CN111607469B - Instant antibacterial masterbatch and preparation method thereof - Google Patents
Instant antibacterial masterbatch and preparation method thereof Download PDFInfo
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- CN111607469B CN111607469B CN202010649349.3A CN202010649349A CN111607469B CN 111607469 B CN111607469 B CN 111607469B CN 202010649349 A CN202010649349 A CN 202010649349A CN 111607469 B CN111607469 B CN 111607469B
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Abstract
The invention provides an instant antibacterial master batch and a preparation method thereof, belonging to the technical field of antibiosis. An instant antibacterial master batch is prepared by the following steps: s01, preparing the guanidine salt polymer and the polyethylene glycol into the composite antibacterial agent by a physical mixing method according to the proportion; s02, mixing the guanidine salt polymer/polyethylene glycol antibacterial agent with the zinc-carrying antibacterial agent; s03: mixing the guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent, water, surfactant, builder, sodium carboxymethylcellulose and essence uniformly, carrying out extrusion granulation by an internal mixing kneading extrusion strand granulator, and carrying out S04: coating with sodium stearate micropowder. The prepared instant antibacterial master batch has good fluidity and is not easy to adhere, and can be quickly dissolved after meeting water, thereby playing the functions of quick sterilization and degerming.
Description
Technical Field
The invention relates to the technical field of antibiosis, in particular to an instant antibacterial master batch which can be quickly dissolved in water and has the functions of sterilization and degerming and a preparation method thereof.
Background
In recent years, with the increasing economic level of people, the requirement for sanitation in life is higher, and a certain amount of disinfectant is often added by consumers when clothes are washed. Common disinfectant in the market, generally include sodium hypochlorite, effective component such as Parachlorometaxylenol (PCMX), but sodium hypochlorite, strong oxidizing property has, probably can cause the clothing to fade, and Parachlorometaxylenol (PCMX) itself is difficult for being dissolved in water, it is inconvenient to use, the producer is only through adding a large amount of surfactants, other components such as alcohols make up it into the liquid state, its effective content is in thousandth to several percent within range, effective concentration is low, and the addition is great when washing at every turn, it is inaccurate to hold the addition when the consumer adds, can lead to bactericidal effect greatly reduced, the performance is not out its best effect.
The guanidine salt polymer (polyguanidine) is a polymer based on a guanidine group, has the excellent performances of high safety, broad sterilization spectrum, low effective concentration, high action speed, stable property, easy water dissolution and the like, is harmless to human body temperature, is an environment-friendly antibacterial agent, and has extremely wide application in industry, agriculture, medical use and daily life. The currently available types of guanidine salt polymers include polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, or other inorganic and organic acid salts of polyhexamethylene (bis) guanidine, polyoxyethylene guanidine, etc., and many new guanidine salt polymers are being developed.
The water-soluble guanidine salt polymer is used as a sterilization component, and the sterilization effect can be achieved by adding a small amount of the polymer each time, but the polyhexamethylene guanidine hydrochloride, the polyhexamethylene biguanide hydrochloride and the like are easy to absorb moisture, the polyhexamethylene guanidine hydrochloride sold in the market is usually required to be stored in a sealed manner, the polyhexamethylene guanidine hydrochloride absorbs moisture and blocks quickly after being unsealed, the surface is sticky, and a consumer is difficult to directly take the polymer when using the polymer, so that the operation is inconvenient; in addition, the polyhexamethylene guanidine hydrochloride has high safety requirements, non-professional persons are not required to directly contact the polyhexamethylene guanidine hydrochloride with hands and skins, dust samples generate dust when poured and are inhaled by people, and the dust samples are not suitable for health, and when the dust samples are used, the addition amount of the powdery product is not controlled well by consumers, and is not easy to measure more or less.
If polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride and the like are prepared into an aqueous solution, the problem of inaccurate metering also exists, and the problems of plastic package recycling or plastic white pollution are caused because a plastic container is used for liquid packaging, and in addition, most of water is used during transportation, so the energy consumption is high, and the effective transportation efficiency is low.
Aiming at the situation, the invention provides an instant antibacterial master batch and a preparation method thereof, and the prepared instant antibacterial master batch has the guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent content of more than 45 wt%. The uniformity is good, convenient to use, and when washing, add a certain amount of antibiotic master batch ball, not only the quantity is easily measured, can also release bactericidal composition such as guanidine salt polymer germicide, zinc ion antibacterial agent, essence fast, play the efficiency of disinfecting, degerming.
