anion after being dried.This environmental protection cloth can be used for preparing footwear, cap, clothes, the tablecloth, curtain, mouth mask, automobile-used decoration etc.
embodiment 2 ~ 5 and comparative example 1
Embodiment 2 ~ 5 is from the difference of embodiment 1: material proportion and the condition of prepared anion material are different, and anion material is different from the ratio of glue, specifically in table 1.
Comparative example 1 is with the difference of embodiment 1: the high-frequency electrical of not carrying out in the time preparing anion material of comparative example 1 intensifies.
Table 1 embodiment 2 ~ 5
embodiment 6
The water soluble negative ionic material of selecting Lingshou County Li Jing mineral products processing factory to produce, the latex rubber cement that Dong Qiao chemical plant, Guangdong produces, prepares the antibacterial glue of anion.
In pottery bucket, add the water-soluble negative ion powder of 1 weight portion and the water of 1 weight portion, limit drips KOH solution with ceramic dispersion impeller high-speed stirred limit dissolves anion completely, and regulator solution pH to 11.0, makes negative solution;
The latex rubber cement of 5 weight portions is poured in the charging basket of high speed dispersor, in the rubber cement of high-speed stirred, slowly added above-mentioned negative solution, after negative solution adds, then stir 5 minutes.
As shown in Figure 2, the antibacterial glue of anion that the present embodiment makes makes lining 3 and fabric 4 laminatings form composite material (closing cloth) as adhesive, in the middle of dry rear lining 3 and fabric 4, is the antibacterial glue-line 5 of anion.The material of lining 3 and fabric 4 can be the same or different, and if lining 3 is pure cotton canvas, fabric 4 is chemical fibre cloth.Prepared composite material can be used for preparing canvas rubber shoe, shoe-pad, clothes, home textile product.
embodiment 7 ~ 9 and comparative example 2
Embodiment 7 ~ 9 is preparation condition as shown in table 2 with the difference of embodiment 6, wherein embodiment 7 and 8 is in the time preparing anion water solution, water preheat to 60 DEG C, in the rubber cement of high-speed stirred, slowly add again above-mentioned negative solution, after negative solution adds, continue to stir 10 minutes, temperature is down to the rubber cement bucket that slowly adds again high-speed stirred after normal temperature.
Comparative example 2 is water-soluble negative ion powder to be directly dissolved in rubber cement with the difference of embodiment 6.
Table 2
Embodiment 10 and comparative example 3
The non-dissolubility anion material (model 25kg 6000ions 500 order types) of selecting Lingshou County Li Jing mineral products processing factory to produce, the latex rubber cement that Dong Qiao chemical plant, Guangdong produces, prepares the antibacterial glue of anion.
Get the non-dissolubility anion material of 1 weight portion and the pure water of 0.7 weight portion, add ball grinder, regulate pH to 11, ball milling makes the aqueous dispersion of anion for 12 hours; The latex rubber cement of 10 weight portions is poured in the charging basket of high speed dispersor, in the rubber cement of high-speed stirred, slowly added the aqueous dispersion of above-mentioned anion, after interpolation, then stir 10 minutes.
Comparative example 3 is from the different of embodiment 10: by the non-dissolubility anion material of 1 weight portion directly with the latex rubber cement mix and blend of 10 weight portions.
experimental example 1
Detect the various embodiments described above and the antibacterial glue of the prepared anion of comparative example all once, anion release rate and radioactivity, wherein blank is the generic latex rubber cement that does not add anion composition.Experimental result is in table 3.
Detection method: the square sample that cuts 300x300mm from being coated with the cloth (cloth that Fig. 1 mode makes) of the antibacterial glue of anion detects.
Anion release rate detects: use the U.S. to produce AIC2000 type anion test instrument, tester is placed in to sample and covers glue face top detection 60 seconds, get the median of number range.
Radiological measuring detects: use JB4060A gamma meter, first detector Geiger detector is placed on desk and is measured, radiation value is 0.154uSv/h, and then sample is covered to glue placed face down on desk, Geiger detector is placed on the cloth cover of sample, within 60 seconds, records mean value.
Test environment: 20 degrees Celsius, relative humidity 50%, in the airtight room that there is no Air Flow.
Table 3
Experimental result shows: the anion material adding in rubber cement is more, and the anion release rate of obtained cloth is more, but radiance also increases to some extent thereupon.In the time using homemade anion material, the release rate of anion is obviously better than commercially available material, and radiance is also lower simultaneously, and its addition in rubber cement can reach 3 ~ 20%; Wherein the release rate of the antibacterial glue anion of the prepared anion of embodiment 1 is higher, and radiance is lower, is optimum embodiment of the present invention.
