CN101434719A - Raw material dry state proportion for rubber latex for producing ultrathin condom and formulating vulcanization process thereof - Google Patents
Raw material dry state proportion for rubber latex for producing ultrathin condom and formulating vulcanization process thereof Download PDFInfo
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Abstract
The invention relates to a dried material ratio of rubber latex for producing ultra-thin condoms and a sulfuration technology for preparing the rubber latex. The dried weight ratios are respectively as follows: 1.20 portions of sulfur, 0.70 portion of ZnO, 0.40 portion of zinc diethyl dithiocarbamate, 1.00 portion of 2, 6-bis-tert buty-4-methyl phenol, 0.08 portion of KOH, 0.25 portion of fatty alcohol polyoxyethylene (20) ether, 0.05 portion of sodium hexametaphosphate, 0.10 portion of sodium methylene dinaphthyl sulphonate, 100.00 portions of natural rubber and 3.00 portions to 5.00 portions of modified rubber latex. The sulfuration technology comprises 10 steps and can be used for the preparation of the rubber latex for producing the ultra-thin condoms. The rubber latex can be used for the production of ultra-thin and ultra ultra-thin condom products with the thickness of about 0.050mm. Under the premise of guaranteeing the strength quality and meeting the national and international standards, the products have excellent comfortableness when in use, can realize effective contraception and also more effectively prevent the spread of diseases, such as AIDS, gonorrhea and chancroid and the like.
Description
Technical field
The invention belongs to the condom manufacture technical field, more particularly relate to the raw material dry state proportioning of rubber latex for producing ultrathin condom and the improvement and the innovation of formulating vulcanization process thereof.
Background technology
The natural latex rubber condom is a kind of rubber film goods of making of film forming characteristics that utilize the sulfuration natural rubber latex, is mainly used in preventative transmission of disease and contraception.Along with domestic and international human consumer to improving constantly that the condom comfortableness requires, under the prerequisite that guarantees product strength, product thickness is got over Bao Yuehao.This will seek survival and produce enterprise and update production technique, produce can reach requirement of strength, meet country and relevant international standard, the propagation of virus such as can effectively prevent AIDS, can guarantee the ultra-thin and ultra-thin condom of comfort again.
The tradition condom adopts the production of pure natural latex, has following defective:
When 1, thickness was the 0.050mm left and right sides, product was difficult to reach the ideal blasting performance.Therefore, the one-tenth-value thickness 1/10 of the ultra-thin product of the first in the world brand Du Leisi is about about 0.06mm at present; Though the ridge of Japan this declare can the production bilayer thickness at the ultra-thin series product of 0.03-0.04mm, about the product thickness value average out to 0.055mm of effective sale.
2, can effectively practise contraception, but the propagation of virus such as can not effectively prevent AIDS.Its reason is the dry of natural latex condom between the 5000-70000 nanometer, and what can prevent the human body sperm well passes through to realize the contraception function; But the diameter of hiv virus has only 120 nanometers, certainly drives straight in.In fact, according to the nearest report of " New England Journal of Medicine " and " Britain's social science medical journal ", the mortality that present commercially available traditional condom prevents AIDS reaches 16.7% and 31% respectively.A large amount of statistical information and result of study explanation, present widely used condom is very undesirable to the prevention performance of diseases such as acquired immune deficiency syndrome (AIDS), gonorrhoea, venereal ulcer, hodgkin, chlamydozoan, syphilis, genital herpes and pointed condyloma.
Summary of the invention
Purpose of the present invention just is to overcome above-mentioned shortcoming and defect, and a kind of raw material dry state proportioning and formulating vulcanization process thereof of rubber latex for producing ultrathin condom is provided.It can be used for producing thickness is ultra-thin and ultra-thin condom products about 0.050mm, this product in the proof strength quality, meet under the prerequisite of country and relevant international standard, have good comfort, can prevent AIDS preferably, transmission of disease such as gonorrhoea, venereal ulcer, hodgkin, chlamydozoan, syphilis, genital herpes and pointed condyloma.
