CN114292453B

CN114292453B - Antibacterial condom and preparation method thereof

Info

Publication number: CN114292453B
Application number: CN202111649956.0A
Authority: CN
Inventors: 徐永平
Original assignee: Suzhou Carraway New Materials Co ltd
Current assignee: Suzhou Carraway New Materials Co ltd
Priority date: 2021-12-30
Filing date: 2021-12-30
Publication date: 2022-11-01
Anticipated expiration: 2041-12-30
Also published as: CN114292453A

Abstract

The application relates to the field of condoms, and particularly discloses an antibacterial condom and a preparation method thereof. The antibacterial condom is prepared from the following raw materials in parts by weight: 100 parts of natural latex, 50-100 parts of waterborne polyurethane, 5-12 parts of zinc oxide fiber, 3-9 parts of moringa seed oil, 0.4-0.6 part of sulfur and 0.2-0.5 part of accelerator. The preparation method of the antibacterial condom comprises the steps of preparing working latex, dipping, curling, leaching, dipping a separant, post-vulcanizing, demoulding and the like. According to the application, the obtained condom has good antibacterial property through the synergistic cooperation of the zinc oxide fibers and the moringa seed oil. Meanwhile, the zinc oxide fiber can also improve the mechanical property of the condom; the moringa seed oil can reduce the surface tension of the condom, is beneficial to curling and demoulding of the condom, and reduces the damage of zinc oxide fibers.

Description

Antibacterial condom and preparation method thereof

Technical Field

The present application relates to the field of condoms, and more particularly, it relates to an antibacterial condom and a method of making the same.

Background

Condoms are the most common and simplest contraceptive tools in the world. The condom has the characteristics of safety, reliability, simplicity and economy, and is not only a birth control tool but also an effective tool for preventing the spread of sexual diseases.

At present, the base material of the condom is mainly natural latex; the natural latex has the characteristics of good film forming property, large elasticity, high strength, small influence on human bodies and the like, so that the natural latex is widely applied to the production of condoms. However, since condoms produced from natural latex have a risk of cancer caused by residual nitrosamines, aqueous polyurethanes have begun to be used in the production of condoms to replace natural latex.

In addition to the base material, some auxiliary materials are added in the production of the condom to improve various properties of the condom and increase the functionality of the condom. Because the condom is a tool worn close to the skin, the antibacterial property of the condom is a concern; therefore, it is an important research direction to improve the antibacterial property of condoms.

Disclosure of Invention

In order to improve the antibacterial property of the condom, the application provides an antibacterial condom and a preparation method thereof.

In a first aspect, an antibacterial condom is provided, which adopts the following technical scheme:

the antibacterial condom is prepared from the following raw materials in parts by weight: 100 parts of natural latex, 50-100 parts of waterborne polyurethane, 5-12 parts of zinc oxide fiber, 3-9 parts of moringa seed oil, 0.4-0.6 part of sulfur and 0.2-0.5 part of accelerator.

By adopting the technical scheme, the natural latex and the waterborne polyurethane are matched with each other to form the base material of the condom; the zinc oxide fiber and the moringa seed oil are dissolved in the base material, and the condom has good antibacterial performance through mutual synergistic matching. Meanwhile, the zinc oxide fiber can also improve the mechanical property of the condom; the moringa seed oil can also play a role in lubrication, so that the problem of surface tension rise of the condom caused by the introduction of the waterborne polyurethane is reduced, the curling and the demoulding of the condom are facilitated, the damage of the condom caused by the demoulding is reduced, and the moringa seed oil has positive significance for protecting zinc oxide fibers and further keeping good antibacterial property.

Optionally, the zinc oxide fiber is prepared by the following method:

putting polyethylene glycol, zinc acetate and sodium bicarbonate into an organic solvent, and uniformly mixing to obtain a spinning solution, wherein the mass ratio of the polyethylene glycol, the zinc acetate, the sodium bicarbonate to the organic solvent is (0.5-1): 1: (0.01-0.02): (4-6);

performing electrostatic spinning on the spinning solution to obtain polyethylene glycol/zinc acetate composite fibers;

calcining the polyethylene glycol/zinc acetate composite fiber at 500-600 ℃ for at least 3h to obtain zinc oxide fiber;

the zinc oxide fiber is immersed in an ethanol solution of a surfactant, and then taken out and dried to be surface-dry.

