CN104017383A - Manufacturing process of high-stability antibacterial plastic bottle cap - Google Patents
Manufacturing process of high-stability antibacterial plastic bottle cap Download PDFInfo
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- CN104017383A CN104017383A CN201410259935.1A CN201410259935A CN104017383A CN 104017383 A CN104017383 A CN 104017383A CN 201410259935 A CN201410259935 A CN 201410259935A CN 104017383 A CN104017383 A CN 104017383A
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Abstract
The invention relates to the technical field of processing of plastic bottle caps, and in particular relates to a manufacturing process of a high-stability antibacterial plastic bottle cap; the bottle cap is formed by injection moulding mixed plastic particles and plastic raw materials; and the manufacturing process of the high-stability antibacterial plastic bottle cap disclosed by the invention comprises the following steps of: mixing water-soluble poly-guanidine inorganic acid salt or organic acid salt aqueous solution with water-soluble silicate aqueous solution, uniformly stirring, adding water-soluble metal salt aqueous solution into the mixture, precipitating, drying and crushing to obtain an antibacterial agent, mixing the antibacterial agent with the plastic raw materials, and then, obtaining the plastic bottle cap. After water-soluble poly-guanidine inorganic acid salt or organic acid salt is mixed with water-soluble silicate, silicate can be gradually hydrolyzed to generate silicic acid; after metal salt is added, mutually entangled molecular chains of polysilicic acid and poly-guanidine in the aqueous solution system are interacted with metal ion, so that flocculation is generated, therefore, precipitation is formed; the molecular chains of poly-guanidine are difficultly separated from the formed poly-guanidine/polysilicate system, so that a hydrophobic poly-guanidine composite antibacterial agent is formed; in addition, the high-stability antibacterial plastic bottle cap manufactured by the invention is applied to raw materials of plastic bottle caps, and therefore, the stability of the antibacterial component is greatly increased.
Description
Technical field
The present invention relates to plastic bottle closure processing technique field, refer in particular to a kind of manufacturing process of high stability antibiotic plastic bottle cap.
Background technology
Along with the raising of people's living standard and the enhancing of health consciousness, and multiple infectious disease popular in recent years, people are constantly increased the requirement of various anti-biotic material goods.Recently, also there is research to attempt the antibacterial application for fields such as plastics, rubber by poly-guanidine.For example, patent CN101037503A, invented a kind of production method of preparing polyhexamethylene guanidine propionic salt powder, this invention utilizes ion isolation exchange membrane, successfully polyhexamethylene guanidine propionic salt is separated from the aqueous solution, make powdered samples, make it can be for the antibacterial auxiliary agent of plastics, rubber.But this polyhexamethylene guanidine propionic salt still has certain moisture absorption, after adding in plastics or rubber, if after soaking in the water of being everlasting or often contacting with water, after long-time, can from plastics or rubber, separate out gradually, antimicrobial efficiency can reduce, and even disappears.Therefore, be difficult to meet the antibiotic plastic that some are had relatively high expectations to water tolerance.
At present, plastic containers are widely used in industrial production and daily life, particularly be widely used in the packing of various food and medicine products, container closure of plastic, as the auxiliary products of plastic containers, plays important effect equally in the packing of various food and medicine products.In actual applications, the inside and outside portion of food and medicine plastic containers very easily infects and breed bacteria, and the inside and outside of supporting plastic packaging container cover equally also very easily infects and breed bacteria with it.
Bacterial infection in plastic wrapping for food and medicine, can cause food and medicine rotten or shorten packing validity period, and food and medicine very easily makes people intersect with the outer bacterial infection of plastic wrapping to spread germs, affect the healthy of people.
The plastic packaging container cover of existing various food and medicine is by plastic warp compression molding, and the sterilization of product is to complete in machine-shaping process, general cleaning and sterilizing no longer all after machine-shaping.
