CN105421019A - Bleaching process of human hair fiber - Google Patents
Bleaching process of human hair fiber Download PDFInfo
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- CN105421019A CN105421019A CN201510982709.0A CN201510982709A CN105421019A CN 105421019 A CN105421019 A CN 105421019A CN 201510982709 A CN201510982709 A CN 201510982709A CN 105421019 A CN105421019 A CN 105421019A
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Abstract
The invention discloses a bleaching process of human hair fibers, which includes the following steps: 1) surface pre-treatment to the human hair fibers; 2) oxidizing treatment to the pre-treated human hair fibers in a batched material feeding manner; and 3) reduction treatment to the oxidized human hair fibers. The process is simple, is low in cost, is easy to industrialize, solves the problems of low yield and high fiber damage in a bleaching process of human hair fibers, and has excellent development prospect and economic value.
Description
Technical field
The invention belongs to textile dyeing and finishing field, particularly the fiber bleached technique of a kind of human hair.
Background technology
Along with growth in the living standard, wig has become the rare crowd of hair and the necessary article of the personage that likes to be beautiful, and these people need the wig of more color to prick up oneself.In addition, to like to be beautiful fashion as one, wear wig liking deeply by many stars and high consumption crowd, and people are more and more frequent for the renewal of wig, this wig industrial expansion just promoted.Although the wig color of chemical fibre class is beautiful and cheap, if wear-time is long, the senses of discomfort such as stuffy, dry can be brought to people, even may cause disease of skin.And human hair belongs to natural fabric, sucting wet air permeability and anti-flammability etc. are better than chemical fibre class wig far away, are therefore still the first-selection of people with the wig that human hair is made.Chinese Hair color is based on black, even yellow etc. variegated with bletilla, for meeting the different requirements of different crowd to wig look, must carry out bleaching and dyeing process to human hair.
The basis of hair is keratin protein, keratin protein is made up of amino acid, their improve nutrition needed for natural on-off cycles of hair growth and composition, each seed amino acid fiber is wound around mutually crosslinked by mechanism that is spiral, spring, form the intensity of keratoprotein and pliable and tough, thus impart the exclusive strong and unyielding performance of hair.So bleaching in human hair fiber process the destruction also will avoiding the complete crosslinking method of each seed amino acid fiber while that to propose in human hair fiber melanic, the human hair fibre technology technology that damage is little, yield is high so just can be obtained.
Liu Baojiang etc. disclose a kind of method for bleaching of human hair fiber low-carbon (LC) in Chinese patent application 201010598676.7, by adding protease, photooxidation bleaching and washing, obtain the fiber bleached technique of the human hair with certain bleaching effect.In addition, Liu Baojiang etc. disclose a kind of method for bleaching of human hair fibers at low temperature with low damage in Chinese patent application 201010598379.2, by adding agent pretreatment fluid of scaling in human hair fiber, and then human hair fiber is put into pre-matchmaker's treatment fluid, last low-temperature activated bleaching, obtains the fiber bleached technique of the human hair with certain fibre whiteness.Above-mentioned report adopts diverse ways to carry out bleaching to human hair fiber, but does not do further investigated to the fiber bleached whiteness of human hair, contradiction between yield and intensity.Chemicals adds comparatively complicated simultaneously, and the current technology for enterprise need do larger amendment.
Sun Yunfei etc. are in " wool spinning science and technology " paper that the 42nd volume the 7th phase 21-24 page was delivered in 2014, adopt oxalic acid and ferrous ion first to form complex compound and catalytic pretreatment is carried out to human hair fiber, take hydrogen peroxide as drift agent, investigated oxalic acid and ferrous salt consumption, catalytic reaction temperature and time to the impact of bleaching people's degree of blushing and ultimate strength.But the research emphasis of this paper is the process optimization of catalytic pretreatment, in yield, whiteness and intensity, do not have further investigated.
In recent years, the market demand of human hair fiber increases, and price is more and more higher.And report from current correlative study, the fiber bleached whiteness of human hair, contradiction between yield and intensity still fail effectively to be overcome, the fiber bleached technique of human hair of high yield pulp1, high whiteness, low damage, the bleaching process being simultaneously applicable to existing enterprise's process modification is the dual needs improving the quality of products, meet the need of market.