In order to achieve the above object, the raw material dry state proportioning of rubber latex for producing ultrathin condom of the present invention comprises according to the dry state sulphur of extra fine quality ratio, ZnO, zinc diethyldithiocarbamate, 2,6 di tert butyl 4 methyl phenol, KOH, aliphatic alcohol polyethenoxy (20) ether, Sodium hexametaphosphate 99, sodium metnylene bis-naphthalene sulfonate and natural rubber latex.The dry state mass ratio is followed successively by 1.20 parts sulphur, 0.70 part ZnO, 0.40 part zinc diethyldithiocarbamate, 1.00 parts 2,6 di tert butyl 4 methyl phenol, 0.08 part KOH, 0.25 part aliphatic alcohol polyethenoxy (20) ether, 0.05 part Sodium hexametaphosphate 99,0.10 part sodium metnylene bis-naphthalene sulfonate and 100.00 parts natural rubber latex, the modified latex of 3.00-5.00 part.
Modified latex is a MMA grafted natural rubber latex.Trade(brand)name is GAPOLY PM 49HS.MMA grafted natural rubber latex is to preserve latex with a kind of high ammonia of methacrylate modification, and it is to utilize copolyreaction poly-methyl acrylate to be grafted on the polyisoprene units of natural rubber latex to prepare.Be used as the natural rubber latex additive to improve the physicals of finished product.In addition, it can also be used to produce and has the special product that coheres effect to connect the nonrubber article as additive.
Other raw-material effect is as follows: Sodium hexametaphosphate 99 and sodium metnylene bis-naphthalene sulfonate can make pressed powder be evenly dispersed in the liquid, and not reassemble as dispersion agent.Aliphatic alcohol polyethenoxy (20) ether used as stabilizers.KOH is a latex stabilizer, regulates the pH value of latex mixing.Sulphur is vulcanizing agent, makes between the rubber molecule to produce crosslinkedly, forms tridimensional network.Zinc diethyldithiocarbamate is a vulcanization accelerator, can accelerate vulcanization rate.2,6 di tert butyl 4 methyl phenol is an anti-aging agent, can delay the aging of rubber item.ZnO is a promoting agent, can increase the promotor activity.
The formulating vulcanization process of rubber latex for producing ultrathin condom may further comprise the steps:
(1) respectively aforementioned starting material is mixed with the aqueous solution or emulsion or be dispersed in the water, the shared mass ratio of its mass concentration or solid is respectively: natural rubber latex-60%, modified latex-50%, sulphur-50%, ZnO-50%, zinc diethyldithiocarbamate-50%, 2,6-di-tert-butyl-4-methy phenol-40%, KOH-25%, aliphatic alcohol polyethenoxy (20) ether-20%, Sodium hexametaphosphate 99-20%, sodium metnylene bis-naphthalene sulfonate-10%, modified latex is a MMA grafted natural rubber latex;
(2) will add according to the natural rubber latex emulsion 835Kg of step (1) preparation in the vulcanizing boiler;
(3) will add according to the modified latex emulsion 29.76-49.6Kg of step (1) preparation in the vulcanizing boiler;
(4) the 10-20Kg ammonia soln is added in the vulcanizing boiler, this ammonia soln is the deionized water solution of ammoniacal liquor, and wherein the ratio of deionized water and ammoniacal liquor is 3: 1;
(5) will add in the vulcanizing boiler according to following order and quality according to the solution or the dispersion liquid of step (1) preparation: Sodium hexametaphosphate 99 1.25Kg, sodium metnylene bis-naphthalene sulfonate 5.00Kg, aliphatic alcohol polyethenoxy (20) ether 6.25Kg, KOH1.6Kg, sulphur 12.00Kg, zinc diethyldithiocarbamate 4.00Kg, 2,6 di tert butyl 4 methyl phenol 12.50Kg and ZnO7.00Kg;
(6) add deionized water 80-100Kg and stir, should make total solids 〉=53% of vultex;
(7) start vulcanizing boiler and heat, begin insulation after being warming up to 55 ℃-59 ℃;
(8) begin to clock from insulation, play per sampling half an hour in 2 hours and survey swelling coefficient, when swelling coefficient reaches 2.6-2.4, open the cooling system of vulcanizing boiler, latex is lowered the temperature, laboratory indexes when the latex temperature is reduced to 39 ± 1 ℃ should reach total solids 〉=53%, pH value 〉=10.5, ammonia content 0.50-0.75%, is discharged to whizzer after index is qualified;
(9) latex that will park more than 12 hours carries out centrifugal treating;
(10) laboratory indexes once more should reach total solids 〉=51%, pH value 〉=10.5, swelling coefficient 2.1-2.4.After latex after qualified is parked 48h-96h, be delivered to down the preface board and park jar.