Because the cleaning and sterilizing of moulding product will be used alcohol, chlorinated lime, hypochlorous acid to receive and the medicament such as hydrogen peroxide or use ultraviolet ray, microwave irradiation or use disinfection with high pressure steam sterilizing.And use alcohol, chlorinated lime, when hypochlorous acid is received and the medicament such as hydrogen peroxide carries out disinfection, easily residual harmful Chemical Composition, is used ultraviolet ray, microwave irradiation or use disinfection with high pressure steam sterilizing, these method for disinfection and sterilization expenses are high, increase cost.Even if adopt these method for disinfection and sterilization, sterilization effect is poor.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind ofly to be had the water of being insoluble in, not to affect goods color, and has the manufacturing process of the high stability antibiotic plastic bottle cap of long-term antibacterial and fungistatic effect.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme: a kind of manufacturing process of high stability antibiotic plastic bottle cap comprises the following steps:
1), by water-soluble poly guanidine inorganic acid salt or the organic acid salt aqueous solution and water-soluble silicate aqueous solution, stir, obtain mixture, described water-soluble poly guanidine inorganic acid salt or organic acid salt are poly (hexamethylene) hydrochloride, polyhexamethylene guanidine propionic salt, polyhexamethylene guanidine nitrate, polyhexamethylene guanidine carbonate or water miscible polyoxyethylene groups guanidine inorganic acid salt or organic acid salt;
2), water-soluble metal salt brine solution is joined in the mixture obtaining in step 1), stir, be precipitated thing
3), by step 2) in the drying precipitate obtaining, pulverize and to obtain antiseptic-germicide, standby;
4), each raw material gets the raw materials ready by following mass percent, inorganic powder is 75～78%, dispersion agent is 3～4%, lubricant is 1～3%, coupling agent is 3～6%, thermo-stabilizer is 0.8～1.3%, vector resin is 15～25%;
5), first high-speed mixer is warming up to 110～120 ℃, constant temperature 10～20 minutes;
6), drop into inorganic powder and the coupling agent that step 4) prepares carry out activation treatment in mixing machine, first start stirring at low speed 1～2min, then start high-speed stirring and mix 5～7min, reach 105～115 ℃ to material temperature;
7) drop into dispersion agent, lubricant and the thermo-stabilizer that step 4) is prepared, continue high-speed stirring until material temperature reaches 115～120 ℃;
8) convert stirring at low speed to, and drop into rapidly the vector resin that step 4) prepares and be uniformly mixed 1～2min, blowing is cooling;
9) step 8) gained material is extruded, is obtained the plastic raw materials that can increase plastic bottle closure intensity, toughness and transparency after granulation, standby;
10) antiseptic-germicide obtaining in step 3) is penetrated in the plastic raw materials of melted state equably; After evenly mixing, fusion under the condition of 180 ℃～210 ℃, tie rod, cooling, cut-out, make mixed plastic particles;
11) and then by the mixed plastic particles that accounts for gross weight 9～12% mix with the plastic raw materials that accounts for gross weight 88～91%, after evenly mixing, under the condition of 170 ℃～230 ℃, through injection moulding machine injection moulding moulded section, manufacture high stability antibiotic plastic bottle cap.
Wherein, described step 2) water-soluble metal salt in is zine ion salt, calcium ion salts, aluminum ion salt, cupric ion salt, iron ion salt, one or more in silver ions salt and cerium ion salt.
Wherein, the water-soluble poly guanidine inorganic acid salt in described step 1) or organic acid salt and water-soluble silicate mol ratio are 1:1～1:3, and water-soluble silicate and water-soluble metal salt mol ratio are 6:1～7:1.
Wherein, the water-soluble silicate in described step 1) is water glass or potassium silicate.
Beneficial effect of the present invention is:
Compared with prior art, plastic raw materials provided by the present invention, with low cost, after Substitute For Partial synthetic resins, can significantly reduce production costs; Plastic raw materials of the present invention, because inorganic powder has wherein passed through special surperficial coupling activation treatment, after Substitute For Partial synthetic resins, can significantly reduce the system viscosity of mixture, reduce system extrusion pressure, enhance productivity, simultaneously because plastic raw materials has high thermal conductivity, prepared plastic bottle closure cooling forming speed, makes product occur anisotropy, contributes to the raising of product mechanical property.