Summary of the invention
Object of the present invention, be to provide a kind of human hair fiber bleached technique, this technique is the improvement of industrialization process, in the fed batch technique of oxidation processes section, effectively can reduce the oxidant concentration in bleach system, add when oxidant concentration is lower in good time, and realize the post-bleach of human hair fiber in reduction treatment section.Have that technique is simple, with low cost, efficiency is high, it is little to pollute, energy consumption is low, easy suitability for industrialized production, good to the bleaching effect of human hair fiber, damage little, there is good development prospect and economic worth.
In order to realize above-mentioned object, the solution of the present invention is:
The fiber bleached technique of a kind of human hair, is characterized in that, comprise the following steps:
Step one, the surface preparation of human hair fiber:
In human hair fiber, add a certain amount of pretreatment fluid, the bath raio of human hair fiber and pretreatment fluid is 1:4 ~ 1:30, at constant temperature 50 ~ 95 DEG C, and process 0.5 ~ 8h;
Step 2, the fed batch oxidation processes of human hair fiber after preliminary treatment:
Be 1:4 ~ 1:30 in bath raio, temperature is under 30 ~ 80 DEG C of conditions, carries out oxidation processes; Divide the agent of the oxidisability drift needed for 2 ~ 8 batches of inputs, the total addition of oxidisability drift agent and over dry human hair fiber quality are than being 0.1:1 ~ 5:1, often criticize interval 0.5 ~ 24h, total bleaching time controls at 1 ~ 48h, and before feeding intake the last time, add the crosslinking agent being equivalent to over dry human hair fiber quality 0.1% ~ 5%, continue reaction 0.5 ~ 24h, with clear water washing to neutral;
Step 3, the reduction treatment of human hair fiber after oxidation processes:
After above-mentioned oxidation processes, add the Reductive Bleaching agent being equivalent to over dry human hair fiber quality 0.1% ~ 5% in human hair fiber, bath raio is 1:4 ~ 1:30, processes 0.5 ~ 5h under constant temperature 40 ~ 95 DEG C of conditions.With clear water washing to neutral.
In one embodiment of the invention, the pretreatment fluid in described step one is organic acid soln and ferrous salt solution mass ratio is the mixed solution of 1:1 ~ 5:1.
In one embodiment of the invention, the organic acid soln in the pretreatment fluid in described step one is the one in tartaric acid, oxalic acid.
In one embodiment of the invention, the ferrous salt solution in the pretreatment fluid in described step one is the one in ferrous oxide, ferrous sulfate.
In one embodiment of the invention, the oxidisability drift agent in described step 2 is hydrogen peroxide.
In one embodiment of the invention, the crosslinking agent in described step 2 is the one in citric acid, glutaraldehyde, TGase (TG), peroxidase (POD), polyphenol oxidase (PPO).
In one embodiment of the invention, the Reductive Bleaching agent described in step 3 is the one in sodium dithionite, thiourea dioxide, urea.
By prior art scheme, the invention has the beneficial effects as follows:
The surface scale of pretreated human hair fiber partially opens, and can realize melanic effective efficient oxidation and decompose, and effectively reduce the oxidant concentration in bleach system, reduce oxidation bleaching to the destructiveness of fibre strength performance.Add when oxidant concentration is lower, the oxidant concentration in maintenance system in good time.Finally carrying out the supplementary multiple drift of reduction, the damage to human hair fiber in oxidation bleaching process can be reduced, improve yield and the whiteness of human hair fiber.Thus obtain having the human hair fiber of high yield pulp1, high whiteness and low damage.
Detailed description of the invention
The technological means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, illustrating the present invention further.For the technological parameter do not indicated especially, can refer to routine techniques and carry out.
Realize technological means of the present invention and should be not limited to following examples, and can adjust within the scope of the technical conditions of foregoing invention content.
The fiber bleached technique of a kind of human hair, is characterized in that, comprise the following steps:
Step one, the surface preparation of human hair fiber:
In human hair fiber, add a certain amount of pretreatment fluid, the bath raio of human hair fiber and pretreatment fluid is 1:4 ~ 1:30, at constant temperature 50 ~ 95 DEG C, and process 0.5 ~ 8h.
Step 2, the fed batch oxidation processes of human hair fiber after preliminary treatment:
Be 1:4 ~ 1:30 in bath raio, temperature is under 30 ~ 80 DEG C of conditions, carries out oxidation processes.Divide the agent of the oxidisability drift needed for 2 ~ 8 batches of inputs, oxidisability floats the total addition of agent (mass concentration is the hydrogen peroxide of 30%) with over dry human hair fiber quality than being 0.1:1 ~ 5:1, often criticize interval 0.5 ~ 24h, total bleaching time controls at 1 ~ 48h, and before feeding intake the last time, add the crosslinking agent being equivalent to over dry human hair fiber quality 0.1% ~ 5%, continue reaction 0.5 ~ 24h.With clear water washing to neutral.
Step 3, the reduction treatment of human hair fiber after oxidation processes:
After above-mentioned oxidation processes, add the Reductive Bleaching agent being equivalent to over dry human hair fiber quality 0.1% ~ 5% in human hair fiber, bath raio is 1:4 ~ 1:30, processes 0.5 ~ 5h under constant temperature 40 ~ 95 DEG C of conditions.With clear water washing to neutral; Reductive Bleaching agent described in step 3 is the one in sodium dithionite, thiourea dioxide, urea.
Further, the pretreatment fluid wherein in step one is organic acid soln and ferrous salt solution mass ratio is the mixed solution of 1:1 ~ 5:1, and the organic acid soln in pretreatment fluid in step one is the one in tartaric acid, oxalic acid; Usually, the ferrous salt solution in pretreatment fluid is the one in ferrous oxide, ferrous sulfate.
Oxidisability drift agent wherein in step 2 is hydrogen peroxide, and the crosslinking agent in step 2 is the one in citric acid, glutaraldehyde, TGase (TG), peroxidase (POD), polyphenol oxidase (PPO).
embodiment 1:
(1) pretreatment fluid is to the preliminary treatment of human hair fiber:
Ferrous ion in pretreatment fluid has good suction-operated to the melanin in protein fibre, can realize again the catalytic decomposition to hydrogen peroxide simultaneously.In over dry human hair fiber, add the copperas solution of 35g/L tartaric acid, 20g/L, bath raio is 1:8, and constant temperature water bath is 80 DEG C of process 3h.
(2) fed batch oxidation bleaching human hair fiber:
Oxidisability drift agent is explained in the bleaching time-division and is put active oxygen, and then active oxygen acts on melanic chromophoric group, and pigmentary structures is destroyed, and fiber is decoloured.Also can produce strong destruction to feather keratin simultaneously, make the large intermolecular disulfide bond fracture of cutin, cause hair fiber to be badly damaged.And the large energy discharged during peroxide decomposition can promote the decomposition of itself, so, drop into hydrogen peroxide in batches and can reduce over the active oxygen of the energy promotion of hydrogen oxide decomposition release itself to the damage of human hair fiber.
First, add equal with over dry human hair fiber quality in above-mentioned human hair fiber, mass concentration is the hydrogen peroxide drift agent of 30%, and being adjusted to bath raio is 1:12, and temperature is 45 DEG C of bleaching 3h;
Secondly, continue to add over dry human hair fiber quality 50% in above-mentioned human hair fiber, mass concentration is the hydrogen peroxide drift agent of 30%, and bath raio is 1:12, and temperature is 45 DEG C of bleaching 5h;
Finally, continue the citric acid adding over dry human hair fiber quality 0.2% in above-mentioned human hair fiber, temperature is 45 DEG C of bleaching 5h.Extremely neutral with clear water washing in room temperature again.
(3) reduction of human hair fiber is floated again:
The active oxygen produced due to oxidisability drift agent in oxidation bleaching is large to keratoprotein brokenization of human hair fiber, so reduce the oxidation bleaching time can reduce the damage of oxidation bleaching to human hair fiber, but can reduce human hair fibre whiteness again.Therefore, after oxidation bleaching, continue the multiple drift of reduction, can available protecting human hair fibre strength reach required whiteness.
In above-mentioned human hair fiber, add the sodium dithionite Reductive Bleaching agent being equivalent to over dry human hair fiber quality 3.0%, be 1:15 in bath raio, and constant temperature is process 1h at 50 DEG C, more extremely neutral with clear water washing in room temperature.
embodiment 2:
(1) pretreatment fluid is to the preliminary treatment of human hair fiber:
Ferrous ion in pretreatment fluid has good suction-operated to the melanin in protein fibre, can realize again the catalytic decomposition to hydrogen peroxide simultaneously.In over dry human hair fiber, add the copperas solution of 35g/L tartaric acid, 20g/L, bath raio is 1:8, and constant temperature water bath is 80 DEG C of process 3h.
(2) fed batch oxidation bleaching human hair fiber:
Oxidisability drift agent is explained in the bleaching time-division and is put active oxygen, and then active oxygen acts on melanic chromophoric group, and pigmentary structures is destroyed, and fiber is decoloured.Also can produce strong destruction to feather keratin simultaneously, make the large intermolecular disulfide bond fracture of cutin, cause hair fiber to be badly damaged.And the large energy discharged during peroxide decomposition can promote the decomposition of itself, so, drop into hydrogen peroxide in batches and can reduce over the active oxygen of the energy promotion of hydrogen oxide decomposition release itself to the damage of human hair fiber.
First, add equal with over dry human hair fiber quality in above-mentioned human hair fiber, mass concentration is the hydrogen peroxide drift agent of 30%, and being adjusted to bath raio is 1:15, and temperature is 45 DEG C of bleaching 3h;
Secondly, continue to add over dry human hair fiber quality 50% in above-mentioned human hair fiber, mass concentration is the hydrogen peroxide drift agent of 30%, and bath raio is 1:15, and temperature is 45 DEG C of bleaching 5h;
Again, continue to add over dry human hair fiber quality 50% in above-mentioned human hair fiber, mass concentration is the hydrogen peroxide drift agent of 30%, and bath raio is 1:15, and temperature is 45 DEG C of bleaching 5h;
Finally, continue the citric acid adding over dry human hair fiber quality 0.5% in above-mentioned human hair fiber, temperature is 45 DEG C of bleaching 5h.Extremely neutral with clear water washing in room temperature again.
(3) reduction of human hair fiber is floated again:
The active oxygen produced due to oxidisability drift agent in oxidation bleaching is large to keratoprotein brokenization of human hair fiber, so reduce the oxidation bleaching time can reduce the damage of oxidation bleaching to human hair fiber, but can reduce human hair fibre whiteness again.Therefore, after oxidation bleaching, continue the multiple drift of reduction, can available protecting human hair fibre strength reach required whiteness.
In above-mentioned human hair fiber, add the sodium dithionite Reductive Bleaching agent being equivalent to over dry human hair fiber quality 2.0%, be 1:25 in bath raio, and constant temperature is process 2h at 50 DEG C, more extremely neutral with clear water washing in room temperature.
embodiment 3:
(1) pretreatment fluid is to the preliminary treatment of human hair fiber:
Ferrous ion in pretreatment fluid has good suction-operated to the melanin in protein fibre, can realize again the catalytic decomposition to hydrogen peroxide simultaneously.In over dry human hair fiber, add the copperas solution of 35g/L tartaric acid, 20g/L, bath raio is 1:8, and constant temperature water bath is 80 DEG C of process 3h.
(2) fed batch oxidation bleaching human hair fiber:
Oxidisability drift agent is explained in the bleaching time-division and is put active oxygen, and then active oxygen acts on melanic chromophoric group, and pigmentary structures is destroyed, and fiber is decoloured.Also can produce strong destruction to feather keratin simultaneously, make the large intermolecular disulfide bond fracture of cutin, cause hair fiber to be badly damaged.And the large energy discharged during peroxide decomposition can promote the decomposition of itself, so, drop into hydrogen peroxide in batches and can reduce over the active oxygen of the energy promotion of hydrogen oxide decomposition release itself to the damage of human hair fiber.
First, add equal with over dry human hair fiber quality in above-mentioned human hair fiber, mass concentration is the hydrogen peroxide drift agent of 30%, and being adjusted to bath raio is 1:12, and temperature is 40 DEG C of bleaching 5h;
Secondly, continue to add over dry human hair fiber quality 50% in above-mentioned human hair fiber, mass concentration is the hydrogen peroxide drift agent of 30%, and bath raio is 1:12, and temperature is 40 DEG C of bleaching 7h;
Finally, continue the citric acid adding over dry human hair fiber quality 1.0% in above-mentioned human hair fiber, temperature is 40 DEG C of bleaching 5h.Extremely neutral with clear water washing in room temperature again.