Disclosure of Invention
The invention provides an instant antibacterial master batch and a preparation method thereof, which can prepare the antibacterial master batch with the content of a guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent being more than 45 wt%, and when clothes are washed, a small amount of the antibacterial master batch is added, so that the antibacterial master batch can be quickly dissolved in the washing process and fully acts with fabrics, and the antibacterial and degerming effects are achieved.
An instant antibacterial master batch is prepared by the following steps:
s01: guanidine salt polymer and polyethylene glycol are mixed fully and uniformly by physical mixing methods such as stirring according to the proportion to prepare the composite antibacterial agent, the weight ratio of the guanidine salt polymer to the polyethylene glycol is 90: 10-99: 1, the preferable weight ratio is 95: 5-99: 1, the polyethylene glycol has good water solubility, when the molecular weight is too large, the water solubility of the polyethylene glycol is slow, the compatibility with the guanidinium polymer is relatively poor, the polyethylene glycol with the molecular weight of 600-2000 is preferably selected, and after the polyethylene glycol and the guanidinium polymer are fully and physically mixed, can fully mix the molecular chain of the guanidinium polymer with the molecular chain of the polyethylene glycol, increase the instant solubility of the guanidinium polymer, in addition, after polyethylene glycol is introduced, the sterilization efficiency is obviously improved;
s02, mixing the guanidine salt polymer/polyethylene glycol composite antibacterial agent and the zinc-loaded antibacterial agent by physical mixing methods such as stirring and the like to fully and uniformly mix the guanidine salt polymer/polyethylene glycol composite antibacterial agent and the zinc-loaded antibacterial agent, wherein the weight ratio is 70: 30-95: 5, the preferable weight ratio is 80: 20-90: 10, the composite antibacterial agent with good uniform hydrophilicity can be formed by optimizing the ratio of the guanidine salt polymer, the polyethylene glycol and the zinc ion antibacterial agent and fully and uniformly stirring the guanidine salt polymer, the guanidine salt polymer/polyethylene glycol composite antibacterial agent and the zinc ion antibacterial agent are compounded, and the zinc ion antibacterial agent of an inorganic carrier is introduced to compound zinc ions and the guanidine salt polymer, so that the antibacterial effect is further improved;
s03, compounding the guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent prepared in the step S02 with a surfactant, a builder, water, sodium carboxymethylcellulose and essence, carrying out banburying meshing processing in a banburying kneading extrusion bracing granulator, kneading for more than 10 minutes to fully mix the components uniformly, and carrying out extrusion granulation to prepare uniform spherical antibacterial master batches, wherein the ratio of the components is as follows (weight percentage):
guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent: 50-80%;
surfactant (b): 3-5%, the surfactant is added to promote the water solubility of the composite antibacterial agent system, the water solubility of the composite antibacterial agent system can be fully acted with oily pollutants and bacteria in the fabric, the antibacterial efficiency is improved, excessive surfactant can cause excessive foam and waste of washing water, and the preferable surfactant is 3-5%;
builder: 1-2%, the builder is used as a detergent assisting agent and an antibacterial synergist, the antibacterial performance is obviously improved after the builder is added, the content is not too high, the alkalinity of a washing system is too strong, and the addition amount is preferably 1-2%;
water: 10-30%, the water addition amount cannot be too high, the viscosity can be reduced due to too high water addition amount, the brace cannot be extruded, granulated and formed, the water addition amount is too small, the system viscosity is too high, the dispersibility is not good, and the preferable content is 10-30%;
sodium carboxymethylcellulose: 3-20%, the sodium carboxymethyl cellulose can improve the viscosity of the whole system of the antibacterial master batch, so that the antibacterial master batch can be extruded into bracing strips, too much viscosity can cause too high viscosity, too much fine powder can cause too low viscosity during extrusion, and the viscosity cannot be extruded into strips, preferably 3-20%, and more preferably 10-15%;
essence: 0.02-0.2%, the essence can bring fresh smell, and has an auxiliary antibacterial effect, at least one of tea tree oil, peppermint oil, ginger oil, vanillin, thymol and cinnamaldehyde is preferably selected, the content of the essence is too high, the smell is not obvious when the content of the essence is low, the antibacterial synergistic effect is not strong, and the content of the essence is preferably 0.02-0.2%;