By adopting the technical scheme, the compatibility of the zinc oxide fiber and the natural latex-polyurethane base material can be improved by dipping the surface active agent in the zinc oxide fiber, so that the dispersibility of the zinc oxide fiber in the natural latex-polyurethane base material is improved, and the function of the zinc oxide fiber can be better played. Meanwhile, sodium bicarbonate is introduced in the preparation of the zinc oxide fiber, and can be decomposed to generate carbon dioxide due to heating; a porous structure can be formed on the surface of the obtained zinc oxide fiber through the generation and the escape of carbon dioxide; the surface porous structure increases the associativity of the surfactant and the zinc oxide fiber, thereby being beneficial to further improving the dispersibility of the zinc oxide fiber in the natural latex-polyurethane base material and being beneficial to more fully playing the role of the zinc oxide fiber.

Optionally, the organic solvent is ethanol.

By adopting the technical scheme, the ethanol has wide source and small toxicity to human bodies.

Optionally, during the electrostatic spinning, the voltage is controlled to be 6-12kV, and the temperature is 35-45 ℃.

By adopting the technical scheme, the technological parameters of electrostatic spinning are optimized, and the zinc oxide fiber with better performance is obtained.

Optionally, the surfactant is one of sucrose fatty acid ester, sorbitan fatty acid ester and lecithin.

Optionally, the preparation method of the waterborne polyurethane comprises the following steps:

according to the molar ratio of isocyanate group to hydroxyl group being (1.5-2): 1, mixing polyisocyanate and polyol to react isocyanate groups with hydroxyl groups to obtain a polyurethane prepolymer;

adding a chain extender into the polyurethane prepolymer to improve the molecular weight of the polyurethane prepolymer; then adding hydrogenated castor oil into the polyurethane prepolymer with the improved molecular weight, reacting for 3-6h, and controlling the temperature to be 65-80 ℃; then triethylamine is added for neutralization to obtain a polyurethane prepolymer;

and adding water into the polyurethane prepolymer, and stirring and emulsifying to obtain the waterborne polyurethane.

By adopting the technical scheme, hydroxyl contained in the hydrogenated castor oil can participate in the reaction with isocyanate to generate carbamate, and the lipophilic chain segment is connected to the molecular chain of polyurethane; the introduction of the oleophylic chain segment is beneficial to reducing the surface tension of the aqueous polyurethane, so that the adhesiveness between the condom and the die is reduced, the damage of the condom during curling and demoulding is reduced, and the problem that the antibacterial performance of the condom is damaged due to the damage of the zinc oxide fiber is reduced.

Optionally, the mass ratio of the hydrogenated castor oil to the polyisocyanate (0.1-0.2): 1.

by adopting the technical scheme, the ratio of the hydrogenated castor oil to the polyisocyanate is optimized, and the lipophilic chain segment can be better connected to the molecular chain of the polyurethane.

Optionally, the polyisocyanate is toluene diisocyanate or isophorone diisocyanate; the polyalcohol is one or more of polytetramethylene glycol, diethylene glycol, propylene glycol and neopentyl glycol.

Optionally, the chain extender is dimethylolpropionic acid.

In a second aspect, a preparation method of the antibacterial condom is provided, and the following technical scheme is adopted:

the preparation method of the antibacterial condom comprises the following steps:

weighing the raw materials according to a formula, mixing to obtain working latex, and adding water into the working latex to control the solid content of the working latex to be 40-50wt%;

dipping a mould in the working latex for 10-40s, and then dehydrating, vulcanizing and crosslinking;

curling, leaching, impregnating with a release agent, and post-vulcanizing to obtain a finished condom product; and then demoulding.

By adopting the technical scheme, the condom is prepared smoothly.

In summary, the present application has at least one of the following beneficial technical effects:

1. according to the application, the obtained condom has good antibacterial property through the synergistic cooperation of the zinc oxide fibers and the moringa seed oil. Meanwhile, the zinc oxide fiber can also improve the mechanical property of the condom; the moringa seed oil can reduce the surface tension of the condom, is beneficial to curling and demoulding of the condom, and reduces the damage of zinc oxide fibers.

2. According to the preparation method, the zinc oxide fibers are impregnated with the surfactant, so that the compatibility of the zinc oxide fibers and the natural emulsion-polyurethane base material is improved, the zinc oxide fibers are dispersed more uniformly in the natural emulsion-polyurethane base material, and the effect of the zinc oxide fibers can be better exerted.

3. The application introduces the sodium bicarbonate when preparing the zinc oxide fiber, thereby endowing the obtained zinc oxide fiber with a porous surface structure, being beneficial to better combination of the zinc oxide fiber and the surfactant, further better playing the role of the surfactant and enabling the zinc oxide fiber to be more uniformly dispersed in the natural latex-polyurethane base material.

