CN102746537B - Raw material dry-state proportion and preparation vulcanization process of latex for producing low-nitrosamine condom - Google Patents
Raw material dry-state proportion and preparation vulcanization process of latex for producing low-nitrosamine condom Download PDFInfo
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- CN102746537B CN102746537B CN201210262113.XA CN201210262113A CN102746537B CN 102746537 B CN102746537 B CN 102746537B CN 201210262113 A CN201210262113 A CN 201210262113A CN 102746537 B CN102746537 B CN 102746537B
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Abstract
The invention relates to a raw material dry-state proportion and a preparation vulcanization process of latex for producing low-nitrosamine condom. The dry-state proportion comprises 0.9-1 part of sulfur, 0.5-0.7 part of ZnO, 0.3-0.6 part of environment-friendly type vulcanization accelerator A, 0-0.3 part of environment-friendly type vulcanization accelerator B, 0.6-1 part of an anti-aging agent, 0.08 part of sodium methylene dinaphthyl sulfonate, 0.25 part of casein, 0.08 part of KOH and 100 parts of natural latex. The vulcanization process comprises ten steps, and can be used for preparation vulcanization production of latex for producing low-nitrosamine condom. In the natural latex rubber condom produced by the latex, the nitrosamine residue, namely the content of N-nitrosamine is smaller than 0.01mg/kg or is not basically detected, therefore, the use is safe and reliable and the carcinogenesis risk is greatly reduced.
Description
Technical field
The invention belongs to condom manufacture technical field, relate in particular to raw material dry state proportioning and the formulating vulcanization process thereof of latex for low-nitrosamine condom manufacture.
Background technology
Condom, as simple, effective contraceptive device, is extensively promoted in countries in the world, and is accepted by masses.Natural rubber latex is because having excellent over-all properties, and the medical product of preparing with it is widely used in the world, and the material that is usually used at present condom more than 90% is natural rubber latex.Latex main component is polyisoprene, and content is more than 90%, its structural formula: (CH
2-C=CH-CH
2)
n, molecular weight is between 10 1 180 ten thousand.Latex has good film-forming properties and elasticity, and wet gel brute force is high, good mechanical properties, and mechanical stability is high, good stability.Latex, after processing, can reach very excellent over-all properties.
Nearest research shows: in numerous latex condoms, contain excessive strong carcinogen--nitrosamine.Its reason is due to when producing condom, and in order to make condom glued membrane have certain physical and mechanical properties, and some vulcanization accelerators that add contain nitrosamine, or produce nitrosamine in sulfidation in these auxiliary agents.
Nitrosamine is organic compound, and its structural formula is:
it is a kind of very strong carcinogenic substance, in more than the 300 kind of N-nitrosamine compound having detected, confirmed that 90% at least can induce a kind of animal carcinogenic, wherein ethyl nitrosamine, diethylnitrosamine and N-nitrosodimethylamine at least have carcinogenic activity to 20 kinds of animals.In the natural and elastomeric course of processing, nitrosamine and its precursor are used as catalyzer, antioxidant, toughener to strengthen intensity and elasticity.In condom, studied discovery nitrosamine.Nitrosamine is strong carcinogenic substance, and the formation of vagina endogenous nitrosamine is considered to cause the reason of cervical cancer.By inference, from the exogenous nitrosamine of condom, also may cause the cancer of reproductive organ and other its organ to occur.Than people such as generations difficult to understand, within 1997, find in vitro in experiment, in 24 hours, the N-up to 88 nanogram(ng)s from condom can transfer to the private film of uterine cervix by nitroso compound.In sexual intercourse process, because short-time contact condom, as about 10 minutes, the migration of nearly 0.6 nanogram(ng) in female sex organs anvil film.A certain amount of nitrosamine also can shift in skin of penis.We and investigator both domestic and external confirm: at Syria hamster zooscopy with it, show, when skin or brill film topical application nitrosamine, can induce part and/or general tumour, especially liver neoplasm.2004, Germany < < Die Welt > > report, the researchist of Germany detects the content of nitrosamine and nitroso compound in 32 kinds of latex condoms on German market, the content that finds that there is nitrosamine and nitroso compound in 29 kinds of condoms surpasses limit standard (93/11/EEC), content is 10-660 μ g/kg, be 1.5～3 times of nitrosamine exposed amount in food, therefore suggestion should be made laws and be limited the content of nitrosamine in latex condom.China, as populous nation, consumes more than 30 hundred million condoms (approximately 30,000,000,000 of international market demand amounts) every year, and its security is also closely bound up with the common people's health.