The PH=7.0 of deionized water ± 0.5, specific conductivity≤5 μ s/cm.
Task of the present invention comes to this and finishes.
The ultra-thin condom of latex production of the present invention and pure natural latex products be compared as follows table:
| Average burstpressures (kPa) | Thickness minimum value (mm) | Maximum thickness (mm) | |
| Natural rubber latex is produced the normal thickness product | 2.18 | 0.065 | 0.070 |
| Natural rubber latex is produced ultra-thin product | 1.6 | 0.057 | 0.062 |
| Natural rubber latex+modified latex is produced ultra-thin product | 1.99 | 0.056 | 0.060 |
| Natural rubber latex+modified latex is produced ultra-thin product | 1.54 | 0.046 | 0.049 |
By the table in as can be seen, the present invention mainly utilizes modified latex and natural rubber latex to mix the blasting performance that improves ultra-thin condom products, on the basis that guarantees product performance, constantly reduce product thickness, thereby make product satisfy the requirement and the consumer demand of international standard.The employing of this modified latex changes the branched structure of latex molecular chain, has improved the blasting performance of product, and product thickness is reached about 0.050mm, and this is that domestic each manufacturing enterprise is unsurpassable at present.After this ultra-thin product innovation success, every product will be saved natural rubber latex about 15%, and cost is also corresponding to decrease, and product is ultra-thin comfortable again, can promote China's condom competitive power in the international market greatly.
Be the ultra-thin condom of latex production of the present invention and the contrast of the ultra-thin product of Du Leisi below:
| Manufacturer | Average burstpressures | Triadic mean thickness 1 | Triadic mean thickness 2 |
| The ultra-thin product that latex of the present invention is produced | 1.536kPa | 0.049mm | 0.046mm |
| The ultra-thin product of Du Leisi | 1.448kPa | 0.062mm | 0.055mm |
The present invention can be used for the formulating vulcanization of rubber latex for producing ultrathin condom.It is ultra-thin and ultra-thin condom products about 0.050mm that this latex can be used for producing thickness.This product in the proof strength quality, meet under the prerequisite of country and relevant international standard, has good comfort, can effectively practise contraception, can also prevent AIDS preferably, transmission of disease such as gonorrhoea, venereal ulcer, hodgkin, chlamydozoan, syphilis, genital herpes and pointed condyloma.
Embodiment
Embodiment 1.A kind of raw material dry state proportioning of rubber latex for producing ultrathin condom.Comprise dry state sulphur, ZnO, zinc diethyldithiocarbamate, 2,6 di tert butyl 4 methyl phenol, KOH, aliphatic alcohol polyethenoxy (20) ether, Sodium hexametaphosphate 99, sodium metnylene bis-naphthalene sulfonate and natural rubber latex according to the extra fine quality ratio.The dry state mass ratio is followed successively by 1.20 parts sulphur, 0.70 part ZnO, 0.40 part zinc diethyldithiocarbamate, 1.00 parts 2,6 di tert butyl 4 methyl phenol, 0.08 part KOH, 0.25 part aliphatic alcohol polyethenoxy (20) ether, 0.05 part Sodium hexametaphosphate 99,0.10 part sodium metnylene bis-naphthalene sulfonate and 100.00 parts natural rubber latex, 3.00 parts modified latex.Modified latex is a MMA grafted natural rubber latex.
Embodiment 2.A kind of raw material dry state proportioning of rubber latex for producing ultrathin condom.Comprise dry state sulphur, ZnO, zinc diethyldithiocarbamate, 2,6 di tert butyl 4 methyl phenol, KOH, aliphatic alcohol polyethenoxy (20) ether, Sodium hexametaphosphate 99, sodium metnylene bis-naphthalene sulfonate and natural rubber latex according to the extra fine quality ratio.The dry state mass ratio is followed successively by 1.20 parts sulphur, 0.70 part ZnO, 0.40 part zinc diethyldithiocarbamate, 1.00 parts 2,6 di tert butyl 4 methyl phenol, 0.08 part KOH, 0.25 part aliphatic alcohol polyethenoxy (20) ether, 0.05 part Sodium hexametaphosphate 99,0.10 part sodium metnylene bis-naphthalene sulfonate and 100.00 parts natural rubber latex, 3.50 parts modified latex.Modified latex is a MMA grafted natural rubber latex.