4. According to the application, hydrogenated castor oil is introduced in the preparation of waterborne polyurethane, and an oily chain segment is introduced to a molecular chain of the polyurethane through the combination of the hydrogenated castor oil and the waterborne polyurethane, so that the surface tension of the waterborne polyurethane is favorably reduced, the damage of a condom during curling and demolding is reduced, and the problem of the damage of the antibacterial performance of the condom caused by the damage of zinc oxide fibers is favorably reduced.

Drawings

FIG. 1 is a scanning electron micrograph of a zinc oxide fiber obtained in production example 3.

Detailed Description

The present application will be described in further detail with reference to examples.

Preparation examples and examples of the materials used: the polyethylene glycol is PEG-200, hydroxyl value is 510-623mgKOH/g, and molecular weight is 180-220. The toluene diisocyanate was 80/20 in type. The polytetramethylene glycol was PTMEG 2000 with a hydroxyl number of 56mgKOH/g. Hydrogenated castor oil is medical grade and purchased from Xian jin Xiang pharmaceutic adjuvant Co., ltd. Natural latex is available from the chemical company of Jinanke Ruida. Moringa seed oil is purchased from Biotech limited company of the scientific and scientific interest in Wuhan Hua.

Preparation example

Preparation example 1

The preparation example discloses a preparation method of zinc oxide fibers, which specifically comprises the following steps:

p1, accurately weighing 5g of polyethylene glycol, 10g of zinc acetate and 40g of ethanol; and uniformly mixing the raw materials to obtain a spinning solution.

And P2, putting the spinning solution obtained from the P1 into an electrostatic spinning instrument, and electrospinning the spinning solution into polyethylene glycol/zinc acetate composite fibers under the conditions that the voltage is 6kV, the temperature is 35 ℃, the distance between a spinning nozzle and a receiving device is 10cm, and the feeding flow rate is 3 mL/h.

And P3, placing the polyethylene glycol/zinc acetate composite fiber obtained from the P2 in a muffle furnace, heating to 600 ℃ at a speed of 5 ℃/min, calcining, and preserving heat for 3h to obtain the zinc oxide fiber.

Preparation example 2

This preparation is substantially the same as preparation 1, except that: after obtaining the zinc oxide fiber, the zinc oxide fiber is dipped in an ethanol solution of a surfactant.

The method specifically comprises the following steps:

And P2, placing the spinning solution obtained from the P1 into an electrostatic spinning instrument, and electrospinning the spinning solution into polyethylene glycol/zinc acetate composite fibers under the conditions that the voltage is 6kV, the temperature is 35 ℃, the distance between a spinning nozzle and a receiving device is 10cm, and the feeding flow rate is 3 mL/h.

And P3, placing the polyethylene glycol/zinc acetate composite fiber obtained from the P2 in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, calcining, and preserving heat for 3h to obtain the zinc oxide fiber.

And P4, soaking the zinc oxide fiber obtained in the step P3 in an ethanol solution (with the concentration of 30 wt%) of sucrose fatty acid ester for 2 hours, and taking out and drying until the surface of the fiber is dry.

Preparation example 3

This preparation is essentially the same as preparation 1, except that: sodium bicarbonate was also added to P1.

The method comprises the following specific steps:

p1, accurately weighing 5g of polyethylene glycol, 10g of zinc acetate, 0.1g of sodium bicarbonate and 40g of ethanol; and uniformly mixing the raw materials to obtain a spinning solution.

And observing the microscopic morphology of the obtained zinc oxide fiber by adopting a scanning electron microscope. Referring to fig. 1, the diameter of the obtained zinc oxide fiber reaches nanometer level, and the surface of the zinc oxide fiber has a porous structure.

Preparation example 4

This preparation is substantially the same as preparation 3, except that: in P1 to P4, the control parameters are changed.

The method comprises the following specific steps:

p1, accurately weighing 10g of polyethylene glycol, 10g of zinc acetate, 0.2g of sodium bicarbonate and 6g of ethanol; and uniformly mixing the raw materials to obtain a spinning solution.

And P2, putting the spinning solution obtained from the P1 into an electrostatic spinning instrument, and electrospinning the spinning solution into polyethylene glycol/zinc acetate composite fibers under the conditions that the voltage is 12kV, the temperature is 45 ℃, the distance between a spinneret and a receiving device is 18cm, and the feeding flow rate is 8 mL/h.

And P3, placing the polyethylene glycol/zinc acetate composite fiber obtained from the P2 in a muffle furnace, heating to 500 ℃ at a speed of 3 ℃/min, calcining, and preserving heat for 6 hours to obtain the zinc oxide fiber.

And P4, soaking the zinc oxide fibers obtained in the step P3 in an ethanol solution (with the concentration of 20 wt%) of sucrose fatty acid ester for 5 hours, and taking out and drying until the surfaces of the fibers are dry.