Have research data to show, the traditional vulcanization accelerator adopting at present easily produces the N-nitrosamine of carinogenicity in Natural Rubber Latex Products production process, and it becomes the greatest problem that Natural Rubber Latex Products faces.American-European countries pays much attention to human health, and issuable poisonous and harmful substances in rubber item has been formulated to relevant laws and regulations and standard.Europe and the U.S. have formulated nitrosamine equal size standard to rubber item, and European Union stipulates that every kilogram of the total content of N-nitrosamine in rubber must not surpass 0.01mg.
The preparation method > > contriver of a Chinese invention patent 200810116911.5 < < latex prophylactic finds detected the content of N-nitrosamine in several famous brand name condoms in China market by European standard method after, and existence conditions institute can detected seven kinds of nitrosamine all surpasses to some extent European standard and limits the quantity of.And the every inspecting standard GB7544-2009 of China's condom and disposable use sanitary product hygienic standard GB15979-2002 all do not make minimum requirements to minimum the limiting the quantity of of the objectionable impurities of material therefor yet.
The TC157 technical discussion that hold in Shanghai in October, 2010 can be gone up, just submitted to the testing standard (draft) of N-content of nitrosamines in natural latex condom---ISO DIS_29941_ (E), iso standard organize relevant latex condom nitrosamine material limit standard formulation with implement very close.Therefore, reduce and thoroughly remove the strong carcinogen nitrosamine in condom, and it is imperative to formulate corresponding national standard.
In the latex condom that proposes in the preparation method > > of a Chinese invention patent 200810116911.5 < < latex prophylactic by the mode of the special-purpose chemical cleaning solution of preparation (containing the Multiple components such as vitamins C, tartaric acid, Mierocrystalline cellulose) washing, usual manner to be made after condom is shaped, the residual volume N-nitrosamine of nitrosamine is less than 0.01m/kg.This scheme fundamentally eliminate to produce the factor of N-nitrosamine, and whether matting is brought, and new security risk is residual not yet obtains comprehensive assessment and confirmation.
Summary of the invention
The object of the invention is to overcome the defect of prior art and a kind of condom manufacture raw material dry state proportioning and formulating vulcanization process thereof with latex be provided.It can be used for producing the natural latex rubber condom of low-nitrosamine residual (or not containing nitrosamine), this product in proof strength quality, meet under the prerequisite of country and relevant international standard, its N-nitrosamine residual quantity is less than 0.01mg/kg or basic inspection does not measure nitrosamine.
The object of the present invention is achieved like this:
The raw material dry state proportioning of latex for a kind of low-nitrosamine condom manufacture of the present invention, this raw material dry state proportioning comprises the starting material of following weight part: the sulphur of 0.9-1 part, the anti-aging agent of the environment-friendly type vulcanization accelerator A of the ZnO of 0.5-0.7 part, 0.3-0.6 part, the environment-friendly type vulcanization accelerator B of 0-0.3 part, 0.6-1 part, the sodium metnylene bis-naphthalene sulfonate of 0.08 part, the casein food grade of 0.25 part, the KOH of 0.08 part and the natural rubber latex of 100 parts, wherein
Described environment-friendly type vulcanization accelerator A is zinc dibenzyldithiocarbamate, zinc diisobutyldithiocarbamate, dibutyl dithio zinc formate or zinc dialkyl dithiophosphate;
Described environment-friendly type vulcanization accelerator B is tetrabenzyl thiuram-disulfide or four isobutyl-thiuram-disulfides;
Described anti-aging agent is 2,6 di tert butyl 4 methyl phenol or p-cresol and dicyclopentadiene butylation product.
Above-mentioned raw-material effect is as follows: sodium metnylene bis-naphthalene sulfonate, as dispersion agent, can make pressed powder be evenly dispersed in liquid, and not reassemble.Casein food grade used as stabilizers.KOH is latex stabilizer, regulates the pH value of latex mixing.Sulphur is vulcanizing agent, makes to produce and be cross-linked between rubber molecule, forms tridimensional network.Environment-friendly type vulcanization accelerator A is selected from a kind of, environment-friendly type sulfuration in four kinds of zinc dibenzyldithiocarbamate, zinc diisobutyldithiocarbamate, dibutyl dithio zinc formate and zinc dialkyl dithiophosphates and promotes that short B is a kind of in two kinds of tetrabenzyl thiuram-disulfide and four isobutyl-thiuram-disulfides, can accelerate vulcanization rate.Anti-aging agent is 2,6 di tert butyl 4 methyl phenol or KY616 (p-cresol and dicyclopentadiene butylation product), can delay the aging of rubber item.ZnO is promoting agent, can increase promotor activity.