After water-soluble poly guanidine inorganic acid salt of the present invention or organic acid salt mix with water-soluble silicate, silicate can be hydrolyzed to silicic acid gradually, and be wound around mutually with the high molecular molecular chain of poly-guanidine, after adding metal-salt, the molecular chain that poly-silicic acid and poly-guanidine are mutually wound around in water solution system and metal ion interact, produce flocculation, thereby the precipitation of formation, make like this molecular chain of poly-guanidine be difficult to shake off out the system of the poly-guanidine/polysilicate from forming, thereby form the poly-guanidine complex antimicrobials of hydrophobe, be applied to greatly improve in the raw material of plastic bottle closure the stability of antibacterial composition.
Preparation method of the present invention is simple, can at room temperature carry out, and antiseptic-germicide of the present invention is insoluble in water, and germ-killing efficiency is high, and does not affect goods color, and application prospect is bright.
Embodiment
For the ease of those skilled in the art's understanding, below in conjunction with embodiment, the present invention is further illustrated, and the content that embodiment is mentioned not is limitation of the invention.
Embodiment mono-
1, a manufacturing process for high stability antibiotic plastic bottle cap, comprises the following steps:
1), by water-soluble poly guanidine inorganic acid salt or the organic acid salt aqueous solution and water-soluble silicate aqueous solution, stir, obtain mixture, described water-soluble poly guanidine inorganic acid salt or organic acid salt are poly (hexamethylene) hydrochloride, polyhexamethylene guanidine propionic salt, polyhexamethylene guanidine nitrate, polyhexamethylene guanidine carbonate or water miscible polyoxyethylene groups guanidine inorganic acid salt or organic acid salt;
2), water-soluble metal salt brine solution is joined in the mixture obtaining in step 1), stir, be precipitated thing
3), by step 2) in the drying precipitate obtaining, pulverize and to obtain antiseptic-germicide, standby;
4), each raw material gets the raw materials ready by following mass percent, inorganic powder is 75%, dispersion agent is 3%, lubricant is 3%, coupling agent is 6%, thermo-stabilizer is 0.8%, vector resin is 25%;
5), first high-speed mixer is warming up to 110 ℃, constant temperature 20 minutes;
6), drop into inorganic powder and the coupling agent that step 1) prepares carry out activation treatment in mixing machine, first start stirring at low speed 1min, then start high-speed stirring and mix 7min, reach 105 ℃ to material temperature;
7) drop into dispersion agent, lubricant and the thermo-stabilizer that step 4) is prepared, continue high-speed stirring until material temperature reaches 115 ℃;
8) convert stirring at low speed to, and drop into rapidly the vector resin that step 4) prepares and be uniformly mixed 1min, blowing is cooling;
9) step 8) gained material is extruded, is obtained the plastic raw materials that can increase plastic bottle closure intensity, toughness and transparency after granulation, standby;
10) antiseptic-germicide obtaining in step 3) is penetrated in the plastic raw materials of melted state equably; After evenly mixing, fusion under the condition of 180 ℃～190 ℃, tie rod, cooling, cut-out, make mixed plastic particles;
11) and then by the mixed plastic particles that accounts for gross weight 9% mix with the plastic raw materials that accounts for gross weight 91%, after evenly mixing, under the condition of 170 ℃, through injection moulding machine injection moulding moulded section, manufacture high stability antibiotic plastic bottle cap.
In the present embodiment, described step 2) water-soluble metal salt in is zine ion salt, calcium ion salts, aluminum ion salt, cupric ion salt, iron ion salt, one or more in silver ions salt and cerium ion salt.
In the present embodiment, the water-soluble poly guanidine inorganic acid salt in described step 1) or organic acid salt and water-soluble silicate mol ratio are 1:1, and water-soluble silicate and water-soluble metal salt mol ratio are 6:1.
In the present embodiment, the water-soluble silicate in described step 1) is water glass.
It should be added that, stirring at low speed refers to that the rotating speed of mixing component in stirrer is at 0～1000 rev/min, and high-speed stirring refers to that the rotating speed of mixing component in stirrer is at 1000～1500 revs/min.
In the present invention, the molar ratio of water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate can regulate in certain scope, preferably poly-guanidine inorganic acid salt or organic acid salt and silicate mol ratio are 1:1～1:3, record through actual experimental data: when poly-guanidine inorganic acid salt or organic acid salt and silicate mol ratio are 1:2.5, the amount that poly-guanidine maintenance water soluble state is present in the aqueous solution is minimum, the productive rate of poly-guanidine/polysilicate that poly-guanidine is converted into hydrophobe is the highest, and the effective antimicrobial component in the poly-guanidine/polysilicate that makes to prepare, poly-guanidine content is higher, make antimicrobial efficiency higher, also greatly reduce its processing to bottle cap when preparation high stability antibiotic plastic bottle cap simultaneously, the impact of mechanics and surface property.
In the present invention, the molar ratio of water-soluble silicate and water-soluble metal salt also can regulate within the specific limits, and preferably silicate and metal-salt mol ratio are 1: 4～1: 5.If metal-salt relative proportion is too low, can cause the productive rate of poly-guanidine/polysilicate to reduce, this is because do not have enough metal-salts that the poly-silicic acid macromolecular chain that gathers guanidine and hydrolyzed silicate formation in the aqueous solution is precipitated out from water; If metal-salt relative proportion is too high, can cause unnecessary waste.
But silicate and metal-salt mol ratio are 1: 4.5 o'clock, can not only guarantee that poly-guanidine/polysilicate has higher productive rate, and greatly reduce the metal-salt ratio of antiseptic-germicide, reduce bottle cap and produced input cost.
In the time of gathering the guanidine aqueous solution and aqueous silicate solution mix and blend in the present invention, the time of stirring is preferably 20 minutes～and 1 hour.Churning time is not confined to this scope, but churning time is too short, silicate is difficult to that all hydrolysis become poly-silicic acid or the polymerization degree is large not, poly-like this silicic acid and poly-guanidine winding degree in the aqueous solution are inadequate, also can make poly-guanidine to detest water degree inadequate, if and overlong time surpasses 2 hours, cause temporal waste.When aqueous metal salt is slowly poured in mixing solutions, stirring velocity is faster, and the particle diameter of poly-guanidine/polysilicate particle of generation is just less,
The preparation of complex antimicrobials of the present invention can at room temperature be carried out, and certainly, also can heat and carry out, and making hydrolyzed silicate is that the speed of poly-silicic acid is faster, accelerates reaction process.The last infusible precipitate forming of reaction can be purified by suction filtration, also can place for some time, and throw out can be deposited to container bottom from water, and upper water liquid is drained, and lower sediment is collected and dry, pulverize.Therefore, the preparation method of complex antimicrobials of the present invention is simple, and reaction conditions is gentle, is easy to suitability for industrialized production.
Complex antimicrobials preparation method of the present invention is: will gather guanidine inorganic acid salt or the organic acid salt aqueous solution and aqueous silicate solution and mix, and obtain mixture, and then water-soluble metal salt brine solution be joined in mixture obtained above, stir, be precipitated thing, dry, pulverize.
By the method for drying precipitate, can be common drying means, comprise that nature dries, oven for drying, or utilize spray-drying process etc.Dried product exhibited is pulverized, and breaking method does not limit yet.
Preparation method of the present invention is simple, can at room temperature carry out, and antiseptic-germicide of the present invention is insoluble in water, and germ-killing efficiency is high, and does not affect goods color, and application prospect is bright.
Embodiment bis-
1, a manufacturing process for high stability antibiotic plastic bottle cap, comprises the following steps:
1), by water-soluble poly guanidine inorganic acid salt or the organic acid salt aqueous solution and water-soluble silicate aqueous solution, stir, obtain mixture, described water-soluble poly guanidine inorganic acid salt or organic acid salt are poly (hexamethylene) hydrochloride, polyhexamethylene guanidine propionic salt, polyhexamethylene guanidine nitrate, polyhexamethylene guanidine carbonate or water miscible polyoxyethylene groups guanidine inorganic acid salt or organic acid salt;
2), water-soluble metal salt brine solution is joined in the mixture obtaining in step 1), stir, be precipitated thing
3), by step 2) in the drying precipitate obtaining, pulverize and to obtain antiseptic-germicide, standby;
4), each raw material gets the raw materials ready by following mass percent, inorganic powder is 76%, dispersion agent is 3.5%, lubricant is 2%, coupling agent is 4.5%, thermo-stabilizer is 1.9%, vector resin is 20%;
5), first high-speed mixer is warming up to 115 ℃, constant temperature 16 minutes;
6), drop into inorganic powder and the coupling agent that step 1) prepares carry out activation treatment in mixing machine, first start stirring at low speed 1.5min, then start high-speed stirring and mix 6.5min, reach 112 ℃ to material temperature;
7) drop into dispersion agent, lubricant and the thermo-stabilizer that step 4) is prepared, continue high-speed stirring until material temperature reaches 118 ℃;
8) convert stirring at low speed to, and drop into rapidly the vector resin that step 4) prepares and be uniformly mixed 1.6min, blowing is cooling;
9) step 8) gained material is extruded, is obtained the plastic raw materials that can increase plastic bottle closure intensity, toughness and transparency after granulation, standby;
10) antiseptic-germicide obtaining in step 3) is penetrated in the plastic raw materials of melted state equably; After evenly mixing, fusion under the condition of 190 ℃～200 ℃, tie rod, cooling, cut-out, make mixed plastic particles;
11) and then by the mixed plastic particles that accounts for gross weight 10% mix with the plastic raw materials that accounts for gross weight 90%, after evenly mixing, under the condition of 190 ℃, through injection moulding machine injection moulding moulded section, manufacture high stability antibiotic plastic bottle cap.
In the present embodiment, described step 2) water-soluble metal salt in is zine ion salt, calcium ion salts, aluminum ion salt, cupric ion salt, iron ion salt, one or more in silver ions salt and cerium ion salt.
In the present embodiment, the water-soluble poly guanidine inorganic acid salt in described step 1) or organic acid salt and water-soluble silicate mol ratio are 1:2, and water-soluble silicate and water-soluble metal salt mol ratio are 6.5:1.
In the present embodiment, the water-soluble silicate in described step 1) is potassium silicate.
Embodiment tri-
1, a manufacturing process for high stability antibiotic plastic bottle cap, comprises the following steps:
1), by water-soluble poly guanidine inorganic acid salt or the organic acid salt aqueous solution and water-soluble silicate aqueous solution, stir, obtain mixture, described water-soluble poly guanidine inorganic acid salt or organic acid salt are poly (hexamethylene) hydrochloride, polyhexamethylene guanidine propionic salt, polyhexamethylene guanidine nitrate, polyhexamethylene guanidine carbonate or water miscible polyoxyethylene groups guanidine inorganic acid salt or organic acid salt;
2), water-soluble metal salt brine solution is joined in the mixture obtaining in step 1), stir, be precipitated thing
3), by step 2) in the drying precipitate obtaining, pulverize and to obtain antiseptic-germicide, standby;
4), each raw material gets the raw materials ready by following mass percent, inorganic powder is 78%, dispersion agent is 4%, lubricant is 1%, coupling agent is 3%, thermo-stabilizer is 1.3%, vector resin is 15%;
5), first high-speed mixer is warming up to 120 ℃, constant temperature 10 minutes;
6), drop into inorganic powder and the coupling agent that step 4) prepares carry out activation treatment in mixing machine, first start stirring at low speed 2min, then start high-speed stirring and mix 5min, reach 115 ℃ to material temperature;
7) drop into dispersion agent, lubricant and the thermo-stabilizer that step 4) is prepared, continue high-speed stirring until material temperature reaches 120 ℃;
8) convert stirring at low speed to, and drop into rapidly the vector resin that step 4) prepares and be uniformly mixed 2min, blowing is cooling;
9) step 8) gained material is extruded, is obtained the plastic raw materials that can increase plastic bottle closure intensity, toughness and transparency after granulation, standby;
10) antiseptic-germicide obtaining in step 3) is penetrated in the plastic raw materials of melted state equably; After evenly mixing, fusion under the condition of 200 ℃～210 ℃, tie rod, cooling, cut-out, make mixed plastic particles;
11) and then by the mixed plastic particles that accounts for gross weight 12% mix with the plastic raw materials that accounts for gross weight 88%, after evenly mixing, under the condition of 230 ℃, through injection moulding machine injection moulding moulded section, manufacture high stability antibiotic plastic bottle cap.
In the present embodiment, described step 2) water-soluble metal salt in is zine ion salt, calcium ion salts, aluminum ion salt, cupric ion salt, iron ion salt, one or more in silver ions salt and cerium ion salt.
In the present embodiment, the water-soluble poly guanidine inorganic acid salt in described step 1) or organic acid salt and water-soluble silicate mol ratio are 1:3, and water-soluble silicate and water-soluble metal salt mol ratio are 7:1.
In the present embodiment, the water-soluble silicate in described step 1) is water glass.
Above-described embodiment is preferably implementation of the present invention, and in addition, the present invention can also realize by alternate manner, and under the prerequisite that does not depart from inventive concept of the present invention, any apparent replacement is all within protection scope of the present invention.
Claims (4)
1. the manufacturing process of a high stability antibiotic plastic bottle cap: it is characterized in that comprising the following steps:
1), by water-soluble poly guanidine inorganic acid salt or the organic acid salt aqueous solution and water-soluble silicate aqueous solution, stir, obtain mixture, described water-soluble poly guanidine inorganic acid salt or organic acid salt are poly (hexamethylene) hydrochloride, polyhexamethylene guanidine propionic salt, polyhexamethylene guanidine nitrate, polyhexamethylene guanidine carbonate or water miscible polyoxyethylene groups guanidine inorganic acid salt or organic acid salt;
2), water-soluble metal salt brine solution is joined in the mixture obtaining in step 1), stir, be precipitated thing;
3), by step 2) in the drying precipitate obtaining, pulverize and to obtain antiseptic-germicide, standby;
4), each raw material gets the raw materials ready by following mass percent, inorganic powder is 75～78%, dispersion agent is 3～4%, lubricant is 1～3%, coupling agent is 3～6%, thermo-stabilizer is 0.8～1.3%, vector resin is 15～25%;
5), first high-speed mixer is warming up to 110～120 ℃, constant temperature 10～20 minutes;
6), drop into inorganic powder and the coupling agent that step 4) prepares carry out activation treatment in mixing machine, first start stirring at low speed 1～2min, then start high-speed stirring and mix 5～7min, reach 105～115 ℃ to material temperature;
7) drop into dispersion agent, lubricant and the thermo-stabilizer that step 4) is prepared, continue high-speed stirring until material temperature reaches 115～120 ℃;
8) convert stirring at low speed to, and drop into rapidly the vector resin that step 4) prepares and be uniformly mixed 1～2min, blowing is cooling;
9) step 8) gained material is extruded, is obtained the plastic raw materials that can increase plastic bottle closure intensity, toughness and transparency after granulation, standby;
10) antiseptic-germicide obtaining in step 3) is penetrated in the plastic raw materials of melted state equably; After evenly mixing, fusion under the condition of 180 ℃～210 ℃, tie rod, cooling, cut-out, make mixed plastic particles;
11) and then by the mixed plastic particles that accounts for gross weight 9～12% mix with the plastic raw materials that accounts for gross weight 88～91%, after evenly mixing, under the condition of 170 ℃～230 ℃, through injection moulding machine injection moulding moulded section, manufacture high stability antibiotic plastic bottle cap.
2. the manufacturing process of high stability antibiotic plastic bottle cap according to claim 1, is characterized in that: the water-soluble metal salt described step 2) is zine ion salt, calcium ion salts, aluminum ion salt, cupric ion salt, iron ion salt, one or more in silver ions salt and cerium ion salt.
3. the manufacturing process of high stability antibiotic plastic bottle cap according to claim 1, it is characterized in that: the water-soluble poly guanidine inorganic acid salt in described step 1) or organic acid salt and water-soluble silicate mol ratio are 1:1～1:3, water-soluble silicate and water-soluble metal salt mol ratio are 6:1～7:1.
4. the manufacturing process of high stability antibiotic plastic bottle cap according to claim 1, is characterized in that: the water-soluble silicate in described step 1) is water glass or potassium silicate.
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Cited By (1)
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| TWI746251B (en) * | 2020-11-05 | 2021-11-11 | 禾聯碩股份有限公司 | A mixing process with metal particles of guiding flow element and guiding flow element thereof |
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