adjusting the components of a guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent, water, a surfactant, a builder, sodium carboxymethylcellulose and essence, and performing a large amount of proportion blending tests, so that the guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent can be fully and uniformly stirred in a kneading cavity, has certain viscoelasticity, can be extruded from an extruder, can be stably pulled into strips, has certain strength during granulation, cannot be cut into pieces, and forms excessive fine powder;
s04, performing primary physical mixing on the uncoated spherical antibacterial master batch prepared in the S03 and the flaky sodium stearate micro powder, stirring the mixture in a stirrer at a low speed to coat a layer of sodium stearate micro powder on the surface of the mixture, immediately performing rotary coating treatment by using a coating machine, blowing hot air at the temperature of 100-150 ℃, softening the sodium stearate, uniformly and compactly coating the softened sodium stearate on the surface of the antibacterial master batch, and preparing the instant antibacterial master batch, wherein the ratio of the uncoated spherical antibacterial master batch to the sodium stearate is 95: 5-99: 1;
further, the surface of the uncoated spherical antibacterial master batch which is extruded and cut into granules is coated, so that the spherical antibacterial master batch is not easy to adhere to each other and cause agglomeration. The inventor tries various coating systems, including inorganic powder, such as zeolite, montmorillonite, kaolin and the like, organic powder includes an antioxidant, calcium stearate and the like, but the problems of poor coating effect, easy adhesion, or excessive use amount and the like exist, the inorganic powder is too much, the calcium stearate and the like are not easy to dissolve in water, and adverse effects can be caused to washing of a washing machine, a flaky sodium stearate coating formula is preferably selected through a large amount of formula screening, and sodium stearate particles are not easy to be too large, otherwise the surface coating property of the antibacterial master batch is poor, and through a large amount of screening, the sodium stearate coating effect of a flaky structure is found to be good, coating can be carried out by adding as little as possible, the antibacterial composite system is suitable for the invention, and the ratio of the uncoated spherical antibacterial master batch to the sodium stearate is 95: 5-99: 1, the sodium stearate micro powder is flaky, and the particle size is preferably 300 to 500 meshes.
Further, the effective content of the guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent prepared in the S02 in the uncoated spherical antibacterial master batch is 50-80 wt%.
Further, the guanidine salt polymer is at least one of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, polyhexamethylene guanidine nitrate, polyhexamethylene biguanide nitrate, polyhexamethylene guanidine carbonate, polyhexamethylene biguanide carbonate, polyhexamethylene guanidine propionate, polyhexamethylene biguanide propionate, polyhexamethylene guanidine phosphate and polyhexamethylene biguanide phosphate.
Furthermore, the zinc ion antibacterial agent is an antibacterial agent with zinc ions as a main antibacterial component, the carrier is 4A zeolite, 5A zeolite, natural zeolite, diatomite, montmorillonite and kaolin, the content of the zinc ions is 10-50 wt%, the 4A zeolite is preferred, the content of the zinc ions is preferably 20-30 wt%, the proportion of the zinc ion antibacterial agent is too high, or the content of the zinc ions in the antibacterial agent is too high, so that the dissolved zinc ions are too fast, a complex compound can be formed with a guanidinium polymer, the activity of the molecular chain movement of the guanidinium polymer is reduced, the content of the zinc ion antibacterial agent is too low, or the content of the zinc ions in the antibacterial agent is too low, so that the antibacterial efficiency is too low. The zeolite-carried zinc has better effect and is possibly related to the cubic form, hardness, particle size and the like of the zeolite, and inorganic carriers such as the zeolite and the like can generate friction with fabrics in the washing process, so that the molecular chain of the guanidine salt polymer is driven to act on the fabrics, and the antibacterial effect is further improved.
The sodium stearate micro powder is flaky, the particle size is preferably 300-500 meshes, and the sodium stearate with different particle sizes and particle rows can be uniformly coated on the surface of the antibacterial master batch to play a role in isolation protection, improve the water locking property of the antibacterial master batch, keep better wettability, and be quickly dissolved in water to play a role in quick antibiosis;
the molecular weight of the polyethylene glycol is 600-20000, preferably 600-2000;
the essence is at least one of tea tree oil, oleum Menthae Dementholatum, ginger oil, vanillin, thymol, and cinnamaldehyde.
Further, the surfactant is at least one of sodium dodecyl benzene sulfonate, sodium lauryl sulfate and fatty alcohol-polyoxyethylene ether sodium sulfate.
Further, the builder is sodium carbonate and/or potassium carbonate.
Further, the temperature of the guanidine salt polymer, the polyethylene glycol and the zinc-loaded antibacterial agent when mixed according to the proportion is not more than 40 ℃.
The invention provides a preparation method of an instant antibacterial master batch, which comprises the steps of uniformly mixing components comprising a guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent, water, a surfactant, a builder, sodium carboxymethylcellulose and essence according to the sequence and content, and then carrying out extrusion granulation by an internal mixing kneading extrusion bracing granulator.
Further, after the composite components are granulated, the composite components are immediately and physically mixed with the flaky sodium stearate micro powder to coat a layer of sodium stearate micro powder on the surface, then a coating machine is immediately used for coating, hot air is blown in, and rotary coating is carried out, so that the surface of the uncoated spherical antibacterial master batch is uniformly and densely coated after the sodium stearate is softened.
The invention also provides the instant antibacterial master batch prepared by the preparation method of the instant antibacterial master batch, and the instant antibacterial master batch can quickly and continuously release guanidine salt polymer and zinc ion components after encountering water, is added when clothes are washed, and has the functions of quick sterilization and degerming.
The invention compounds guanidinium polymer and polyethylene glycol firstly, improves the hydrophilicity of guanidinium and the affinity to fabrics, tests show that polyethylene glycol is helpful for improving antibacterial efficiency, then compounds guanidinium polymer/polyethylene glycol composite antibacterial agent and zinc-carrying antibacterial agent, further improves antibacterial efficiency, improves the sterilization rate during washing, researches water, surfactant, synergistic detergent, processing aid and the like according to the performance of the existing antibacterial agent after preparing an efficient composite antibacterial formula system, carries out a large amount of formula researches, invents an uncoated spherical antibacterial master batch which can be smoothly extruded into balls and has the effective content of the guanidinium polymer/polyethylene glycol/zinc-carrying antibacterial agent three-component composite antibacterial agent of 50-80 percent, and carries out surface coating by using flaky sodium stearate through the researches, the prepared water-soluble antibacterial agent can be quickly dissolved when clothes are washed, can not be adhered in a storage period, keeps good hydrophilicity, can be quickly dissolved after meeting water and stirring in use, and plays a role in sterilization and degerming.
The invention provides an instant antibacterial master batch, which has good fluidity and can be quickly dissolved in water, and a small amount of antibacterial master batch is added when clothes are washed by a washing machine, so that the washing machine can be effectively assisted to remove pathogenic microorganisms such as bacteria and fungi, the functions of quick sterilization and degerming can be achieved, the clothes are cleaner and more sanitary, and the instant antibacterial master batch has the advantages of high safety, convenience in use and high efficiency in degerming.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of the instant antibacterial masterbatch prepared after extrusion granulation and coating.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete description of the present invention will be given below with reference to specific embodiments, and it is obvious that the described embodiments are some but not all embodiments of the present invention, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
The raw materials and equipment involved in the embodiment of the invention are as follows:
polyhexamethylene guanidine hydrochloride: hubeidingchengjingshikai pharmaceutical chemical Co., Ltd, CAS No.57028-96-3, powder;
zinc-loaded antimicrobial agents: zinc content 30%, Z301, powder, commercially available;
polyethylene glycol: molecular weight of 600-2000, chemical purity, commercially available
Sodium dodecylbenzenesulfonate: chemically pure, commercially available
Sodium carbonate: chemically pure, commercially available
Sodium carboxymethylcellulose: fushan Ri Special chemical Co., Ltd, commercially available
Essence: is commercially available
Banburying kneading extrusion brace granulator: the full-automatic pill making machine has an internal mixing kneading cavity, can extrude, brace and cut into granules, and has the model of WK-300
A coating machine: water chestnut type coating machine, model WKY-600
Preparation of instant antibacterial masterbatch
1. Preparation of guanidine salt polymer/polyethylene glycol composite antibacterial agent
The water-soluble polyhexamethylene guanidine hydrochloride and polyethylene glycol (different molecular weights) are uniformly stirred in a stirrer according to the proportion shown in the table 1 to prepare the guanidine salt polymer/polyethylene glycol composite antibacterial agent.
Table 1.
2. Preparation of guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent
The prepared water-soluble polyhexamethylene guanidine hydrochloride and polyethylene glycol are uniformly stirred in a stirrer, and then the parts of the zinc-loaded antibacterial agent shown in the table 2 are added for continuous uniform stirring to prepare the guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent.
Table 2.
3. Preparation of uncoated spherical antibacterial masterbatch
Firstly, uniformly mixing the prepared guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent, water, sodium dodecyl benzene sulfonate, sodium carbonate, sodium carboxymethyl cellulose and essence in a low-speed mixer according to the proportion designed in the table 3, carrying out banburying meshing processing in a banburying kneading extrusion brace granulator, kneading for more than 10 minutes to fully and uniformly mix, and carrying out extrusion granulation to prepare the spherical antibacterial master batch.
Table 2.
4. Preparation of instant antibacterial masterbatch
The prepared spherical antibacterial master batch and sodium stearate micro powder are preliminarily mixed in a low-speed mixer according to the proportion designed in the table 3, so that the surface of the spherical antibacterial master batch is coated with a layer of sodium stearate micro powder, then the coating machine is immediately used for carrying out rotary coating treatment, hot air with the temperature of 100 ℃ and 120 ℃ is blown in, the uniform rotary stirring is carried out for 10-30 minutes, the sodium stearate is softened, uniformly and compactly coated on the surface of the spherical antibacterial master batch, the surface is smooth, and the sodium stearate micro powder and the spherical antibacterial master batch are not adhered to each other.
TABLE 3
Second, application of antibacterial masterbatch prepared by preparation method of instant antibacterial masterbatch
After the instant antibacterial master batch meets water, the guanidine salt polymer and the zinc ion component can be quickly and continuously released, and the quick antibacterial master batch is added when clothes are washed, so that the functions of quick sterilization and degerming are achieved. As shown in figure 1, the antibacterial master batch is prepared into granular antibacterial master batch.
Thirdly, evaluation of degerming effect of instant antibacterial masterbatch after washing in water
The prepared instant type antibacterial mother granules of comparative example 34, comparative example 35 and example 36 were used for evaluation of sterilizing effect at the time of washing clothes. Referring to the sterilization detection method of GB21551.5-2010 antibacterial, sterilization and purification functions of household and similar electric appliances-Special requirements of washing machines, standard washing materials are added into a common 10 kg washing machine without sterilization function: the bleaching medium plain cloth required by GB/T411 is characterized in that a kerchief of 330mm x 330mm is prepared by desizing treatment of 21 +/-2 counts of warp yarns and 21 +/-2 counts of weft yarns. Test sample cloth: the bleaching medium plain cloth required by GB/T411 is characterized in that 21 +/-2 counts of warp yarns and 21 +/-2 counts of weft yarns are subjected to desizing treatment to prepare square cloth with the thickness of 100mm multiplied by 100mm, and the total weight is 3 kilograms.
Uniformly coating 1mL of a diluted solution of a bacterial solution on each piece of test sample cloth with the thickness of 100mm multiplied by 100mm, preparing 2 washing machines with the same model according to an appendix AA in GB21551.5 in an operation method, adding the instant antibacterial master batch into one washing machine, not adding the instant antibacterial master batch into the other washing machine (reference sample), starting a washing program, taking out the test cloth after the washing is finished, and testing the number of the residual viable bacteria on the test sample cloth by adopting a fire bacteria counting method. And (3) detecting bacteria: staphylococcus aureus, Escherichia coli, and bacterial liquid concentration of 1.0 × 109～9.0×109CFU/mL. The experiment was repeated 3 times, and the sterilization rate was calculated, and the average value, the amount of the instant antibacterial masterbatch and the sterilization effect are shown in table 4.
The calculation formula is as follows:
table 4.
The sterilizing effect is shown in table 4, when the adding amount of the instant type antibacterial master batch is more than 0.1g, the sterilizing rate of escherichia coli and staphylococcus aureus reaches 99.9%, and a good antibacterial effect can be achieved, when the adding amount of the instant type antibacterial master batch is far more than 0.1g, the antibacterial effect achieved is basically the same as that when the adding amount is slightly more than 0.1g, but in specific application, the dosage can be properly increased by adjusting the dosage, for example, hospital polluted clothes and the like according to the pollution degree of the washed clothes, the dosage of different washing machines is different in capacity, rotating speed and power, and the dosage of the antibacterial master batch is different. In the embodiment, when clothes are washed, the addition amount of the instant antibacterial master batch is between 0.1g and 1g, so that the antibacterial fabric has a good antibacterial effect and can save resources. In specific application, the usage amount of the instant antibacterial master batch can be properly increased according to the degree of clothes pollution.
The preparation method of the guanidine salt polymer/polyethylene glycol composite antibacterial agent comprises the steps of preparing polyethylene glycol which contains a large amount of hydroxyl groups and has good water solubility, preferably selecting polyethylene glycol with the molecular weight of 600-2000, preparing polyethylene glycol with the molecular weight of 60000 in a comparative example 12, wherein the polyethylene glycol has the advantages of large molecular weight, low water solubility and relatively poor compatibility with guanidine salt polymers, and the instant antibacterial master batch prepared with the molecular weight of 60000 has the disadvantages of low dissolution speed, poor water solubility caused by high molecular weight polyethylene glycol, low interaction between the antibacterial agent and clothes and low sterilization rate, so that after washing of a washing machine in a comparative example 48, a small amount of undissolved solid particles are found on the surface of clothes, and the sterilization rate is relatively low. The weight ratio of the guanidine salt polymer to the polyethylene glycol is 90: 10-99: 1, and the preferable weight ratio is 95: 5-99: 1.
The preparation method comprises the steps of preparing a guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent, wherein the proportion of the zinc-loaded antibacterial agent in a comparative example 18 is too large, and when the water-soluble polyhexamethylene guanidine hydrochloride/polyethylene glycol and the zinc-loaded antibacterial agent in the comparative example 21 are uniformly stirred, the formed composite antibacterial agent is poor in hydrophilicity and is not easy to be drawn into strips, so that the guanidine salt polymer/polyethylene glycol composite antibacterial agent and the zinc-loaded antibacterial agent are mixed in a weight ratio of 70: 30-95: 5, and the preferable weight ratio is 80: 20-90: 10.
The guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent is compounded with a surfactant, a builder, water, sodium carboxymethylcellulose and essence, and the comparative example 22 shows that when the proportion of the guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent is low, the antibacterial effect is slightly poor; when the ratio of the guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent is high, the brace granulation stability is poor, and the forming is difficult, so that the guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent has the weight ratio of 50-80%; the spherical antibacterial master batch prepared in the comparative examples 24-25 has the advantages that when the water content is too low, the mixed material is dried, the bracing strips are easy to break, the granules are easy to crack, when the water content is too high, the extruded mixture is in a flowing water shape, the extruded mixture cannot be formed into strips due to excessive dilution, the material is easy to stick to walls, and the production is difficult, so that the weight part ratio of the water is 10-30%; in the spherical antibacterial master batch prepared in the comparative example 26, the extrusion bracing rate is reduced when the content of sodium dodecyl benzene sulfonate is too low, the surface smoothness of the antibacterial master batch is reduced, the solubility of the antibacterial master batch is poor after the antibacterial master batch is stirred in water, and in the comparative example 27, when the content of sodium dodecyl benzene sulfonate is too high, more foam substances are separated out from the surface of the particles during extrusion granulation, which is not favorable for further coating treatment, so that the weight part ratio of the sodium dodecyl benzene sulfonate is 3-5%; compared with the optimized formula examples 25-26, the spherical antibacterial master batches prepared in the comparative examples 28-29 have the advantages that when the content of sodium carbonate is too high, the alkalinity of a washing system is easily too strong, and when the content is too low, the oily stains on polluted clothes are not easily removed, and the sterilization rate is influenced, so that the weight part ratio of the sodium carbonate is 1-2%; in the case of the spherical antibacterial master batches prepared in comparative examples 30 to 31 and examples 27 to 29, when the proportion of the hydroxymethyl cellulose is low, the viscosity is insufficient, the strip cannot be drawn, and when the proportion is too high, the viscosity is too high, and the strip is extruded and broken, so that the proportion of the weight part of the sodium carboxymethyl cellulose is 3 to 20 percent; the spherical antibacterial master batches prepared in comparative examples 32-33 and examples 30-31 have high essence content and too much smell, and have unobvious smell when the essence content is low, and the preferable content is 0.02-0.2%. If the guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent is compounded with the surfactant, the builder, water, sodium carboxymethylcellulose and the essence, the designed proportion is not proper, and the spherical antibacterial master batch cannot be successfully prepared.
Compared with the optimized formula examples 35-36, when the spherical antibacterial master batch prepared in the comparative example 38 is mixed with sodium stearate, the sodium stearate micro powder is too much, the powder is easy to fall off, the instant solubility is influenced, the sterilization efficiency is low during washing, in the comparative example 47, the sodium stearate micro powder is too little, the surface is sticky and easy to adhere, and after the mixture is placed for 2 months, the water retention rate of the particles is low, and undissolved granular substances exist in the washing time of the particles; the mesh number of sodium stearate is low excessively, and the granule is coarse, and the surface coating is incomplete, and the globular size of the antibiotic master batch of making is inhomogeneous, and the surface is coarse, and the mesh number of sodium stearate is too high, and the granule is fine, and in low-speed mixer, the surface can only adhere a small amount of sodium stearate, and the sodium stearate layer of cladding is too thin in the capsule machine, and the sodium stearate layer on antibiotic master batch surface cracks easily and falls the powder, follows from this, and the proportion of globular antibiotic granule and sodium stearate is 95: 5-99: 1, the particle size of the sodium stearate micro powder is preferably 300-500 meshes.
In summary, the embodiments of the present invention can at least achieve the following beneficial effects:
1. the invention provides a spherical particle-shaped quick-dissolving antibacterial master batch containing a guanidinium polymer, which is characterized in that a plurality of particles to dozens of particles are added during washing of a washing machine, and can be quickly dissolved to assist in washing away pathogenic microorganisms such as bacteria.
2. By compounding the guanidine salt polymer and the polyethylene glycol, the dissolving speed of the polyguanidine antibacterial master batch after being added into water can be improved, the polyguanidine antibacterial master batch is compatible with fabrics and other detergents, the permeability of the polyguanidine antibacterial master batch to the fabrics is improved, and a better antibacterial effect is achieved.
3. By compounding the guanidine salt polymer and the zinc-loaded antibacterial agent, the broad-spectrum antibacterial property can be improved, the antibacterial efficiency can be improved, the using amount can be reduced, and the washing and sterilizing time can be shortened.
4. Preferably, the zeolite zinc-loaded antibacterial agent and the guanidine salt polymer are compounded, and when the fabric is washed, the water-soluble guanidine salt polymer antibacterial agent and zinc ions are released simultaneously by utilizing the friction between the zeolite and the fabric, and the antibacterial agent and the microorganisms such as bacteria on the surface of the fabric are contacted repeatedly by cooperating with the antibacterial effect, so that a better antibacterial effect is achieved.
5. The guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent is blended with water, sodium dodecyl benzene sulfonate and sodium carboxymethyl cellulose according to different proportions, a large amount of experiments are carried out, an optimized relative proportion is obtained, the composite antibacterial agent can have good viscoelasticity and can be extruded into strips, the surfaces of the extruded strips are not easy to adhere to each other, further coating treatment can be carried out, if the proportion is not adjusted, the extruded strips can flow too fast to form a water flow shape and cannot be pulled into strips, or the extruded strips are dry and astringent, the surfaces of the extruded strips are not smooth and easy to break, and continuous production cannot be carried out.
6. The addition of sodium carbonate can enhance the detergency to oily stains and bacteria therein, improve oil removal, and improve sterilization efficiency.
7. Through a large amount of formula screening, a flaky sodium stearate coating agent is preferably selected, a layer of protective film can be formed on the surface of the prepared water-soluble spherical instant antibacterial master batch, so that the water-soluble spherical instant antibacterial master batch is not easy to absorb moisture and produce adhesion in the long-term keeping process, and the sodium stearate contains a long fatty chain, so that the antibacterial agent can be easily permeated into a stain-polluted fabric layer to play a role in quick sterilization and degerming when oily stains are washed.
8. Through a large number of experiments, the types of essences with fragrance and antibacterial effects are screened, so that the fragrance can be increased, natural antibacterial components can be added, and the synergistic antibacterial effect can be achieved.
Finally, it is to be noted that: the above description is only a preferred embodiment of the present invention, and is only used to illustrate the technical solutions of the present invention, and not to limit the protection scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (7)
1. The instant antibacterial master batch is characterized by being prepared by the following method:
s01, preparing a guanidine salt polymer/polyethylene glycol composite antibacterial agent by physically mixing a guanidine salt polymer and polyethylene glycol according to a proportion, wherein the weight ratio of the guanidine salt polymer to the polyethylene glycol is 90: 10-99: 1;
s02, mixing the guanidine salt polymer/polyethylene glycol composite antibacterial agent with the zinc-loaded antibacterial agent in a weight ratio of 70: 30-95: 5;
s03, compounding the guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent prepared in S02 with a surfactant, a builder, water, sodium carboxymethylcellulose and essence, carrying out banburying kneading processing in a banburying kneading extrusion bracing granulator for more than 10 minutes to fully mix the components uniformly, and carrying out extrusion granulation to prepare uniform spherical antibacterial master batches, wherein the proportion of each component is as follows by weight percent:
guanidine salt polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent: 50 to 80 percent
Surfactant (b): 3 to 5 percent
Builder: 1 to 2 percent
Water: 10 to 30 percent
Sodium carboxymethylcellulose: 3 to 20 percent
Essence: 0.02-0.2%;
the molecular weight of the polyethylene glycol is 600-2000;
the guanidine salt polymer is polyhexamethylene guanidine hydrochloride;
the zinc-carrying antibacterial agent is an antibacterial agent with zinc ions as a main antibacterial component, the carrier is 4A zeolite, 5A zeolite and natural zeolite, and the zinc ion content is 30% by weight;
s04, performing primary physical mixing on the uncoated spherical antibacterial master batch prepared in the S03 and the flaky sodium stearate micro powder to coat a layer of sodium stearate micro powder on the surface of the spherical antibacterial master batch, immediately performing rotary coating treatment by using a coating machine, and blowing hot air to ensure that the spherical antibacterial master batch is uniformly and compactly coated on the surface of the spherical antibacterial master batch after the sodium stearate is softened to prepare the instant antibacterial master batch, wherein the ratio of the spherical antibacterial particles to the sodium stearate is 95: 5-99: 1.
2. the instant antibacterial masterbatch according to claim 1,
the sodium stearate micro powder is flaky and has a particle size of 300-500 meshes;
the essence is at least one of tea tree oil, oleum Menthae Dementholatum, ginger oil, vanillin, thymol, and cinnamaldehyde.
3. The instant antibacterial masterbatch according to claim 2, wherein the surfactant is at least one of sodium dodecylbenzene sulfonate, sodium lauryl sulfate, and sodium fatty alcohol-polyoxyethylene ether sulfate.
4. The instant antimicrobial concentrate of claim 3, wherein the builder is sodium carbonate and/or potassium carbonate.
5. The fast-dissolving antimicrobial master batch according to any one of claims 1 to 4, wherein the guanidine salt polymer, the polyethylene glycol, and the zinc-loaded antimicrobial agent are mixed in a ratio such that the temperature of the mixture does not exceed 40 ℃.
6. The preparation method of the instant antibacterial masterbatch according to any one of claims 1 to 5, wherein the components comprising the guanidinium polymer/polyethylene glycol/zinc-loaded antibacterial agent three-component composite antibacterial agent, water, surfactant, builder, sodium carboxymethylcellulose and essence are uniformly mixed according to the sequence and content of claim 1, and then are subjected to banburying kneading processing by a banburying kneading extrusion strand granulator, and are subjected to extrusion granulation to prepare the uniform spherical antibacterial masterbatch.
7. The method of claim 6, wherein the uncoated spherical antimicrobial master batch is physically mixed with the flaky sodium stearate micro powder immediately, and then the surface of the spherical antimicrobial master batch is coated with a layer of sodium stearate micro powder, and then the spherical antimicrobial master batch is coated immediately by a coating machine, and hot air is blown into the spherical antimicrobial master batch for rotary coating, so that the uncoated spherical antimicrobial master batch is uniformly and densely coated after the sodium stearate is softened, and the instant antimicrobial master batch is prepared.
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| CN111733027B (en) * | 2020-07-08 | 2022-03-11 | 青岛拜士特新材料有限公司 | Instant washing antibacterial master batch and preparation method thereof |
| CN111690469B (en) * | 2020-07-08 | 2022-03-11 | 青岛拜士特新材料有限公司 | Degerming washing powder containing zinc pyrithione antibacterial agent and preparation method thereof |
| CN111733021B (en) * | 2020-07-08 | 2022-03-29 | 青岛拜士特新材料有限公司 | Sterilizing washing powder containing PCMX and preparation method thereof |
| KR102564030B1 (en) * | 2021-03-12 | 2023-08-04 | 도레이첨단소재 주식회사 | Method of preparing insect repellent materbatch for non-woven fabric, insect repellent materbatch for non-woven fabric made according to the method, non-woven fabric including the materbatch, and article including the non-woven fabric |
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