Preparation examples 5 to 8

Preparation examples 5 to 8 are substantially the same as preparation example 3, except that: the amount of sodium bicarbonate added varied.

Specifically, the method comprises the following steps:

in preparation example 5: the spinning solution is prepared by uniformly mixing 5g of polyethylene glycol, 10g of zinc acetate, 0.05g of sodium bicarbonate and 4g of ethanol.

In preparation example 6: the spinning solution is prepared by uniformly mixing 5g of polyethylene glycol, 10g of zinc acetate, 0.15g of sodium bicarbonate and 4g of ethanol.

In preparation example 7: the spinning solution is prepared by uniformly mixing 5g of polyethylene glycol, 10g of zinc acetate, 0.2g of sodium bicarbonate and 4g of ethanol.

In preparation example 8: the spinning solution was prepared by mixing 5g of polyethylene glycol, 10g of zinc acetate, 0.25g of sodium bicarbonate and 4g of ethanol.

Preparation example 9

This preparation is essentially the same as preparation 6, except that: in P4, the sucrose fatty acid ester is replaced by a sorbitan fatty acid ester.

Preparation example 10

This preparation is essentially the same as preparation 6, except that: in P4, sucrose fatty acid ester was replaced by lecithin.

Preparation example 11

The preparation example discloses a preparation method of waterborne polyurethane, which specifically comprises the following steps:

p10, accurately weighing 26.1g of toluene diisocyanate, 3.18g of diethylene glycol, 2.28g of 1, 3-propylene glycol and 4.16g of neopentyl glycol; placing toluene diisocyanate in a reaction vessel, and stirring at a stirring speed of 80 rpm; uniformly mixing diethylene glycol, 1, 3-propylene glycol and neopentyl glycol, and adding the mixture into a reaction container in three batches; then the temperature is raised to 85 ℃ for reaction for 3h. In this step, the isocyanate group of toluene diisocyanate reacts with the hydroxyl group of the mixed alcohol to give a polyurethane prepolymer.

P20, adding 6g of dimethylolpropionic acid serving as a chain extender into the polyurethane prepolymer obtained from the P10, and reacting for 5 hours to improve the molecular weight of the polyurethane prepolymer; the reaction temperature was controlled at 80 ℃.

And P30, maintaining the reaction temperature, and adding 3g of triethylamine into the polyurethane prepolymer obtained from the P20 to perform neutralization reaction for 0.5h to obtain a polyurethane prepolymer.

And P40, adding water into the polyurethane prepolymer obtained from the P30, stirring and emulsifying to obtain the aqueous polyurethane emulsion, wherein the solid content is controlled to be 40wt%.

Preparation example 12

This preparation is substantially the same as preparation 11 except that: p20 also has a step of adding hydrogenated castor oil.

The method specifically comprises the following steps:

p10, accurately weighing 26.1g of toluene diisocyanate, 3.18g of diethylene glycol, 2.28g of 1, 3-propylene glycol and 4.16g of neopentyl glycol; placing toluene diisocyanate in a reaction vessel, and stirring at a stirring speed of 80 rpm; uniformly mixing diethylene glycol, 1, 3-propylene glycol and neopentyl glycol, adding the mixture into a reaction vessel in three batches, and then heating to 85 ℃ to react for 3 hours. In this step, the isocyanate group of toluene diisocyanate reacts with the hydroxyl group of the mixed alcohol to give a polyurethane prepolymer.

P20, adding 6g of dimethylolpropionic acid serving as a chain extender into the polyurethane prepolymer obtained from the P10, and reacting for 2h to improve the molecular weight of the polyurethane prepolymer; controlling the reaction temperature to be 80 ℃; keeping the reaction temperature, adding 2.6g of hydrogenated castor oil into the polyurethane prepolymer, and continuing to react for 3 hours; in this step, the hydroxyl group contained in the hydrogenated castor oil reacts with the isocyanate to participate in the formation of urethane, and the lipophilic segment is bonded to the polyurethane prepolymer.

Preparation example 13

This preparation is substantially the same as preparation 12 except that: the amount of hydrogenated castor oil added was 3.9g (mass ratio to toluene diisocyanate 0.15.

Preparation example 14

This preparation example is substantially the same as preparation example 12 except that: the amount of hydrogenated castor oil added was 5.2g (mass ratio to toluene diisocyanate was 0.2.

Preparation example 15

This preparation example is substantially the same as preparation example 12 except that: the amount of hydrogenated castor oil added was 6.5g (mass ratio to toluene diisocyanate 0.25.