Above-mentioned low-nitrosamine condom manufacture is with in the raw material dry state proportioning of latex, in described environment-friendly type vulcanization accelerator A and B, can only add environment-friendly type vulcanization accelerator A, and not add environment-friendly type vulcanization accelerator B, the weight part of environment-friendly type vulcanization accelerator B is got 0 value.
The present invention also provides the formulating vulcanization process of a kind of low-nitrosamine condom manufacture with latex, comprises the following steps:
(1) respectively aforementioned starting material are mixed with to the aqueous solution or emulsion dispersion in water, its mass percent concentration is respectively: natural rubber latex-60%, sulphur-50%, ZnO-50%, environment-friendly type vulcanization accelerator A-50%, environment-friendly type vulcanization accelerator B-50%, anti-aging agent-40%, KOH-10%, casein food grade-10%, sodium metnylene bis-naphthalene sulfonate-10%;
(2) will add in vulcanizing boiler according to the natural rubber latex emulsion of step (1) preparation;
(3) ammonia soln is added in vulcanizing boiler, regulate ammonia content to reach 0.6～0.7%, the deionized water solution that this ammonia soln is ammonia, wherein the ratio of deionized water and ammoniacal liquor is 3: 1;
(4) will add successively in vulcanizing boiler in the following order according to solution or the dispersion liquid of step (1) preparation: KOH, sodium metnylene bis-naphthalene sulfonate, casein food grade, sulphur, environment-friendly type vulcanization accelerator A, environment-friendly type vulcanization accelerator B, anti-aging agent and ZnO;
(5) add deionized water and stirring, should make the total solids > 53% of vultex;
(6) start vulcanizing boiler and heat, start insulation after being warming up to 50 ℃～60 ℃;
(7) from insulation, start to clock, within 2 hours, play per sampling half an hour and survey swelling coefficient, when swelling coefficient reaches 2.4～2.6, open the cooling system of vulcanizing boiler, latex is lowered the temperature, laboratory indexes when latex temperature is down to 38 ± 1 ℃, should reach total solids > 53%, pH value > 10.5, ammonia content 0.50～0.75%, is discharged to and parks tank after qualified;
(8) by parking 48 hours above latex, carry out centrifugal treating;
(9) laboratory indexes again, should reach total solids > 51%, pH value > 10.5, swelling coefficient 2.1～2.4;
(10) latex after qualified is parked after 24h～72h, is delivered to lower order board and parks tank.
The formulating vulcanization process of latex for above-mentioned low-nitrosamine condom manufacture, wherein, the pH of described deionized water is 7.0 ± 0.5, resistivity is 2M Ω.
The present invention can be used for low-nitrosamine condom manufacture and produces with the formulating vulcanization of latex, the natural latex rubber condom of producing with latex of the present invention, the residual volume of its nitrosamine is that the content of N-nitrosamine is less than 0.01mg/kg and even substantially examines and do not measure, safe and reliable, greatly reduce carcinogenic risk.
Embodiment
Below by embodiment, the invention will be further described.
Embodiment 1
A formulating vulcanization process for latex for low-nitrosamine condom manufacture, comprises the following steps:
(1) by the weight part in following table 1, take respectively the starting material of appointment, and be mixed with the aqueous solution or emulsion dispersion in water, its mass percent concentration is respectively: natural rubber latex-60%, sulphur-50%, ZnO-50%, environment-friendly type vulcanization accelerator A-50%, environment-friendly type vulcanization accelerator B-50%, anti-aging agent-40%, KOH-10%, casein food grade-10%, sodium metnylene bis-naphthalene sulfonate-10%, wherein, environment-friendly type vulcanization accelerator A selects zinc dibenzyldithiocarbamate, environment-friendly type vulcanization accelerator B selects tetrabenzyl thiuram-disulfide, anti-aging agent selects 2, 6-di-tert-butyl-4-methy phenol,
(2) will add in vulcanizing boiler according to the natural rubber latex emulsion of step (1) preparation;
(3) ammonia soln is added in vulcanizing boiler, regulate ammonia content to reach 0.6～0.7%, this ammonia soln is as the stablizer of latex, the deionized water solution that this ammonia soln is ammonia, and wherein the ratio of deionized water and ammoniacal liquor is 3: 1;
(4) will add successively in vulcanizing boiler in the following order according to solution or the dispersion liquid of step (1) preparation: KOH, sodium metnylene bis-naphthalene sulfonate, casein food grade, sulphur, environment-friendly type vulcanization accelerator A, environment-friendly type vulcanization accelerator B, anti-aging agent and ZnO;
(5) add deionized water and stirring, should make the total solids > 53% of vultex;
(6) start vulcanizing boiler and heat, start insulation after being warming up to 50 ℃～60 ℃;
(7) from insulation, start to clock, within 2 hours, play per sampling half an hour and survey swelling coefficient, when swelling coefficient reaches 2.4～2.6, open the cooling system of vulcanizing boiler, latex is lowered the temperature, laboratory indexes when latex temperature is down to 38 ± 1 ℃, should reach total solids > 53%, pH value > 10.5, ammonia content 0.50～0.75%, is discharged to and parks tank after qualified;
(8) by parking 48 hours above latex, carry out centrifugal treating;
(9) laboratory indexes again, should reach total solids > 51%, pH value > 10.5, swelling coefficient 2.1～2.4;
(10) latex after qualified is parked after 24h～72h, is delivered to lower order board and parks tank.
The formulating vulcanization process of latex for above-mentioned low-nitrosamine condom manufacture, wherein, the pH of described deionized water is 7.0 ± 0.5, resistivity is 2M Ω.
Embodiment 2
By the weight part in following table 1, take the method for the starting material repetition embodiment 1 of appointment, wherein, environment-friendly type vulcanization accelerator A selects zinc diisobutyldithiocarbamate, environment-friendly type vulcanization accelerator B selects tetrabenzyl thiuram-disulfide, anti-aging agent to select 2,6 di tert butyl 4 methyl phenol.
Embodiment 3
By the weight part in following table 1, take the method for the starting material repetition embodiment 1 of appointment, wherein, environment-friendly type vulcanization accelerator A selects dibutyl dithio zinc formate, and environment-friendly type vulcanization accelerator B selects four isobutyl-thiuram-disulfides, anti-aging agent to select p-cresol and dicyclopentadiene butylation product.
Embodiment 4
By the weight part in following table 1, take the method for the starting material repetition embodiment 1 of appointment, wherein, environment-friendly type vulcanization accelerator A selects zinc dialkyl dithiophosphate, and environment-friendly type vulcanization accelerator B selects four isobutyl-thiuram-disulfides, anti-aging agent to select p-cresol and dicyclopentadiene butylation product.
Embodiment 5
By the weight part in following table 1, take the method for the starting material repetition embodiment 1 of appointment, wherein, environment-friendly type vulcanization accelerator A selects zinc diisobutyldithiocarbamate, and anti-aging agent is selected p-cresol and dicyclopentadiene butylation product, and does not add environment-friendly type vulcanization accelerator B.
Embodiment 6
By the weight part in following table 1, take the method for the starting material repetition embodiment 1 of appointment, wherein, environment-friendly type vulcanization accelerator A selects dibutyl dithio zinc formate, and anti-aging agent is selected p-cresol and dicyclopentadiene butylation product, and does not add environment-friendly type vulcanization accelerator B.
Embodiment 7
By the weight part in following table 1, take the method for the starting material repetition embodiment 1 of appointment, wherein, environment-friendly type vulcanization accelerator A selects zinc dibenzyldithiocarbamate, and anti-aging agent selects 2,6-di-tert-butyl-4-methy phenol, and do not add environment-friendly type vulcanization accelerator B.
Embodiment 8
The method that takes the starting material repetition embodiment 1 of appointment by the weight part in following table 1, wherein, environment-friendly type vulcanization accelerator A selects zinc dialkyl dithiophosphate, and anti-aging agent is selected 2,6 di tert butyl 4 methyl phenol, and does not add environment-friendly type vulcanization accelerator B.
Table 1
Embodiment 1 to 8 can be used for low-nitrosamine condom manufacture and produces with the formulating vulcanization of latex, the natural latex rubber condom that this latex is produced, through high performance liquid chromatography and capillary gas chromatography-mass spectrometric detection, the total content of its N-nitrosamine is all less than 0.005mg/kg, safe and reliable, greatly reduce carcinogenic risk.
Above embodiment is used for illustrative purposes only, but not limitation of the present invention, person skilled in the relevant technique, without departing from the spirit and scope of the present invention, can also make various conversion or modification, therefore all technical schemes that are equal to also should belong to category of the present invention, should be limited by each claim.