Embodiment 3.A kind of raw material dry state proportioning of rubber latex for producing ultrathin condom.Comprise dry state sulphur, ZnO, zinc diethyldithiocarbamate, 2,6 di tert butyl 4 methyl phenol, KOH, aliphatic alcohol polyethenoxy (20) ether, Sodium hexametaphosphate 99, sodium metnylene bis-naphthalene sulfonate and natural rubber latex according to the extra fine quality ratio.The dry state mass ratio is followed successively by 1.20 parts sulphur, 0.70 part ZnO, 0.40 part zinc diethyldithiocarbamate, 1.00 parts 2,6 di tert butyl 4 methyl phenol, 0.08 part KOH, 0.25 part aliphatic alcohol polyethenoxy (20) ether, 0.05 part Sodium hexametaphosphate 99,0.10 part sodium metnylene bis-naphthalene sulfonate and 100.00 parts natural rubber latex, 4.00 parts modified latex.Modified latex is a MMA grafted natural rubber latex.
Embodiment 4.A kind of raw material dry state proportioning of rubber latex for producing ultrathin condom.Comprise dry state sulphur, ZnO, zinc diethyldithiocarbamate, 2,6 di tert butyl 4 methyl phenol, KOH, aliphatic alcohol polyethenoxy (20) ether, Sodium hexametaphosphate 99, sodium metnylene bis-naphthalene sulfonate and natural rubber latex according to the extra fine quality ratio.The dry state mass ratio is followed successively by 1.20 parts sulphur, 0.70 part ZnO, 0.40 part zinc diethyldithiocarbamate, 1.00 parts 2,6 di tert butyl 4 methyl phenol, 0.08 part KOH, 0.25 part aliphatic alcohol polyethenoxy (20) ether, 0.05 part Sodium hexametaphosphate 99,0.10 part sodium metnylene bis-naphthalene sulfonate and 100.00 parts natural rubber latex, 4.50 parts modified latex.Modified latex is a MMA grafted natural rubber latex.
Embodiment 5.A kind of raw material dry state proportioning of rubber latex for producing ultrathin condom.Comprise dry state sulphur, ZnO, zinc diethyldithiocarbamate, 2,6 di tert butyl 4 methyl phenol, KOH, aliphatic alcohol polyethenoxy (20) ether, Sodium hexametaphosphate 99, sodium metnylene bis-naphthalene sulfonate and natural rubber latex according to the extra fine quality ratio.The dry state mass ratio is followed successively by 1.20 parts sulphur, 0.70 part ZnO, 0.40 part zinc diethyldithiocarbamate, 1.00 parts 2,6 di tert butyl 4 methyl phenol, 0.08 part KOH, 0.25 part aliphatic alcohol polyethenoxy (20) ether, 0.05 part Sodium hexametaphosphate 99,0.10 part sodium metnylene bis-naphthalene sulfonate and 100.00 parts natural rubber latex, 5.00 parts modified latex.Modified latex is a MMA grafted natural rubber latex.
Embodiment 6.A kind of formulating vulcanization process of rubber latex for producing ultrathin condom.May further comprise the steps:
(1) respectively aforementioned starting material is mixed with the aqueous solution or emulsion or be dispersed in the water, the shared mass ratio of its mass concentration or solid is respectively natural rubber latex-60%, modified latex-50%, sulphur-50%, ZnO-50%, zinc diethyldithiocarbamate-50%, 2,6-di-tert-butyl-4-methy phenol-40%, KOH-25%, aliphatic alcohol polyethenoxy (20) ether-20%, Sodium hexametaphosphate 99-20%, sodium metnylene bis-naphthalene sulfonate-10%, modified latex is a MMA grafted natural rubber latex;
(2) will add according to the natural rubber latex emulsion 835Kg of step (1) preparation in the vulcanizing boiler;
(3) will add according to the modified latex emulsion 39.68Kg of step (1) preparation in the vulcanizing boiler;
(4) the 10-20Kg ammonia soln is added in the vulcanizing boiler, this ammonia soln is the deionized water solution of ammoniacal liquor, and wherein the ratio of deionized water and ammoniacal liquor is 3: 1;
(5) will add in the vulcanizing boiler according to following order and quality according to the solution or the dispersion liquid of step (1) preparation: Sodium hexametaphosphate 99 1.25Kg, sodium metnylene bis-naphthalene sulfonate 5.00Kg, aliphatic alcohol polyethenoxy (20) ether 6.25Kg, KOH1.6Kg, sulphur 12.00Kg, zinc diethyldithiocarbamate 4.00Kg, 2,6 di tert butyl 4 methyl phenol 12.50Kg and ZnO7.00Kg;
(6) add deionized water 80-100Kg and stir, should make total solids 〉=53% of vultex;
(7) start vulcanizing boiler and heat, begin insulation after being warming up to 55 ℃;
(8) begin to clock from insulation, play per sampling half an hour in 2 hours and survey swelling coefficient, when swelling coefficient reaches 2.6, open the cooling system of vulcanizing boiler, latex is lowered the temperature, laboratory indexes when the latex temperature is reduced to 40 ℃ should reach total solids 〉=53%, pH value 〉=10.5, ammonia content 0.50-0.75%, is discharged to whizzer after index is qualified;
(9) latex that will park more than 12 hours carries out centrifugal treating;
(10) laboratory indexes once more should reach total solids 〉=51%, pH value 〉=10.5, swelling coefficient 2.1-2.4.After latex after qualified is parked 48h-96h, be delivered to down the preface board and park jar.