Preparation example 16

p10, accurately weighing 22.2g of isophorone diisocyanate and 100g of polytetramethylene glycol; placing isophorone diisocyanate in a reaction vessel, and stirring at a stirring speed of 120 rpm; adding the polytetramethylene glycol into a reaction vessel in five batches, heating to 70 ℃ and reacting for 5 hours.

P20, adding 10.3g of dimethylolpropionic acid serving as a chain extender into the polyurethane prepolymer obtained from the P1, and reacting for 2.5 hours; controlling the reaction temperature to 65 ℃; the reaction temperature was maintained and 4.5g of hydrogenated castor oil were added to the polyurethane prepolymer and the reaction was continued for 6h.

And P30, keeping the reaction temperature, adding 5.4g of triethylamine into the polyurethane prepolymer obtained from the P20, and carrying out neutralization reaction for 1 hour to obtain a polyurethane prepolymer.

And P40, adding water into the polyurethane prepolymer obtained from the P30, stirring and emulsifying to obtain the aqueous polyurethane emulsion, wherein the solid content is controlled to be 45wt%.

Examples

Example 1

The embodiment discloses an antibacterial condom which is prepared from the following raw materials: 100g of natural latex, 50g of waterborne polyurethane, 5g of zinc oxide fiber, 3g of moringa seed oil, 0.6g of sulfur, 0.5g of accelerator and 0.5g of oxidant.

Wherein: in the present embodiment, the aqueous polyurethane was prepared from preparation example 1, and the zinc oxide fiber was prepared from preparation example 11; the accelerator is prepared from an accelerator PX and an accelerator ZDC according to the mass ratio of 3:1 (in other embodiments, the mass ratio of promoter PX to promoter ZDC may also be other values within the range of 1-6; the oxidant is antioxidant WSL.

The embodiment also discloses a preparation method of the condom, which specifically comprises the following steps:

s1, preparing working latex:

s11, weighing 100g of natural latex, 50g of waterborne polyurethane, 5g of zinc oxide fiber, 3g of moringa seed oil, 0.6g of sulfur, 0.5g of accelerator and 0.5g of oxidant according to the formula.

S12, adding the waterborne polyurethane, the sulfur, the accelerator, the moringa seed oil and the oxidant into the natural latex, and mixing for 1 hour at a stirring speed of 100 rpm; and then keeping the stirring speed, adding zinc oxide fibers and continuously stirring for 1 hour to obtain the working latex.

S13, standing the working latex for 12 hours, and then adding deionized water into the working latex to adjust the solid content of the working latex to 40wt%.

S14, centrifuging the working latex obtained in the S13 at the rotating speed of 1000rpm for 30min to remove insoluble substances.

S15, standing the working emulsion obtained in the S14 for 12 hours for later use.

S2, cleaning the die:

s21, cleaning the die through two brushes, and controlling the water temperature to be 25 ℃.

S22, cleaning and soaking the die in clean water at 65 ℃ for 1h.

And S23, naturally drying the mold.

S3, dipping latex:

s31, dipping the cleaned mould into the working latex obtained in the S1, controlling the temperature of the working latex to be 40 ℃ and the dipping time to be 10S; in order to ensure the dipping quality, the air bubbles, impurities and oil stains in the working latex are removed at any time. Then the mold is taken out of the working latex and is placed at the temperature of 65 ℃ for dehydration, vulcanization and crosslinking for 20min.

S32, repeating the step S31 to perform secondary impregnation, except that the temperature of the dehydration vulcanization crosslinking is controlled to be 85 ℃.

S33, repeating S31 for the third impregnation, except that the temperature of the dehydration vulcanization crosslinking is controlled to be 70 ℃.

After dipping in latex for three times, the condom blank is formed outside the mould.

S4, curling: and (3) curling the condom blank obtained in the step (S3) by adopting a roller, wherein the blank is required to be round, solid, free from twisting edges, bevel edges and hollow edges.

S5, leaching: the condom blank obtained in S4 is soaked in potassium hydroxide solution (with the concentration of 0.4 mol/L) at 40 ℃ for 45S to remove water soluble substances.

S6, impregnating a release agent: the condom blank obtained in S5 is immersed in a solution of a release agent (specifically silicon dioxide in this embodiment) for 10S, with the temperature of the release agent solution controlled at 50 ℃ and the solubility at 3wt%.

And S7, cleaning and drying.

S8, post-vulcanization: and (4) vulcanizing the condom blank obtained in the step (S7) at the temperature of 90 ℃ for 20min to obtain a finished condom product.

S9, inspecting, demolding and packaging.

Examples 2 to 9

Examples 2-9 are essentially the same as example 1, except that: the raw materials are in different proportions. See table 1 for details.