Claims (3)
1. a low-nitrosamine condom manufacture latex, it is characterized in that, this latex raw material dry state proportioning comprises the starting material of following weight part: the sulphur of 0.9-1 part, the environment-friendly type vulcanization accelerator A of the ZnO of 0.5-0.7 part, 0.3-0.6 part, the environment-friendly type vulcanization accelerator B of 0-0.3 part but be not 0, the anti-aging agent of 0.6-1 part, the sodium metnylene bis-naphthalene sulfonate of 0.08 part, the casein food grade of 0.25 part, the KOH of 0.08 part and the natural rubber latex of 100 parts, wherein
Described environment-friendly type vulcanization accelerator A is zinc dibenzyldithiocarbamate, zinc diisobutyldithiocarbamate, dibutyl dithio zinc formate or zinc dialkyl dithiophosphate;
Described environment-friendly type vulcanization accelerator B is tetrabenzyl thiuram-disulfide or four isobutyl-thiuram-disulfides;
Described anti-aging agent is 2,6 di tert butyl 4 methyl phenol or p-cresol and dicyclopentadiene butylation product.
2. a formulating vulcanization process for latex for low-nitrosamine condom manufacture as claimed in claim 1, is characterized in that, comprises the following steps:
(1) respectively the starting material described in claim 1 are mixed with to the aqueous solution or emulsion dispersion in water, its mass percent concentration is respectively: natural rubber latex-60%, sulphur-50%, ZnO-50%, environment-friendly type vulcanization accelerator A-50%, environment-friendly type vulcanization accelerator B-50%, anti-aging agent-40%, KOH-10%, casein food grade-10%, sodium metnylene bis-naphthalene sulfonate-10%;
(2) will add in vulcanizing boiler according to the natural rubber latex emulsion of step (1) preparation;
(3) ammonia soln is added in vulcanizing boiler, regulate ammonia content to reach 0.6～0.7%, the deionized water solution that this ammonia soln is ammonia, wherein the ratio of deionized water and ammoniacal liquor is 3:1;
(4) will add successively in vulcanizing boiler in the following order according to solution or the dispersion liquid of step (l) preparation: KOH, sodium metnylene bis-naphthalene sulfonate, casein food grade, sulphur, environment-friendly type vulcanization accelerator A, environment-friendly type vulcanization accelerator B, anti-aging agent and ZnO;
(5) add deionized water and stirring, should make the total solids > 53% of vultex;
(6) start vulcanizing boiler and heat, start insulation after being warming up to 50 ℃～60 ℃;
(7) from insulation, start to clock, within 2 hours, play per sampling half an hour and survey swelling coefficient, when swelling coefficient reaches 2.4～2.6, open the cooling system of vulcanizing boiler, latex is lowered the temperature, laboratory indexes when latex temperature is down to 38 ± 1 ℃, should reach total solids > 53%, pH value > 10.5, ammonia content 0.50～0.75%, is discharged to and parks tank after qualified;
(8) by parking 48 hours above latex, carry out centrifugal treating;
(9) laboratory indexes again, should reach total solids > 51%, pH value > 10.5, swelling coefficient 2.1～2.4;
(10) latex after qualified is parked after 24h～72h, is delivered to lower order board and parks tank.
3. the formulating vulcanization process of latex for low-nitrosamine condom manufacture as claimed in claim 2, is characterized in that, the pH of described deionized water is 7.0 ± 0.5, and resistivity is 2M Ω.
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| CN102936359A (en) * | 2012-12-03 | 2013-02-20 | 上海名邦橡胶制品有限公司 | Preparation method of environment-friendly condom |
| CN103881167B (en) * | 2014-04-04 | 2018-03-30 | 山东海博橡塑制品有限公司 | Medical macromolecular materials and its production method for rubber batching pig |
| CN113337019B (en) * | 2021-06-25 | 2022-11-15 | 山东极美乳胶科技有限公司 | Ultra-thin condom formula and production process thereof |
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| CN101628996B (en) * | 2008-07-18 | 2012-05-30 | 绿神（北京）乳胶业有限公司 | Method for preparing latex condoms |
| CN101434719B (en) * | 2008-12-14 | 2010-12-22 | 青岛双蝶集团股份有限公司 | Raw material dry state proportion for rubber latex for producing ultrathin condom and formulating vulcanization process thereof |
| CN101851359B (en) * | 2010-06-04 | 2011-12-14 | 中国化工橡胶株洲研究设计院 | Antibacterial latex prophylactic and production method thereof |
| CN101891906B (en) * | 2010-06-08 | 2011-10-26 | 郑林 | Nitrosamine-free condom and manufacturing method thereof |
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