(3) reduction of human hair fiber is floated again:
The active oxygen produced due to oxidisability drift agent in oxidation bleaching is large to keratoprotein brokenization of human hair fiber, so reduce the oxidation bleaching time can reduce the damage of oxidation bleaching to human hair fiber, but can reduce human hair fibre whiteness again.Therefore, after oxidation bleaching, continue the multiple drift of reduction, can available protecting human hair fibre strength reach required whiteness.
In above-mentioned human hair fiber, add the sodium dithionite Reductive Bleaching agent being equivalent to over dry human hair fiber quality 1.5%, be 1:15 in bath raio, and constant temperature is process 1h at 50 DEG C, more extremely neutral with clear water washing in room temperature.
embodiment 4:
(1) pretreatment fluid is to the preliminary treatment of human hair fiber:
Ferrous ion in pretreatment fluid has good suction-operated to the melanin in protein fibre, can realize again the catalytic decomposition to hydrogen peroxide simultaneously.In over dry human hair fiber, add the copperas solution of 35g/L tartaric acid, 20g/L, bath raio is 1:8, and constant temperature water bath is 80 DEG C of process 3h.
(2) fed batch oxidation bleaching human hair fiber:
Oxidisability drift agent is explained in the bleaching time-division and is put active oxygen, and then active oxygen acts on melanic chromophoric group, and pigmentary structures is destroyed, and fiber is decoloured.Also can produce strong destruction to feather keratin simultaneously, make the large intermolecular disulfide bond fracture of cutin, cause hair fiber to be badly damaged.And the large energy discharged during peroxide decomposition can promote the decomposition of itself, so, drop into hydrogen peroxide in batches and can reduce over the active oxygen of the energy promotion of hydrogen oxide decomposition release itself to the damage of human hair fiber.
First, add equal with over dry human hair fiber quality in above-mentioned human hair fiber, mass concentration is the hydrogen peroxide drift agent of 30%, and being adjusted to bath raio is 1:15, and temperature is 40 DEG C of bleaching 5h;
Secondly, continue to add over dry human hair fiber quality 50% in above-mentioned human hair fiber, mass concentration is the hydrogen peroxide drift agent of 30%, and bath raio is 1:15, and temperature is 40 DEG C of bleaching 7h;
Again, continue to add over dry human hair fiber quality 50% in above-mentioned human hair fiber, mass concentration is the hydrogen peroxide drift agent of 30%, and bath raio is 1:15, and temperature is 40 DEG C of bleaching 7h;
Finally, continue the citric acid adding over dry human hair fiber quality 1.0% in above-mentioned human hair fiber, temperature is 40 DEG C of bleaching 5h.Extremely neutral with clear water washing in room temperature again.
(3) reduction of human hair fiber is floated again:
The active oxygen produced due to oxidisability drift agent in oxidation bleaching is large to keratoprotein brokenization of human hair fiber, so reduce the oxidation bleaching time can reduce the damage of oxidation bleaching to human hair fiber, but can reduce human hair fibre whiteness again.Therefore, after oxidation bleaching, continue the multiple drift of reduction, can available protecting human hair fibre strength reach required whiteness.
In above-mentioned human hair fiber, add the sodium dithionite Reductive Bleaching agent being equivalent to over dry human hair fiber quality 2.0%, be 1:25 in bath raio, and constant temperature is process 2h at 50 DEG C, more extremely neutral with clear water washing in room temperature.
More than show and describe the general principle of patent of the present invention and the advantage of principal character and patent of the present invention.The technical staff of the industry should understand; patent of the present invention is not restricted to the described embodiments; the principle that patent of the present invention is just described described in above-described embodiment and description; under the prerequisite not departing from patent spirit and scope of the present invention; patent of the present invention also has various changes and modifications, and these changes and improvements all fall in claimed the scope of the claims of the present invention.Patent requirements protection domain of the present invention is defined by appending claims and equivalent thereof.
Claims (7)
1. the fiber bleached technique of human hair, is characterized in that, comprise the following steps:
Step one, the surface preparation of human hair fiber:
In human hair fiber, add a certain amount of pretreatment fluid, the bath raio of human hair fiber and pretreatment fluid is 1:4 ~ 1:30, at constant temperature 50 ~ 95 DEG C, and process 0.5 ~ 8h;
Step 2, the fed batch oxidation processes of human hair fiber after preliminary treatment:
Be 1:4 ~ 1:30 in bath raio, temperature is under 30 ~ 80 DEG C of conditions, carries out oxidation processes; Divide the agent of the oxidisability drift needed for 2 ~ 8 batches of inputs, the total addition of oxidisability drift agent and over dry human hair fiber quality are than being 0.1:1 ~ 5:1, often criticize interval 0.5 ~ 24h, total bleaching time controls at 1 ~ 48h, and before feeding intake the last time, add the crosslinking agent being equivalent to over dry human hair fiber quality 0.1% ~ 5%, continue reaction 0.5 ~ 24h, with clear water washing to neutral;
Step 3, the reduction treatment of human hair fiber after oxidation processes:
After above-mentioned oxidation processes, add the Reductive Bleaching agent being equivalent to over dry human hair fiber quality 0.1% ~ 5% in human hair fiber, bath raio is 1:4 ~ 1:30, processes 0.5 ~ 5h under constant temperature 40 ~ 95 DEG C of conditions, with clear water washing to neutral.
2. the fiber bleached technique of a kind of human hair according to claim 1, is characterized in that, the pretreatment fluid in described step one is the mass ratio of organic acid soln and ferrous salt solution is the mixed solution of 1:1 ~ 5:1.
3. the fiber bleached technique of a kind of human hair according to claim 2, is characterized in that, the organic acid soln in described pretreatment fluid is the one in tartaric acid, oxalic acid.
4. the fiber bleached technique of a kind of human hair according to claim 2, is characterized in that, the ferrous salt solution in described pretreatment fluid is the one in ferrous oxide, ferrous sulfate.
5. the fiber bleached technique of a kind of human hair according to claim 1, is characterized in that, the oxidisability drift agent in described step 2 is hydrogen peroxide.
6. the fiber bleached technique of a kind of human hair according to claim 1, it is characterized in that, the crosslinking agent in described step 2 is the one in citric acid, glutaraldehyde, TGase (TG), peroxidase (POD), polyphenol oxidase (PPO).
7. the fiber bleached technique of a kind of human hair according to claim 1, is characterized in that, the Reductive Bleaching agent described in step 3 is the one in sodium dithionite, thiourea dioxide, urea.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107156975A (en) * | 2017-06-23 | 2017-09-15 | 山东理工大学 | The method of melanin in biological fermentation process removing human hair fiber |
| CN107173896A (en) * | 2017-06-23 | 2017-09-19 | 山东理工大学 | The biological decolouring technique of Yangization Fa treatment oil dyeing human hair fibers |
| CN108252079A (en) * | 2018-01-19 | 2018-07-06 | 安徽富泰发饰文化股份有限公司 | A kind of method of Bleaching of Black Human Hair decoloration |
| CN108729208A (en) * | 2018-06-14 | 2018-11-02 | 许昌学院 | Yi Zhong treatment oil human hair bleaching process |
| CN110424147A (en) * | 2019-06-20 | 2019-11-08 | 许昌学院 | A kind of method of the Shuan oxygen water Piao Bai treatment oil human hair of simple green high-efficient |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107156975A (en) * | 2017-06-23 | 2017-09-15 | 山东理工大学 | The method of melanin in biological fermentation process removing human hair fiber |
| CN107173896A (en) * | 2017-06-23 | 2017-09-19 | 山东理工大学 | The biological decolouring technique of Yangization Fa treatment oil dyeing human hair fibers |
| CN108252079A (en) * | 2018-01-19 | 2018-07-06 | 安徽富泰发饰文化股份有限公司 | A kind of method of Bleaching of Black Human Hair decoloration |
| CN108729208A (en) * | 2018-06-14 | 2018-11-02 | 许昌学院 | Yi Zhong treatment oil human hair bleaching process |
| CN110424147A (en) * | 2019-06-20 | 2019-11-08 | 许昌学院 | A kind of method of the Shuan oxygen water Piao Bai treatment oil human hair of simple green high-efficient |
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| CN105421019B (en) | 2018-06-19 |
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