TABLE 1 raw material compounding ratios of examples 1 to 9

Item	Natural latex	Polyurethane	Fiber	Moringa seed oil	Sulfur	Accelerator	Oxidizing agent
								Example 1	100	50	5	3	0.6	0.5	0.5
Example 2	100	75	5	3	0.5	0.3	0.7
								Example 3	100	100	5	3	0.4	0.2	0.8
Example 4	100	75	7	3	0.5	0.3	0.7
								Example 5	100	75	9	3	0.5	0.3	0.7
Example 6	100	75	12	3	0.5	0.3	0.7
								Example 7	100	75	9	5	0.5	0.3	0.7
Example 8	100	75	9	7	0.5	0.3	0.7
								Example 9	100	75	9	9	0.5	0.3	0.7

Note: the unit of the addition amount of each component is g.

Examples 10 to 18

Examples 10-18 are essentially the same as example 8, except that: the sources of the zinc oxide fibers are different, and are specifically shown in table 2.

Table 2 sources of zinc oxide fibers in examples 10-18

Item	Zinc oxide fiber	Item	Zinc oxide fiber
				Example 10	Preparation example 2	Example 15	Preparation example 7
Example 11	Preparation example 3	Example 16	Preparation example 8
				Example 12	Preparation example 4	Example 17	Preparation example 9
Example 13	Preparation example 5	Example 18	Preparation example 10
				Example 14	Preparation example 6

Examples 19 to 23

Examples 19-23 are essentially the same as example 14, except that: the sources of the waterborne polyurethane are different, and the source is shown in Table 3.

TABLE 3 sources of waterborne polyurethanes in examples 19-23

Item	Aqueous polyurethane	Item	Aqueous polyurethane
				Example 19	Preparation example 12	Example 22	Preparation example 15
Example 20	Preparation example 13	Example 23	Preparation example 16
				Example 21	Preparation example 14

Example 24

This embodiment is substantially the same as embodiment 21 except that: in the preparation method of the condom, part of control parameters are different.

The method comprises the following specific steps:

s1, preparing working latex:

s11, weighing 100g of natural latex, 75g of waterborne polyurethane (prepared from preparation example 14), 9g of zinc oxide fiber (prepared from preparation example 6), 7g of moringa seed oil, 0.5g of sulfur, 0.3g of accelerator and 0.7g of oxidant according to the formula.

S12, adding the waterborne polyurethane, the sulfur, the accelerator, the moringa seed oil and the oxidant into the natural latex, and mixing for 1.5 hours at a stirring speed of 60 rpm; then keeping the stirring speed, adding zinc oxide fiber and continuously stirring for 1 hour to obtain the working latex.

S13, standing the working latex for 48 hours, and then adding deionized water into the working latex to adjust the solid content of the working latex to 50wt%.

S14, centrifuging the working latex obtained in the step S13 at the rotating speed of 800rpm for 60min to remove insoluble substances.

S15, standing the working emulsion obtained in the S14 for 24 hours for later use.

S2, cleaning the die:

s21, cleaning the die through two brushes, and controlling the water temperature to be 20 ℃.

S22, cleaning and soaking the die in clean water at the temperature of 75 ℃ for 0.5 hour.

And S23, naturally drying the die.

S3, dipping latex:

s31, dipping the cleaned mould into the working latex obtained in the S1, controlling the temperature of the working latex to be 30 ℃ and the dipping time to be 40S; in order to ensure the quality of the dipping, the air bubbles, impurities and oil stains in the working latex are removed at any time. Then the mold is taken out of the working latex and is placed at the temperature of 80 ℃ for dehydration, vulcanization and crosslinking for 10min.

S32, repeating the step S31 to perform secondary impregnation, except that the temperature of the dehydration vulcanization crosslinking is controlled to be 95 ℃.

S33, repeating S31 for the third impregnation, except that the temperature of the dehydration vulcanization crosslinking is controlled to be 80 ℃.

S5, leaching: the condom blank obtained in S4 is immersed for 35S in a potassium hydroxide solution (concentration of 0.4 mol/L) at 50 ℃ to remove water-soluble substances.

S6, impregnating a release agent: and (3) soaking the condom blank obtained in the step (S5) in a separant (specifically silicon dioxide in the embodiment) solution for 8 seconds, wherein the temperature of the separant solution is controlled to be 40 ℃, and the solubility is 5wt%.

And S7, cleaning and drying.

S8, post-vulcanization: and (4) vulcanizing the condom blank obtained in the step (S7) at the temperature of 105 ℃ for 12min to obtain a finished condom product.

S9, inspecting, demolding and packaging.

Comparative example

Comparative example 1

The comparative example differs from example 2 in that: the raw materials do not contain zinc oxide fibers.