In the time using commercially available anion material, owing to increasing obviously along with anion addition increases radiance, preferably in rubber cement, addition is controlled at 3 ~ 5%.
According to result of the test, while adopting water soluble negative ion provided by the invention and water-insoluble anion material to prepare anion glue, can obtain the high-quality glue of quality homogeneous, but when the method for directly adding in use prior art, the homogeneity of product is poor, affects the carrying out of subsequent processing.
experimental example 2
Detect respectively the right fungistatic effect of the antibacterial glue of the prepared anion of the various embodiments described above and comparative example, wherein blank is the generic latex rubber cement that does not add anion composition.Experimental result is in table 4.
Detection method is: in plate, inject two-layer agar medium, lower floor is aseptic culture medium, and upper strata is inoculation medium, and Fig. 1 prepared by each embodiment and the each cut-off of Fig. 2 cloth footpath are 25 ± 5mm sample, are placed on respectively on two-layer culture medium.Escherichia coli are uniformly coated on aseptic culture medium.Cultivate after 18 hours, measure sample antibacterial bandwidth, and with the food supplements of contact area below microexamination sample, the anti-microbial property of qualitative evaluation sample.
Table 4
Experimental result shows: no matter be that the anion glue that each embodiment is made is coated on design on fabric surface or closes cloth as adhesive and process prepared cloth, all shown good bacteriostasis property, bacteriostasis rate can reach more than 97%.
experimental example 3
Embodiment 1 ~ 10 and the antibacterial glue of the prepared anion of comparative example 1 ~ 3 being closed to cloth as adhesive, make lining and fabric laminating form composite material, is the antibacterial glue-line of anion in the middle of dry rear lining and fabric, and lining 3 and fabric 4 are cotton.Blank is the white glue with vinyl of not adding anion material.This experimental example is to be coated with and brushes one times glue and close cloth processing, and in the time that reality is used, can select carry out brushing for 1 ~ 3 time closed cloth.Experimental result is in table 5.
Prepared cloth carries out anion release rate and deodorizing test.
Test method: make the textile shoe-pad that contains the antibacterial glue of anion, be distributed to the personnel of serious pin taste, sense organ deodorizing effect.
Anion burst size: use the U.S. to produce AIC2000 type anion test instrument, tester is placed to the cloth of the antibacterial gummed cloth of anion for making shoe-pad, detect 60 seconds, get the median of number range.
Deodorizing test: in order to embody more intuitively anion deodorization functions, we adopt common people's common sense of smell as evaluation criterion, and its standard is not for very smelly, smelly, slightly smelly, smelly.We close cloth with Fig. 2 and have made 14 pairs of shoe-pads, are distributed to foot and like to perspire and test with the smelly personnel of serious pin.Send special messenger's call-on back by phone inquiry deodorizing effect every day, we Continuous Tracking pay a return visit such process 10 days, and we have done gathering below accordingly.
The detection of release duration: hot baking-aging senile experiment, 1, get each two of the composite material that each embodiment and comparative example make and put into air dry oven, temperature is controlled at 90 DEG C ± 1 DEG C; One is toasted 800 hours continuously, and another piece toasts 1000 hours continuously; Test aging before and through 800 hours and 1000 hours toast aging after, the performance of releasing negative oxygen ion; In the sensing chamber of standard, detect, tester is AIC2000 type anion detector.Test condition is 20 DEG C, humidity 60%RH.It has been generally acknowledged that, glue face is equivalent to natural aging 30 years through baking in 800 hours is aging; Approximate natural aging 50 years through baking in 1000 hours.
Table 5
Table 6
Experimental result shows: no matter be that the anion glue that each embodiment is made is coated on design on fabric surface or closes cloth as adhesive and process prepared cloth, the release rate of anion is high, and the duration is more than 30 years or 50 years; The release rate of anion is higher, and bacteriostasis rate is just higher, and bacterium cannot survive under the anion environment of high concentration, so according to said method obtain the deodorizing effect highly significant of cloth.
Claims (10)
1. the antibacterial glue of anion, is characterized in that it adds anion material in rubber cement, and the weight ratio that described anion material accounts for rubber cement is 3% ~ 20%.
2. the antibacterial glue of a kind of anion according to claim 1, is characterized in that described anion material is water soluble negative ionic material or water-insoluble anion material.
3. the antibacterial glue of a kind of anion according to claim 2, is characterized in that described water-insoluble anion material obtains as follows:
Step 1: tourmaline and rare earth grind step by step respectively, screen acquisition granularity and be not less than 500 order ~ 10000 object powder;
Step 2: be mixed to get composition by following parts by weight:
Tourmaline powder: 10 ~ 40 weight portions,
Rare earth: 60 ~ 90 weight portions;
Step 3: step 2 resulting composition is carried out to high-frequency electrical and intensify;
Step 4: the composition that the composition after step 3 gained high-frequency electrical is intensified and step 2 gained intensify without high-frequency electrical is taking weight as 1:(3 ~ 6) ratio be mixed to get composite negative ion material.
4. the antibacterial glue of a kind of anion according to claim 3, is characterized in that described tourmaline and rare earth screen and dispel radioactive material through radioactivity prospecting instrument.
5. the antibacterial glue of a kind of anion according to claim 4, is characterized in that the frequency that described high-frequency electrical intensifies is 800 ~ 1200 megahertzes.
6. the antibacterial glue of a kind of anion according to claim 1, is characterized in that described rubber cement is selected from latex rubber cement, mucilago amyli, polyvinyl alcohol chemistry rubber cement or ternary and closes cloth slurry.
7. according to the antibacterial glue of anion described in claim 1,2 or 6, it is characterized in that the antibacterial glue of described anion prepared by following method:
Step 1: the water-soluble negative ion powder of getting 1 weight portion adds in the water of 0.8 ~ 1.5 weight portion,
Drip while stirring alkali lye anion is dissolved completely, regulator solution pH to 7.0 ~ 11.0;
Step 2: get the rubber cement of 5 ~ 33 weight portions, add while stirring step 1 gained negative solution, continue to stir 5 ~ 30min after interpolation.
8. the antibacterial glue of anion according to claim 7, is characterized in that water preheat described in step 1 is to 50-70 DEG C, and the alkali described in step 1 is KOH or NaOH.
9. according to the antibacterial glue of a kind of anion described in any one of claim 1 ~ 6, it is characterized in that the antibacterial glue of described anion prepared by following method:
Step 1: water-insoluble anion material and water are poured in ball grinder, and wherein the weight ratio of water-insoluble anion material and water is 1:0.6 ~ 0.8, regulates pH to identical with the pH of described rubber cement, and ball milling 8-24 hour makes the aqueous dispersion of anion;
Step 2: the rubber cement of 5 ~ 33 weight portions is poured in the charging basket of high speed dispersor, slowly added the aqueous dispersion of above-mentioned anion in the rubber cement of high-speed stirred, after interpolation, then stir 5 ~ 30 minutes.
10. according to the antibacterial glue of a kind of anion described in any one of claim 1 ~ 6, it is characterized in that its application in bonding and cloth coating at cloth.
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|---|---|---|---|
| CN201410162811.1A CN103938444B (en) | 2014-04-22 | 2014-04-22 | The antibacterial glue of a kind of anion |
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|---|---|---|---|
| CN201410162811.1A CN103938444B (en) | 2014-04-22 | 2014-04-22 | The antibacterial glue of a kind of anion |
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| CN103938444B CN103938444B (en) | 2016-04-27 |
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| CN106263268A (en) * | 2016-08-28 | 2017-01-04 | 杭州锴越新材料有限公司 | Far infrared, warm, health care shoe pad and preparation method thereof |
| CN106360879A (en) * | 2016-08-28 | 2017-02-01 | 杭州锴越新材料有限公司 | Multifunctional healthy negative-ion insoles and making method thereof |
| CN106360880A (en) * | 2016-08-28 | 2017-02-01 | 杭州锴越新材料有限公司 | Bacteriostatic negative ion shoe pad and preparation method thereof |
| CN109736077A (en) * | 2018-11-26 | 2019-05-10 | 福建省绿城环保科技有限公司 | For spraying the liquor and preparation method that shine wall clothing anion function fibrous material |
| CN111875355A (en) * | 2019-07-08 | 2020-11-03 | 中科森之初环保科技有限公司 | Sterilizing and fresh-keeping porcelain ware and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111875355A (en) * | 2019-07-08 | 2020-11-03 | 中科森之初环保科技有限公司 | Sterilizing and fresh-keeping porcelain ware and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN103938444B (en) | 2016-04-27 |
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