The PH=7.0 of deionized water ± 0.5, specific conductivity≤5 μ s/cm.
Embodiment 7.A kind of formulating vulcanization process of rubber latex for producing ultrathin condom.Its step (7) is to begin insulation after being warming up to 57 ℃; Step (8) is when swelling coefficient reaches 2.5, opens the cooling system of vulcanizing boiler, and latex is lowered the temperature; All the other are with embodiment 6.
Embodiment 8.A kind of formulating vulcanization process of rubber latex for producing ultrathin condom.Its step (7) is to begin insulation after being warming up to 59 ℃; Step (8) is when swelling coefficient reaches 2.4, opens the cooling system of vulcanizing boiler, and latex is lowered the temperature; All the other are with embodiment 6.
Embodiment 1～8 can be used for the formulating vulcanization production of rubber latex for producing ultrathin condom.It is ultra-thin and ultra-thin condom products about 0.050mm that this latex can be used for producing thickness.This product in the proof strength quality, meet under the prerequisite of country and relevant international standard, has good comfort, can effectively practise contraception, can also prevent AIDS preferably, transmission of disease such as gonorrhoea, venereal ulcer, hodgkin, chlamydozoan, syphilis, genital herpes and pointed condyloma.
Claims (4)
1. the raw material dry state proportioning of a rubber latex for producing ultrathin condom, comprise dry state sulphur according to the extra fine quality ratio, ZnO, zinc diethyldithiocarbamate, 2, the 6-di-tert-butyl-4-methy phenol, KOH, aliphatic alcohol polyethenoxy (20) ether, Sodium hexametaphosphate 99, sodium metnylene bis-naphthalene sulfonate and natural rubber latex, it is characterized in that the dry state mass ratio is followed successively by 1.20 parts sulphur, 0.70 the ZnO of part, 0.40 the zinc diethyldithiocarbamate of part, 1.00 the 2,6 di tert butyl 4 methyl phenol of part, 0.08 the KOH of part, 0.25 aliphatic alcohol polyethenoxy (20) ether of part, 0.05 the Sodium hexametaphosphate 99 of part, 0.10 sodium metnylene bis-naphthalene sulfonate of part and 100.00 parts natural rubber latex, 3.00-5.00 the modified latex of part.
2. according to the raw material dry state proportioning of the described rubber latex for producing ultrathin condom of claim 1, it is characterized in that said modified latex is a MMA grafted natural rubber latex.
3. formulating vulcanization process according to the dry state proportioning of the described rubber latex for producing ultrathin condom of claim 1 is characterized in that may further comprise the steps:
(1) respectively aforementioned starting material is mixed with the aqueous solution or emulsion or be dispersed in the water, the shared mass ratio of its mass concentration or solid is respectively natural rubber latex-60%, modified latex-50%, sulphur-50%, ZnO-50%, zinc diethyldithiocarbamate-50%, 2,6-di-tert-butyl-4-methy phenol-40%, KOH-25%, aliphatic alcohol polyethenoxy (20) ether-20%, Sodium hexametaphosphate 99-20%, sodium metnylene bis-naphthalene sulfonate-10%, modified latex is a MMA grafted natural rubber latex;
(2) will add according to the natural rubber latex emulsion 835Kg of step (1) preparation in the vulcanizing boiler;
(3) will add according to the modified latex emulsion 29.76-49.6Kg of step (1) preparation in the vulcanizing boiler;
(4) the 10-20Kg ammonia soln is added in the vulcanizing boiler, this ammonia soln is the deionized water solution of ammoniacal liquor, and wherein the ratio of deionized water and ammoniacal liquor is 3:1;
(5) will add in the vulcanizing boiler according to following order and quality according to the solution or the dispersion liquid of step (1) preparation: Sodium hexametaphosphate 99 1.25Kg, sodium metnylene bis-naphthalene sulfonate 5.00Kg, aliphatic alcohol polyethenoxy (20) ether 6.25Kg, KOH1.6Kg, sulphur 12.00Kg, zinc diethyldithiocarbamate 4.00Kg, 2,6 di tert butyl 4 methyl phenol 12.50Kg and ZnO7.00Kg;
(6) add deionized water 80-100Kg and stir, should make total solids 〉=53% of vultex;
(7) start vulcanizing boiler and heat, begin insulation after being warming up to 55 ℃-59 ℃;
(8) begin to clock from insulation, play per sampling half an hour in 2 hours and survey swelling coefficient, when swelling coefficient reaches 2.6-2.4, open the cooling system of vulcanizing boiler, latex is lowered the temperature, laboratory indexes when the latex temperature is reduced to 39 ± 1 ℃ should reach total solids 〉=53%, pH value 〉=10.5, ammonia content 0.50-0.75%, is discharged to whizzer after index is qualified;
(9) latex that will park more than 12 hours carries out centrifugal treating;
(10) laboratory indexes once more should reach total solids 〉=51%, pH value 〉=10.5, swelling coefficient 2.1-2.4.After latex after qualified is parked 48h-96h, be delivered to down the preface board and park jar.
4. according to the formulating vulcanization process of the dry state proportioning of the described rubber latex for producing ultrathin condom of claim 3, it is characterized in that PH=7.0 ± 0.5 of said deionized water, specific conductivity≤5 μ s/cm.
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| CN102276883A (en) * | 2011-07-01 | 2011-12-14 | 青岛双蝶集团股份有限公司 | Production technology for preparing soft condom with grading, low temperature, and long time vulcanization |
| WO2011157033A1 (en) * | 2010-06-14 | 2011-12-22 | 青岛双蝶集团有限公司 | Production method for golden condom |
| CN102718994A (en) * | 2012-06-15 | 2012-10-10 | 杨昆 | Weather monitoring device and application thereof |
| CN102746537A (en) * | 2012-07-26 | 2012-10-24 | 上海名邦橡胶制品有限公司 | Raw material dry-state proportion and preparation vulcanization process of latex for producing low-nitrosamine condom |
| CN102775653A (en) * | 2012-07-21 | 2012-11-14 | 青岛双蝶集团股份有限公司 | Method for manufacturing lithe condoms |
| CN108245222A (en) * | 2018-01-23 | 2018-07-06 | 青岛星创医疗科技有限公司 | The medical preparation method for taking stone sacculus |
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2008
- 2008-12-14 CN CN2008102384496A patent/CN101434719B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011157033A1 (en) * | 2010-06-14 | 2011-12-22 | 青岛双蝶集团有限公司 | Production method for golden condom |
| CN102276883A (en) * | 2011-07-01 | 2011-12-14 | 青岛双蝶集团股份有限公司 | Production technology for preparing soft condom with grading, low temperature, and long time vulcanization |
| CN102276883B (en) * | 2011-07-01 | 2012-07-25 | 青岛双蝶集团股份有限公司 | Production technology for preparing soft condom under low temperature and long time vulcanization by stages |
| CN102718994A (en) * | 2012-06-15 | 2012-10-10 | 杨昆 | Weather monitoring device and application thereof |
| CN102775653A (en) * | 2012-07-21 | 2012-11-14 | 青岛双蝶集团股份有限公司 | Method for manufacturing lithe condoms |
| CN102746537A (en) * | 2012-07-26 | 2012-10-24 | 上海名邦橡胶制品有限公司 | Raw material dry-state proportion and preparation vulcanization process of latex for producing low-nitrosamine condom |
| CN108245222A (en) * | 2018-01-23 | 2018-07-06 | 青岛星创医疗科技有限公司 | The medical preparation method for taking stone sacculus |
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| CN101434719B (en) | 2010-12-22 |
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