The method specifically comprises the following steps: an antibacterial condom is prepared from the following raw materials: 100g of natural latex, 75g of waterborne polyurethane, 3g of moringa seed oil, 0.5g of sulfur, 0.3g of accelerator and 0.7g of oxidant.

Comparative example 2

The comparative example differs from example 5 in that: the raw material does not contain moringa seed oil.

The method comprises the following specific steps: an antibacterial condom is prepared from the following raw materials: 100g of natural latex, 75g of waterborne polyurethane, 9g of zinc oxide fiber, 0.5g of sulfur, 0.3g of accelerator and 0.7g of oxidant.

Performance detection

Taking condoms obtained in examples 1-24 and comparative examples 1-2 for sexual test; the results of the tests are shown in Table 4.

And (3) testing the blasting impact volume and the blasting pressure: the condom blasting pressure tester WB-001 is adopted for testing.

And (3) bacteriostatic testing:

(1) Testing strains: hemolytic streptococcus type a 32213, staphylococcus aureus ATCC25923.

(2) The testing steps are as follows:

a. 1mL of the strain with the concentration of 1X 10⁸CFU/mL-5×10⁸Adding the CFU/mL bacterial liquid into 200mL nutrient agar culture medium, and uniformly mixing; then 10mL of the mixed product was taken out and poured into a dish (60 mm).

b. Taking the condom obtained in the example 1, and cutting a circular sheet with the diameter of 25 mm; placing the circular plate in the plate obtained in the step a.

c. The above procedure was repeated so that discs of condoms obtained in examples 2-26 and comparative examples 1-2 were placed in respective dishes.

d. Culturing each plate at 37 ℃ for 48h; the ring width of the zone of inhibition formed around the disc was measured.

And (3) testing the surface tension: test with American HEAD dyne pen.

TABLE 4 Performance testing of condoms obtained in examples 1-24 and comparative examples 1-2

Item	Volume of blast impact/L	Burst pressure/kPa	Ring width/mm of streptococcal restraining ring	Ring width/mm of Staphylococcus aureus-inhibiting ring	Surface tension/mN. M^-1
						Example 1	28.3	3.3	7.52	10.25	36
Example 2	28.5	3.4	7.56	10.26	38
						Example 3	28.4	3.3	7.53	10.24	40
Example 4	30.9	3.6	7.78	10.51	39
						Example 5	32.3	4.3	8.01	10.78	38
Example 6	32.8	4.5	7.95	10.69	38
						Example 7	32.2	4.3	8.32	11.09	34
Example 8	32.1	4.2	8.53	11.29	35
						Example 9	32.2	4.2	8.49	11.28	35
Example 10	32.5	4.3	8.63	11.41	35
						Example 11	33.0	4.4	8.85	11.63	35
Example 12	33.2	4.6	8.82	11.66	36
						Example 13	33.0	4.2	8.80	11.58	36
Example 14	33.5	4.5	8.90	11.66	35
						Example 15	33.6	4.6	8.92	11.68	34
Example 16	33.6	4.4	8.91	11.67	35
						Example 17	33.4	4.4	8.92	11.68	35
Example 18	33.6	4.5	8.88	11.67	35
						Example 19	33.4	4.4	8.86	11.67	33
Example 20	33.3	4.4	8.90	11.65	30
						Example 21	33.4	4.5	8.88	11.63	31
Example 22	33.5	4.5	8.89	11.60	31
						Example 23	33.7	4.7	8.93	11.67	32
Example 24	33.5	4.6	8.89	11.60	31
						Comparative example 1	25.1	2.9	7.02	9.63	38
Comparative example 2	32.4	4.3	7.45	10.19	41

Referring to Table 4, it can be found from the results of the tests of examples 2,4 to 6 and comparative example 1 that: because the zinc oxide fiber has an antibacterial effect, the widths of the hemolytic streptococcal bacteria inhibiting ring and the golden staphylococcus inhibiting ring of the obtained circular sheet of the condom tend to be increased along with the increase of the adding amount of the zinc oxide fiber, namely the antibacterial performance of the condom is gradually improved. Meanwhile, the addition of the zinc oxide fibers is also beneficial to improving the burst impact volume and the burst pressure of the obtained condom, namely the improvement of the mechanical property of the condom.

From the results of the tests of examples 5,7 to 9 and comparative example 2, it can be found that: with the addition of the moringa seed oil, the widths of the hemolysis-inhibiting streptococcus rings and the golden yellow-inhibiting staphylococcus rings of the obtained condom wafer are increased, which shows that the antibacterial performance of the condom is improved by the addition of the moringa seed oil. Meanwhile, the moringa seed oil can play a role in lubrication, so that the surface tension of the obtained condom can be effectively reduced, the problem that the condom is damaged due to poor condom curling and demolding performance caused by the polyurethane serving as a component of the base material is solved, the damage of the zinc oxide fiber is reduced, and the method has an important significance for keeping good antibacterial property of the condom.

The results of the tests of examples 8 and 10 were analyzed to find that: the sucrose fatty acid ester is used as a surfactant, and can improve the compatibility of the zinc oxide fibers and the natural latex-polyurethane matrix, so that the zinc oxide fibers are dispersed in the natural latex-polyurethane matrix more uniformly, and the function of the zinc oxide fibers is better exerted.

As a result of analyzing the results of the measurements in examples 10 to 11 and 13 to 16, it was found that: with the addition of sodium bicarbonate, the dosage is continuously increased, and the antibacterial performance and the mechanical performance of the obtained condom are increased. This is because the combination of the sucrose fatty acid ester and the zinc oxide fiber is not excellent, and therefore, the effect of the sucrose fatty acid ester is limited, and the improvement of the compatibility between the zinc oxide fiber and the natural latex-polyurethane matrix is also limited (example 10). Sodium bicarbonate is added in the preparation process of the zinc oxide fiber, and the sodium bicarbonate can be decomposed at high temperature to produce carbon dioxide, so that the prepared zinc oxide fiber forms a porous structure on the surface due to the generation and the escape of carbon dioxide gas; the porous structure is beneficial to the combination of sucrose fatty acid ester and zinc oxide fiber, so that the effect of the sucrose fatty acid ester can be more fully exerted, the compatibility between the zinc oxide fiber and a natural latex-polyurethane matrix is improved, and the antibacterial property and the mechanical property of the obtained condom are improved.

As a result of the examination of comparative examples 14, 19 to 21, it was found that: with the addition of hydrogenated castor oil during the synthesis of the waterborne polyurethane, the surface tension of the obtained condom is in a decreasing trend; this is due to: when the waterborne polyurethane is synthesized, the lipophilic chain segment can be grafted onto the molecular chain of the polyurethane by adding the hydrogenated castor oil, so that the waterborne polyurethane with lower surface tension can be obtained, and the adhesion between the condom and the mold can be reduced; the method not only facilitates the curling and the demoulding, but also reduces the damage of the condom during the curling and the demoulding, and is beneficial to reducing the problem of the damage of the antibacterial performance of the condom caused by the damage of the zinc oxide fiber.

Additionally, condoms obtained from examples 1-24 of the present application were tested according to the relevant regulations of ISO 10993-5 (cytotoxicity test) and ISO 10993-10 (irritancy and delayed hypersensitivity test). The detection result shows that: all condoms are able to comply with ISO 10993-5 and ISO 10993-10 requirements and are safe.

The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.

Claims

1. An antibacterial condom is characterized in that: the feed is prepared from the following raw materials in parts by weight: 100 parts of natural latex, 50-100 parts of waterborne polyurethane, 5-12 parts of zinc oxide fiber, 3-9 parts of moringa seed oil, 0.4-0.6 part of sulfur and 0.2-0.5 part of accelerator;

the zinc oxide fiber is prepared by the following method:

electrostatic spinning the spinning solution into polyethylene glycol/zinc acetate composite fibers;

soaking the zinc oxide fibers in an ethanol solution of a surfactant, and then taking out and drying the zinc oxide fibers to be surface-dried; the surfactant is one of sucrose fatty acid ester, sorbitan fatty acid ester and lecithin.

2. The antiseptic condom of claim 1, wherein: the organic solvent is ethanol.

3. The antibacterial condom of claim 2, wherein: during the electrostatic spinning, the voltage is controlled to be 6-12kV, and the temperature is controlled to be 35-45 ℃.

4. The antiseptic condom of claim 1, wherein: the preparation method of the waterborne polyurethane comprises the following steps:

and adding water into the polyurethane prepolymer, stirring and emulsifying to obtain the waterborne polyurethane.

5. The antiseptic condom of claim 4, wherein: the mass ratio of the hydrogenated castor oil to the polyisocyanate (0.1-0.2): 1.

6. the antiseptic condom of claim 4, wherein: the polyisocyanate is toluene diisocyanate or isophorone diisocyanate; the polyalcohol is one or more of polytetramethylene glycol, diethylene glycol, propylene glycol and neopentyl glycol.

7. The antibacterial condom of claim 6, wherein: the chain extender is dimethylolpropionic acid.

8. A process for the preparation of an antibacterial condom according to any one of claims 1 to 7, characterized in that: the method comprises the following steps: