KR20200073750A - Method for preparing antibacterial super absorbent polymer - Google Patents

Abstract

The present invention relates to a method for preparing an antibacterial super absorbent resin capable of providing an enhanced antibacterial effect without any decline in basic absorption performance, preventing odor-causing problems caused by the growth of bacteria, significantly reducing dust generated during a preparation process, and improving anti-caking efficiency. The method comprises the steps of: spraying and mixing to the super absorbent resin an antibacterial agent hydrolysis solution, which contains 0.3 to 1.2 parts by weight of an antibacterial agent, 0.1 to 1.5 parts by weight of citric acid, and 0.5 to 5 parts by weight of water based on 100 parts by weight of a super absorbent resin including: base resin powder containing a crosslinking polymer of a water-soluble ethylene-based unsaturated monomer having an acidic group at least partially neutralized; and a surface crosslinking layer formed on the base resin powder and further crosslinked by the medium of a non-epoxy-based surface crosslinking agent.

Description

Manufacturing method of antimicrobial superabsorbent polymer {METHOD FOR PREPARING ANTIBACTERIAL SUPER ABSORBENT POLYMER}

The present invention relates to a method for producing an antimicrobial superabsorbent polymer having an excellent absorption performance and an ability to inhibit bacterial growth, with reduced dust generation and improved anti-caking efficiency.

Super Absorbent Polymer (SAP) is a synthetic polymer material that has the ability to absorb about 500 to 1,000 times its own weight of water having a hydrophilic (COOH, COO ^- Na ⁺ ) functional group. Each has a different name, such as SAM (Super Absorbency Material) and AGM (Absorbent Gel Material). The superabsorbent resin as described above began to be put into practical use as a sanitary tool, and now, in addition to hygiene products such as paper diapers for children, soil repair agents for horticulture, civil engineering, construction index materials, nursery sheets, and freshness retention agents in the food distribution field, and It is widely used as a material for poultice.

In most cases, these superabsorbent polymers are widely used in the field of sanitary materials such as diapers and sanitary napkins, and the odor as well as the feeling of wearing after absorbing moisture is an important problem in the superabsorbent polymer for diapers. In particular, secondary odors caused by bacterial growth in diapers for adults cause problems that cause discomfort to consumers. Therefore, it is necessary to develop a deodorant/antibacterial superabsorbent resin to suppress the odor caused by substances produced by metabolic activity of microorganisms present in urine and feces.

To solve this problem, attempts have been made to introduce various deodorizing or antibacterial functional ingredients into the superabsorbent polymer composition.

However, in the existing attempts to introduce such various deodorizing/antibacterial functional components, even if the deodorizing/antibacterial characteristics of the superabsorbent polymer are exhibited, there is a large amount of dust during the process, and the processability is poor, and there is a problem of reduced workability due to dust. In addition, in the case of the conventional method, the stability of the super absorbent polymer is lowered, and the functional component itself is too expensive, and thus, the unit cost of the super absorbent polymer composition is too high.

Accordingly, development of a superabsorbent polymer that exhibits improved antimicrobial and deodorant properties and satisfies both stability and fairness as well as improved antibacterial and deodorizing properties without deteriorating the basic absorbent performance of the superabsorbent polymer has been continuously requested.

Accordingly, the present invention can show an improved antibacterial effect without deteriorating the basic absorption performance, thereby preventing odor-causing problems caused by the growth of bacterial bacteria, and also dramatically reducing dust generated during the manufacturing process and improving anti-caking efficiency. An object of the present invention is to provide a method for producing an antimicrobial superabsorbent polymer that can be made.

According to an embodiment of the present invention, at least a portion of the base resin powder comprising a crosslinked polymer of a water-soluble ethylenically unsaturated monomer having a neutralized acidic group; And a surface crosslinking layer formed on the base resin powder and additionally crosslinked through a non-epoxy watch surface crosslinking agent; based on 100 parts by weight of the super absorbent polymer, 0.3 to 1.2 parts by weight of the antibacterial agent, and 0.1 to 1.5 parts by weight of citric acid. Provides a method for producing an antimicrobial superabsorbent polymer, comprising the steps of spraying and mixing the superabsorbent resin with an aqueous solution of an antibacterial agent containing 0.5 to 5 parts by weight of water.

Hereinafter, a super absorbent polymer according to a specific embodiment of the present invention and a method of manufacturing the same will be described in more detail. However, this is provided as an example of the invention, and the scope of rights of the invention is not limited thereby, and it is obvious to those skilled in the art that various modifications to the embodiments are possible within the scope of the invention.

Additionally, unless otherwise stated throughout this specification, "comprising" or "containing" refers to the inclusion of any component (or component) without particular limitation, and the addition of another component (or component). It cannot be interpreted as being excluded.

Method of manufacturing an antimicrobial superabsorbent polymer according to an embodiment of the invention,

A base resin powder comprising a crosslinked polymer of a water-soluble ethylenically unsaturated monomer having an acidic group at least partially neutralized; And a surface crosslinking layer formed on the base resin powder and additionally crosslinked through a non-epoxy watch surface crosslinking agent; based on 100 parts by weight of the super absorbent polymer, 0.3 to 1.2 parts by weight of the antibacterial agent, and 0.1 to 1.5 parts by weight of citric acid. And a step of spraying and mixing the superabsorbent resin with an aqueous solution of an antibacterial agent containing 0.5 to 5 parts by weight of water.

Conventional antimicrobial superabsorbent polymer was prepared by a method of dry mixing the antimicrobial agent after the production of the superabsorbent polymer. However, in this case, there was a problem that the amount of dust generated increased and the manufacturing efficiency of the super absorbent polymer decreased. Accordingly, it was required to add an additive to suppress dust generation and a mixing process therefor.

On the other hand, in the present invention, by spraying and mixing the surface-crosslinked superabsorbent polymer using a hydrolysis solution prepared by dissolving the antibacterial agent uniformly with citric acid, dust generation is reduced, anti-caking efficiency is increased, and In contrast to the presence of an antimicrobial agent only on the surface of the superabsorbent polymer during dry mixing, the antimicrobial agent is uniformly distributed on the surface and inside of the superabsorbent polymer to be produced. Accordingly, it is possible to effectively suppress odor-causing problems caused by bacterial growth in diapers, especially in adult diapers.

Specifically, the aqueous solution containing the antibacterial agent is prepared by homogeneously mixing 0.3 to 1.2 parts by weight of the antibacterial agent, 0.1 to 1.5 parts by weight of citric acid, and 0.5 to 5 parts by weight of water based on 100 parts by weight of the superabsorbent polymer.

The antimicrobial agent acts to inhibit the growth rate of various bacteria, in particular, the proliferation of bacterial bacteria that cause odor, Proteus mirabilis. The antibacterial agent can be used without particular limitation, as long as it is usually used in the production of an antibacterial superabsorbent polymer. However, in the case of a biocide-based antimicrobial agent that breaks down the cell wall of bacteria and kills bacteria, it can kill beneficial bacteria in addition to harmful bacteria. In the manufacturing method according to an embodiment of the present invention, it is necessary for the metabolism of bacterial bacteria such as Proteus mirabilis. Ethylenediamine-N,N,N',N'-tetraacetic acid (EDTA) or a salt thereof, which inhibits the proliferation by inhibiting the metabolism of bacterial bacteria by chelating the polyvalent metals, can be used.

Specific examples include EDTA, EDTA 2Na (ethylenediamine-N,N,N',N'tetraacetic acid, disodium salt), dihydrate EDTA 3Na (ethylenediamine-N,N,N',N'-tetraacetic acid, 3 Sodium salt, trihydrate), EDTA 4Na (ethylenediamine-N,N,N',N'-tetraacetic acid, tetrasodium salt), tetrahydrate EDTA 2K ethylenediamine-N,N,N',N'-tetraacetic acid , Dipotassium salt), dihydrate EDTA 2Li (ethylenediamine N,N,N',N'-tetraacetic acid, iridium salt), monohydrate EDTA (2NH4 ethylenediamine-N,N,N',N' tetraacetic acid , Diammonium salt), EDTA 3K (ethylenediamine-N,N,N',N'-tetraacetic acid, tripotassium salt), dihydrate Ba(II)-EDTA (ethylenediamine-N,N,N',N '-Tetraacetic acid, barium chelate), and the like, and any one or a mixture of two or more of them may be used.

In addition, when the antimicrobial agent is located not only on the surface of the antimicrobial superabsorbent polymer that is finally manufactured, but also on the inside, it can exhibit a better and uniform antibacterial effect. For this, it is required to have excellent solubility in water and completely dissolve in a water solution. Accordingly, among the above-mentioned antibacterial agents, EDTA or alkali metal salts having excellent solubility in water and having safety as an antibacterial agent may be used, and more specifically, alkali metal salts of EDTA or EDTA-4Na may be used. The EDTA-4Na has a particularly good deodorizing effect on the removal of the most critical NH ₃ among various odors of urine.

When preparing a superabsorbent polymer composition having antimicrobial properties, the higher the content of the antimicrobial agent, the better, but if other materials other than the superabsorbent polymer are added, physical properties may be deteriorated. In addition, antimicrobial agents added for antimicrobial activity may be a direct factor that causes fines. Accordingly, it is preferable to optimize the content of the antibacterial agent in consideration of the content of citric acid and water contained in the hydrolysis solution. Specifically, the antimicrobial agent may be included in the aqueous solution in an amount corresponding to 0.3 to 1.2 parts by weight based on 100 parts by weight of the super absorbent polymer. If the content of the antimicrobial agent is less than 0.3 parts by weight, it is difficult to obtain a sufficient antibacterial effect, and when it exceeds 1.2 parts by weight, the physical properties of the antimicrobial superabsorbent polymer may be deteriorated or dust generation may increase. More specifically, it is 0.4 parts by weight or more, or 0.5 parts by weight or more, and 1.1 parts by weight or less, or 1 part by weight or less based on 100 parts by weight of the super absorbent polymer.

On the other hand, despite the action of inhibiting the growth of bacterial bacteria in the antimicrobial agent, some bacteria may remain, and in this case, ammonia may be generated due to the remaining bacteria and odor may occur. These odors can be removed by the citric acid. As a result, the antimicrobial superabsorbent polymer prepared according to one embodiment of the present invention can exhibit better deodorizing and antibacterial properties by synergistic effect of two components, an antibacterial agent and citric acid.

The citric acid is distributed on the inside and the surface of the antimicrobial superabsorbent polymer particles, and generates an acid site. In addition to physically adsorbing bacteria and malodorous components at such an acidic point, the hydrogen cation (H ⁺ ) of the acidic point can be combined with the malodorous component to form an ammonium salt, thereby effectively removing malodorous components. In addition, the citric acid may exhibit an anti-caking effect that does not cause caking when mixed with a super absorbent polymer by controlling the particle size.

The citric acid has a higher human safety than other organic acids such as oxalic acid, fumaric acid, or maleic acid, and has more COOH, so it can exhibit a better effect on deodorizing ammonia, and may exhibit a better effect in terms of anti-caking. . In addition, citric acid may exhibit excellent effects in deodorizing ammonia odor caused by bacterial growth when used in combination with EDTA or a salt thereof, especially EDTA-4Na, among antibacterial agents.

However, the citric acid has a high solubility, and the amount of the superabsorbent polymer is reduced by the amount to be added, so there is a limit to the amount of input. Specifically, the citric acid may be added in an amount of 0.1 to 1.5 parts by weight based on 100 parts by weight of the super absorbent polymer. If the content of citric acid is less than 0.1 parts by weight, the improvement effect according to the introduction of citric acid is insignificant, and if it exceeds 1.5 parts by weight, there is a fear that the physical properties of the antimicrobial superabsorbent polymer are deteriorated. More specifically, 0.3 parts by weight or more, or 0.5 parts by weight or more, and 1.2 parts by weight or less, or 1 part by weight or less based on 100 parts by weight of the superabsorbent polymer may be included.

In addition, water may be added in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the super absorbent polymer. If the content of water is less than 0.5 parts by weight, the penetration of the superabsorbent polymer is not easy due to the increase in the concentration of the hydrolysis solution, and if it exceeds 5 parts by weight, there is a fear that fairness may be reduced due to the caking phenomenon during hydrolysis. More specifically, it is 0.7 parts by weight or more, or 1 part by weight or more, and 3.5 parts by weight or less, or 3 parts by weight or less based on 100 parts by weight of the super absorbent polymer.

The hydrolysis solution containing the antimicrobial agent is prepared by dissolving the above-mentioned antimicrobial agent and citric acid in water. At this time, for homogeneous mixing of the antimicrobial agent and citric acid and complete dissolution in water, a process such as agitation may optionally be further performed.

The wet mixing process for the superabsorbent resin of the hydrolysis solution containing the antibacterial agent may be performed through spraying. When mixed by spraying, it is possible to treat the superabsorbent polymer with a homogeneous thickness for the superabsorbent polymer.

The spraying process may be performed at a temperature condition of 50 to 70°C. When performed within the above-described temperature range, homogeneous mixing is possible without deteriorating the physical properties of the super absorbent polymer. If the temperature is less than 50°C, there is a fear of impairing fairness, and if it exceeds 70°C, as the water evaporation rate increases, it is difficult to uniformly apply the hydrolysis solution, and there is a risk of decreasing mixing efficiency. More specifically, it can be carried out at 60 to 70 ℃.

In addition, the spraying process may be performed while stirring the super absorbent polymer at 200 to 600 rpm. By stirring the superabsorbent polymer, a hydrolysis solution containing an antibacterial agent can be homogeneously surface-treated with respect to the superabsorbent polymer by stirring. When the stirring speed is less than 200 rpm, the improvement effect due to stirring is negligible, and when it exceeds 600 rpm, there is a fear that the superabsorbent particles are broken due to mechanical friction.

In addition, after the spraying process, a mixing process of superabsorbent polymers surface-treated with an antibacterial agent-containing hydrolysis solution is performed.

Through the mixing process, the antimicrobial agent may be uniformly distributed not only on the superabsorbent polymer surface but also inside. The mixing process may be performed according to a conventional method, and may be performed for 10 to 30 minutes in consideration of the uniform distribution of antibacterial agents.

On the other hand, in the method of manufacturing an antimicrobial superabsorbent polymer according to an embodiment of the present invention, the superabsorbent polymer mixed with the aqueous solution containing the antibacterial agent is in powder form, except that it is surface crosslinked with a non-epoxy surface crosslinking agent, in powder form It can be provided according to a generally known method.

Specifically, the superabsorbent polymer comprises: 1a) crosslinking polymerization of a water-soluble ethylenically unsaturated monomer having an acidic group at least partially neutralized in the presence of an internal crosslinking agent to form a hydrogel polymer comprising a crosslinked polymer; 1b) drying, grinding and classifying the hydrogel polymer to form a base resin powder; And 1c) surface crosslinking the base resin powder with a surface crosslinking solution containing a non-epoxy watch surface crosslinking agent. Accordingly, the method for manufacturing an antimicrobial superabsorbent polymer according to an embodiment of the present invention may further include a process for manufacturing the superabsorbent polymer described above.

In addition, the superabsorbent polymer can further increase the effectiveness of the final antibacterial superabsorbent polymer produced by allowing specific material properties to be realized through control of the amount of reactants, reaction conditions, and the like. Specifically, the superabsorbent polymer used in the manufacturing method according to an embodiment of the present invention has a gel permeability under pressure (GPUP) of 19 수학 10E ^-13 to 20 결정 determined according to Equation 1 below. 10E ^-13 m ² .

GPUP is usually a parameter indicating the liquid permeability of the superabsorbent polymer, and by indicating the GPUP in the above-described range, it is possible to improve the liquid permeability of the final antibacterial superabsorbent polymer.

In addition, the super absorbent polymer has a particle size distribution measured using Sieve (20, 30, 50, 100, 325 Mesh standard Sieve) of 20 mesh or more and less than 30 mesh, 30 mesh or more and less than 50 mesh, 50 mesh or more and 100 mesh or more Less than, and 100 mesh or more particle content may be 5 to 10%, 50 to 80%, 15 to 30% and 0.1 to 5%, respectively. As it has such a particle size distribution, it is possible not only to improve the processability and workability by reducing the amount of dust generated, but also to increase the content ratio of the antimicrobial superabsorbent polymer powder having an average particle size of 150 to 850 μm more than before.

The water-soluble ethylenically unsaturated monomers are acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethane sulfonic acid, 2-methacryloylethanesulfonic acid, 2-(meth)acryloyl Propanesulfonic acid, or anionic monomers of 2-(meth)acrylamide-2-methyl propane sulfonic acid and salts thereof; (Meth)acrylamide, N-substituted (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate or polyethylene glycol ( Nonionic hydrophilic monomers of meth)acrylate; And an amino group-containing unsaturated monomer of (N,N)-dimethylaminoethyl (meth)acrylate or (N,N)-dimethylaminopropyl (meth)acrylamide and a quaternized product thereof. It can contain. Among these, an alkali metal salt such as acrylic acid or a salt thereof, for example, acrylic acid in which at least a part of acrylic acid is neutralized and/or a sodium salt thereof may be used, and the use of such monomers leads to the preparation of a super absorbent polymer having better physical properties Becomes possible. When using the acrylic acid and its alkali metal salt as a monomer, it can be used by neutralizing at least a part of acrylic acid with a basic compound such as caustic soda (NaOH).

In addition, as an internal crosslinking agent for crosslinking polymerization of these monomers, bis(meth)acrylamide having 8 to 12 carbon atoms, poly(meth)acrylate of a polyol having 2 to 10 carbon atoms and poly(meth) of a polyol having 2 to 10 carbon atoms One or more selected from the group consisting of allyl ethers can be used. More specifically, the internal crosslinking agent is one selected from the group consisting of polyethylene glycol di(meth)acrylate, polypropyleneoxy di(meth)acrylate, glycerin diacrylate, glycerin triacrylate, and trimethyrol triacrylate. The poly(meth)acrylate of the above polyol can be used suitably. Among these, by using an internal crosslinking agent such as the polyethylene glycol di(meth)acrylate, an internal crosslinking structure is optimized and a base resin powder having a high gel strength, etc. can be obtained. An absorbent resin can be obtained more appropriately.

In addition, 0.005 to 0.1 mol, or 0.005 to 0.1 mol, or 0.005 to 0.05 mol (or more than 0.3 parts by weight compared to 100 parts by weight of acrylic acid), or 0.3 to 0.6 parts by weight). Depending on the content range of the internal crosslinking agent, a base resin powder having a high gel strength before surface crosslinking can be appropriately obtained, and a superabsorbent polymer having excellent physical properties can be obtained through the method of one embodiment.

In addition, after crosslinking and polymerizing the monomer using the internal crosslinking agent, a base resin powder may be obtained through processes such as drying, pulverization, and classification. Through these pulverization and classification processes, the base resin powder and It is appropriate that the resulting superabsorbent polymer is prepared and provided to have a particle diameter of 150 to 850 μm. More specifically, at least 95% by weight or more of the base resin powder and the superabsorbent polymer obtained therefrom has a particle diameter of 150 to 850㎛, and a fine powder having a particle diameter of less than 150㎛ is less than 3% by weight, or less than 1.5% by weight Can be as

In addition, the concentration of the water-soluble ethylenically unsaturated monomer may be 20 to 60% by weight, or 40 to 50% by weight relative to the total monomer composition including each raw material and solvent described above, polymerization time and reaction conditions, etc. It can be adjusted to an appropriate concentration.

In addition, the polymerization initiator is not particularly limited as long as it is generally used for the production of super absorbent polymers. Specifically, the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator according to UV irradiation depending on the polymerization method. However, even with the photopolymerization method, since a certain amount of heat is generated by irradiation with ultraviolet rays or the like and a certain amount of heat is generated as the polymerization reaction that is an exothermic reaction proceeds, a thermal polymerization initiator may be additionally included.

The photopolymerization initiator may be included in an amount of 0.01 to 1.0 parts by weight based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer. If the content of the photopolymerization initiator is too low, the polymerization rate may be slow, and if the content of the photopolymerization initiator is too high, the molecular weight of the super absorbent polymer may be small and the properties may be uneven.

The thermal polymerization initiator may be included in 0.001 to 0.5 parts by weight based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer. When the content of the thermal polymerization initiator is too low, the additional thermal polymerization hardly occurs, so the effect of adding the thermal polymerization initiator may be negligible. If the content of the thermal polymerization initiator is too high, the molecular weight of the super absorbent polymer may be small and the properties may be uneven. have.

In addition, the monomer composition may further include additives such as a thickener, a plasticizer, a preservative stabilizer, and an antioxidant, if necessary.

Raw materials such as the above-described water-soluble ethylenically unsaturated monomer, photopolymerization initiator, thermal polymerization initiator, internal crosslinking agent and additives may be prepared in the form of a solution of a monomer composition dissolved in a solvent.

The solvent that can be used at this time can be used without limitation of its configuration as long as it can dissolve the aforementioned components, for example, water, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, propylene Glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl amyl ketone, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl It can be used in combination of one or more selected from ether, toluene, xylene, butyrolactone, carbitol, methyl cellosolve acetate and N,N-dimethylacetamide.

The solvent may be included in the remaining amount excluding the above-mentioned components with respect to the total content of the monomer composition.

On the other hand, if the method of forming a hydrogel polymer by thermal polymerization or photopolymerization of such a monomer composition is also a commonly used polymerization method, there is no particular limitation on the configuration.

Specifically, the polymerization method is largely divided into thermal polymerization and photopolymerization according to the polymerization energy source, and in general, when performing thermal polymerization, it can be carried out in a reactor having a stirring axis such as a kneader, and when performing photopolymerization, it is movable Although it may be carried out in a reactor equipped with a conveyor belt, the polymerization method described above is an example, and the present invention is not limited to the polymerization method described above.

Subsequently, the obtained hydrogel polymer may be dried, pulverized, and/or classified to obtain a base resin powder according to a well-known method, and thereafter, a superabsorbent polymer of one embodiment may be prepared through a surface crosslinking process. have.

As the surface crosslinking agent used in the surface crosslinking process, a non-epoxy watch compound may be used. In the case of the conventional epoxy-based surface crosslinking agent, there was a problem that is harmful to the human body, such as generating carcinogens by remaining in the diaper. On the other hand, in the present invention, the above-mentioned problems are solved by using a non-epoxy watch compound, and at the same time, human body safety and surface crosslinking properties of the superabsorbent polymer to be produced can be further improved.

Specifically, the non-epoxy watch crosslinking agent is a polyhydric alcohol compound having 3 to 20 carbon atoms, such as 1,3-propanediol (1,3-Propanediol), polyamine compound, oxazoline-based compound, mono-, di- and poly-oxa One or more selected from the group consisting of a zolidinone compound, a cyclic urea compound, a polyvalent metal salt, and an alkylene carbonate compound having 2 to 5 carbon atoms can be used.

In addition, in the surface crosslinking solution, the surface crosslinking agent may be included in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the base resin powder. When the content of the surface crosslinking agent is less than 0.01 part by weight, it is difficult to form a sufficient surface crosslinking layer, and when it exceeds 5 parts by weight, the surface crosslinking layer is formed too thick, and there is a fear that the physical properties of the super absorbent polymer may be deteriorated. More specifically, the surface cross-linking agent is 0.1 part by weight or more, or 0.3 part by weight or more, and 1 part by weight or less, or 0.5 part by weight or less based on 100 parts by weight of the base resin powder.

In addition, the surface crosslinking solution may further include water and/or methanol as a medium.

The surface crosslinking step may be performed by heating reaction at a temperature of 140 to 200° C. for 5 minutes to 80 minutes. Preferably, 5 minutes to 80 minutes, or 10 minutes to 70 minutes, or 20 minutes to 65 minutes at a maximum reaction temperature of 140°C to 200°C or 150°C to 190°C for the base resin powder to which the surface crosslinking solution is added The heat treatment may be performed for a minute to proceed by a method of progressing a surface crosslinking reaction.

The heating means for the surface crosslinking reaction is not particularly limited. The heating medium may be supplied or a heat source may be directly supplied to heat. At this time, as the kind of heat medium that can be used, heated fluid such as steam, hot air, and hot oil may be used, but the present invention is not limited thereto, and the temperature of the supplied heat medium means the means of the heat medium, the rate of temperature increase and the target temperature of temperature increase. It can be appropriately selected in consideration. On the other hand, the heat source supplied directly may include a heating method through electricity and a gas, but is not limited to the above-described example.

The antimicrobial superabsorbent polymer prepared according to the above-described production method includes: a base resin powder comprising a crosslinked polymer of a water-soluble ethylenically unsaturated monomer having an acidic group at least partially neutralized; And a surface crosslinking layer formed on the base resin powder and additionally crosslinked through a non-epoxy watch surface crosslinking agent; and a superabsorbent polymer comprising an antibacterial agent and citric acid homogeneously distributed on the surface and inside the superabsorbent polymer. Includes.

Accordingly, the antimicrobial superabsorbent polymer can exhibit excellent antimicrobial and deodorizing effects through significantly improved bacterial growth inhibition, along with excellent absorption performance and liquid permeability, and can also exhibit reduced dust number and increased anti-caking rate. .

Specifically, the antimicrobial superabsorbent polymer has a gel permeability under pressure (GPUP) of 19 to 20 식 10E ^-13 m ² calculated according to Equation 1 below. GPUP is usually a parameter indicating the liquid permeability of the super absorbent polymer, and by showing the GPUP in the above-described range, it can exhibit excellent liquid permeability in the diaper.

[Equation 1]

GPUP(ⅹ10E ^-13 m ² )=(Ｋⅹηⅹ10/10000)ⅹ1000000

In Equation 1, η is 0.909% by weight of sodium chloride, the viscosity is 0.0009 Pa·s,

K is a value calculated according to the following equation (2)

[Equation 2]

Ｋ(ⅹ10E ^-7 cm ³ s/g)=(Fgⅹt/ρⅹAⅹP)

F _g is the physiological saline weight (g/s) passed through the gel per hour,

t(cm) is the gel thickness ((t1-t0)/10)

ρ is a density of 0.9% by weight sodium chloride 1 g/cm ³ ,

A is the cylinder area used for GPUP measurement is 28.27 cm ² ,

P is the hydrostatic pressure 4920 dyn/cm ² ,

The to and t1 are 2.1 kPa (0.3 psi) of 1.8 kPa (0.3 psi) by adding a superabsorbent polymer 1.8±0.05 g into a cylinder equipped with a piston that gives a load of 0.9 kPa (0.3 psi) When absorbed for 1 hour under the load of ), and the physiological saline composed of 0.9% by weight of sodium chloride aqueous solution is flowed, the weight of the physiological saline passed for 300 seconds from the time when the first drop passes through the swollen gel, t0 Is the height of the piston before the experiment, and t1 is the height of the piston after passing through physiological saline for 300 seconds.

In addition, the antimicrobial superabsorbent polymer may have a centrifugal water retention capacity (CRC) of 25 to 30 g/g, or 27 to 28 g/g. As such, the antimicrobial superabsorbent polymer prepared by the method of one embodiment may exhibit excellent absorbency under no pressure.

The centrifugal water retention capacity (CRC) for the physiological saline can be measured according to the EDANA method WSP 242.3. Specifically, after absorbing the antimicrobial superabsorbent resin into the physiological saline for 30 minutes, the following equation 3 Can be calculated by:

[Equation 3]

CRC(g/g) = {[W ₂ (g)-W ₁ (g)-W ₀ (g)]/W ₀ (g)}

In Equation 3,

W ₀ (g) is the initial weight (g) of the antimicrobial superabsorbent polymer, and W ₁ (g) does not use an antimicrobial superabsorbent polymer and is absorbed by immersion in physiological saline for 30 minutes, followed by centrifugation. The device weight was measured after dehydration at 250G for 3 minutes, and W ₂ (g) was absorbed by immersing the antibacterial superabsorbent resin in physiological saline at room temperature for 30 minutes, and then dehydrating at 250G for 3 minutes. , It is the weight of the device measured including the antimicrobial superabsorbent resin.

In addition, the antimicrobial superabsorbent polymer may have a pressure absorption capacity (AUP) of 20 to 25 g/g, or 20 to 22 g/g. As such, the antimicrobial superabsorbent polymer can exhibit excellent absorbency even under pressure.

This pressure absorbing capacity (AUP) can be calculated according to Equation 4 below after absorbing the antimicrobial superabsorbent resin into physiological saline under a pressure of 0.7 psi over 1 hour:

[Equation 4]

AUP(g/g) = [W ₄ (g)-W ₃ (g)]/ W ₀ (g)

In Equation 4,

W ₀ (g) is the initial weight of the antimicrobial superabsorbent polymer (g), W ₃ (g) is the sum of the weight of the antimicrobial superabsorbent polymer and the weight of the device capable of applying a load to the antimicrobial superabsorbent polymer, W ₄ (g) is the sum of the weight of the antimicrobial superabsorbent polymer and the weight of the device capable of applying a load to the antimicrobial superabsorbent polymer after absorbing physiological saline in the antimicrobial superabsorbent polymer for 1 hour under a load (0.7 psi). to be.

As such, the antimicrobial superabsorbent polymer can exhibit excellent absorption performance such as basic absorption power and absorption power under pressure.

In addition, the antimicrobial superabsorbent polymer may exhibit a high water content of 1.5% or more, and more specifically 1.5 to 5%.

In the present invention, the water content of the antimicrobial superabsorbent polymer is recorded by weighing the weight of the aluminum foil container and recording the weight (W0) by pouring the sample to about 5.0±0.0001g and pouring it into the container to record the weight. (W1), the container is put into an infrared moisture meter preheated to 140±2°C, and after 10 minutes, the container is taken out and immediately put into a desiccator, and after 10 minutes, the container in the desiccator is taken out and the weight is weighed (W2). Using the measured weight values W0, W1 and W2, the water content can be calculated according to Equation 5 below.

[Equation 5]

Water content (%) = (W1-W2)/(W1-W0) x 100

In addition, the antimicrobial superabsorbent polymer can suppress the growth of bacteria and reduce the generation of ammonia, thereby reducing the discomfort caused by odor compared to the conventional one. In particular, when EDTA or a salt thereof is included as an antibacterial agent, it can exhibit excellent proliferation inhibitory efficacy against Proteus mirabilis bacteria.

Specifically, Proteus mirabilis (ATCC29906) put 1 g of a sample of an antimicrobial superabsorbent polymer into 50 ml of artificial urine inoculated with 2,700 CFU/ml, mixed for 1 minute, and incubated at 35° C. for 12 hours to measure and calculate Log[CFU/ ml] is 6.2 or less, more specifically 5 to 6.15.

In addition, when manufacturing the antibacterial superabsorbent polymer according to the above manufacturing method, by using citric acid, it is possible to exhibit a high anti-caking efficiency of 90% or more and a low dust number of 1.1 or less.

Specifically, the anti-caking efficiency, 9cm diameter Petri-dish weight is recorded by weight (W1), Petri-dish sample 2±0.01g is uniformly sprayed, and the temperature is set to 40℃ and humidity 80%RH. After putting it in the constant temperature and humidity chamber for 10 minutes, take out the Petri-dish, turn it over on A4 paper and let it stand for 5 minutes, and after 5 minutes, weigh the sample (S1) and Petri-dish (S2) that fell on the floor. It can be calculated according to the following equation (6).

[Equation 6]

Anti-caking efficiency (%) = [S1/(S2-W1) + S1] ⅹ 100

In addition, the dust generation inhibitory effect, using Dustview II (manufactured by Paras GmbH) that can measure the dust of the antimicrobial superabsorbent polymer with a laser, the dust number in the SAP sample can be calculated according to the following equation (7).

[Equation 7]

Dust number = Max value + 30 sec. value

In Equation 7, Max value represents the maximum dust value, and 30 sec. The value is the value measured 30 seconds after reaching the maximum dust value.

As described above, the antimicrobial superabsorbent polymer produced by the manufacturing method according to one embodiment of the invention has excellent antimicrobial properties, and can maintain or improve basic physical properties such as water retention capacity and pressure absorbing capacity required by the superabsorbent polymer. In addition, the dust content generated in the manufacturing process is reduced, and the anti-caking efficiency can be improved.

Accordingly, according to another embodiment of the present invention, a hygiene product exhibiting excellent antibacterial and deodorizing efficacy may be provided, including the superabsorbent polymer prepared by the above-described manufacturing method and the same.

The hygiene article includes a disposable absorbent product, preferably may include a diaper, and may be a diaper for children or adults. In addition, in the case of the sanitary article, while maintaining basic absorption performance such as water retention capacity and pressure absorption capacity, the antibacterial and deodorizing properties described above are excellent, thereby improving the usability.

According to the present invention, an antimicrobial superabsorbent polymer that exhibits very improved antimicrobial properties against odor-causing bacteria in hygiene products such as diapers for adults and thus deodorant properties is produced without deteriorating basic absorbent performance such as water retention capacity and absorbency under pressure. Can be. In addition, the manufacturing method can greatly reduce the amount of dust generated during the production of a super absorbent polymer, which usually uses an antibacterial agent, and can significantly improve the anti-caking efficiency.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are only illustrative of the present invention and the scope of the present invention is not limited to the following examples.

Production Example: Preparation of super absorbent polymer

With respect to 100 parts by weight of acrylic acid monomer, 40.6 parts by weight of caustic soda (NaOH) and 131.2 parts by weight of water were mixed, and 0.16 parts by weight of sodium persulfate as a thermal polymerization initiator and diphenyl (2,4,6-) as a photopolymerization initiator were added to the mixture. A monomer composition was prepared by adding 0.008 parts by weight of trimethylbenzoyl)-phosphine oxide and 0.35 parts by weight of polyethylene glycol diacrylate as a crosslinking agent.

The internal temperature of the monomer composition is maintained at 80°C, and UV light is flowed at a flow rate of 243 kg/hr on a polymerization belt of a continuous belt polymerization reactor in which a UV irradiation device having an intensity of 10 mW is installed as a mercury UV lamp light source 1 Irradiation was performed for a minute, and then the polymerization reaction was performed in a light-free state for 2 minutes.

After the polymerization was completed, the gel type polymerization sheet was first cut using a shredder type cutter, and then coarsely pulverized through a meat chopper. After drying through a hot air dryer for 30 minutes at a temperature of 180 ℃, pulverized using a rotary mixer and classified to 150㎛ to 850㎛ to prepare a base resin.

After adding 0.45 parts by weight of 1,3-propanediol (1,3-Propanediol) to 100 parts by weight of the base resin, and uniformly mixing, a surface treatment reaction was performed at 180°C for 1 hour to obtain a super absorbent polymer.

As a result of measuring PSD according to the following method for the superabsorbent polymer prepared above, PSD, that is, 20 mesh or more and less than 30 mesh, 30 mesh or more and less than 50 mesh, 50 mesh or more and less than 100 mesh, and particles of more than 100 mesh The size distribution (20/30/50/100) was 8/69/22/1.

Devices and reagents

Electronic scale (precision: 0.01 g), Sieve Shaker, Sieve (20, 30, 50, 100, 325 Mesh standard Sieve), Pan Receiver and Cap, 250 ml Beaker

Test Methods

The Pan Receiver was placed at the bottom and stacked one after the other, Sieve with few meshes. 100 g of the sample was quantitatively weighed in a 250 ml Beaker, placed in the top Sieve, and the lid closed. This was fixed on a Sieve Shaker and shaken for 10 minutes. After shaking for 10 minutes, the samples remaining in each Sieve gold screen were collected and calibrated. At this time, care was taken not to leave the sample outside, and the measurement amplitude was 1.0 mm.

Calculation method

The remaining amount of each sieve was calculated by the following equation (8).

[Equation 8]

record

More than 20 mesh, 20 to 30 mesh, 30 to 50 mesh, 50 to 100 mesh, 100 to 325 mesh, and particles less than 325 mesh were measured, respectively.

At this time, the particle size was set to 2 digits after the decimal point, and the particle size of "below 325 Mesh" was rounded to an effective number and recorded in the Data Sheet.

In addition, gel permeability under pressure (GPUP) was measured in the following manner for the superabsorbent polymer prepared in the preparation example. As a result, it exhibited a gel permeability under pressure (GPUP) of about 19-20 ⅹ10 ^-13 m ² .

A 400 mesh wire mesh made of stainless steel was mounted on a cylindrical bottom of a plastic cylinder having an inner diameter of 60 mm. On top of that, a piston capable of uniformly giving a load of 2.1 kPa (0.3 psi) was slightly smaller than the outer diameter of 60 mm, and there was no gap with the inner wall of the cylinder, and the height was measured after being positioned unobstructed (t0). After uniformly applying the absorbent resin (approximately 1.8±0.05 g) to the cylinder and raising the piston, place a glass filter with a diameter of 90 mm and a thickness of 5 mm inside the petri dish having a diameter of 200 mm, and add physiological saline composed of 0.90% sodium chloride to the glass filter. It was put about 5mm higher from the top and absorbed for 1 hour under load. Thereafter, a physiological saline solution consisting of 0.9% by weight sodium chloride was flowed out, and the weight of the physiological saline solution passed for 300 seconds was measured after the first drop passed through the swollen gel (F _g ). After passing the physiological saline for 300 seconds, the height (t1) of the measuring device was measured, and GPUP was calculated according to Equation 1 below.

[Equation 1]

GPUP(ⅹ10E ^-13 m ² )=(Ｋⅹηⅹ10/10000)ⅹ1000000

In Equation 1, η is the viscosity of 0.9% by weight sodium chloride (~0.0009 [Pa·s]),

K is a value calculated according to the following equation (2)

[Equation 2]

Ｋ(ⅹ10E ^-7 cm ³ s/g)=(Fgⅹt/ρⅹAⅹP)

F _g is the physiological saline weight (g/s) passed through the gel per hour,

t(cm) is the gel thickness ((t1-t0)/10)

ρ is the density of 0.9% by weight sodium chloride (~1g/cm ³ ),

A is the cylinder area (28.27 cm ² ),

P is the hydrostatic pressure (4920 dyn/cm ² ).

<Preparation of antibacterial superabsorbent polymer>

Example 1

Based on 100 parts by weight of the superabsorbent polymer prepared in the preparation example, EDTA-4Na, citric acid and water were used in an amount shown in Table 1 below to prepare a hydrolysis solution, and the superabsorbent polymer was 60°C using a kitchen aid. , While stirring under the conditions of 200 rpm, sprayed with the aqueous solution prepared above, and mixed for 20 minutes to prepare an antibacterial superabsorbent polymer.

Example 2

An antimicrobial superabsorbent polymer was prepared in the same manner as in Example 1, except that water and citric acid in Example 1 were used in the contents shown in Table 1 below.

Comparative Example 1

EDTA-4Na was used in an amount shown in Table 1 below with respect to 100 parts by weight of the superabsorbent polymer prepared in the above Preparation Example, and dry mixed at 500 rpm for 5 minutes using a Ploughshare mixer to prepare an antibacterial superabsorbent polymer.

Comparative Example 2

Dry mixing was performed in the same manner as in Comparative Example 1, except that EDTA-4Na was used in the contents shown in Table 1 below, to prepare an antimicrobial superabsorbent polymer.

Comparative Examples 3 to 6

An antimicrobial superabsorbent polymer was prepared in the same manner as in Example 1, except that citric acid was not used in Example 1, and EDTA-4Na and water were used in amounts shown in Table 1 below.

Comparative Example 7

An antibacterial superabsorbent polymer was prepared in the same manner as in Example 2, except that citric acid was not used in Example 2, and EDTA-4Na was used in excess as described in Table 1 below.

Comparative Example 8

An antimicrobial superabsorbent polymer was prepared by performing the same method as in Example 1, except that only water without input of the antibacterial agent and citric acid was used in the contents shown in Table 1 below.

Comparative Example 9

An antimicrobial superabsorbent polymer was prepared in the same manner as in Example 2, except that the antimicrobial agent was not added in Example 2 and citric acid was added in excess as described in Table 1 below.

EDTA-4Na
(Parts by weight) water
(Parts by weight) Citric acid
(Parts by weight) Example 1 One One 0.5 Example 2 One 3 One Comparative Example 1 0.5 - - Comparative Example 2 One - - Comparative Example 3 0.5 One - Comparative Example 4 0.5 3 - Comparative Example 5 One One - Comparative Example 6 One 3 - Comparative Example 7 3 3 - Comparative Example 8 - 5 - Comparative Example 9 - 3 3

In Table 1, the content unit "parts by weight" of each component is based on 100 parts by weight of the super absorbent polymer.

Experimental Example

For the antimicrobial superabsorbent polymer prepared in Examples and Comparative Examples, GPUP, CRC, AUP, moisture content, anticaking efficiency, and dust number were measured in the following manner.

(1) Gel permeability under pressure (GPUP)

A 400 mesh wire mesh made of stainless steel was mounted on a cylindrical bottom of a plastic cylinder having an inner diameter of 60 mm. On top of that, a piston capable of uniformly adding a load of 2.1 kPa (0.3 psi) was slightly smaller than the outer diameter of 60 mm, without a gap with the inner wall of the cylinder, and the vertical movement was not disturbed and the height was measured (t0). After uniformly applying the absorbent resin (approximately 1.8±0.05 g) to the cylinder and raising the piston, place a glass filter with a diameter of 90 mm and a thickness of 5 mm inside the petri dish with a diameter of 200 mm, and filter the physiological saline composed of 0.90% by weight sodium chloride into a glass filter. It was put about 5mm high from the top side of and was absorbed for 1 hour under load. Thereafter, a physiological saline solution consisting of 0.9% by weight sodium chloride was flowed out, and the weight of the physiological saline solution passed for 300 seconds was measured after the first drop passed through the swollen gel (F _g ). After passing the saline for 300 seconds, the height (t1) of the measuring device was measured, and GPUP was measured according to the following equation.

[Equation 1]

GPUP(ⅹ10E ^-13 m ² )=(Ｋⅹηⅹ10/10000)ⅹ000000

In Equation 1, η is 0.909% by weight of sodium chloride, the viscosity is 0.0009 Pa·s,

K is a value calculated according to the following equation (2)

[Equation 2]

Ｋ(ⅹ10E ^-7 cm ³ s/g)=(Fgⅹt/ρⅹAⅹP)

F _g is the physiological saline weight (g/s) passed through the gel per hour,

t(cm) is the gel thickness ((t1-t0)/10)

ρ is a density of 0.9% by weight sodium chloride 1 g/cm ³ ,

A is a cylinder area of 28.27 cm ² ,

P is a hydrostatic pressure of 4920 dyn/cm ² .

(2) Centrifuge Retention Capacity (CRC)

The water retention capacity of each resin by the load-free absorption magnification was measured according to EDANA WSP 241.3.

Specifically, from the antimicrobial superabsorbent polymer obtained through Examples and Comparative Examples, resins classified with a sieve of #30-50 were obtained. After the resin W ₀ (g) (about 0.2 g) was uniformly put in a nonwoven fabric bag and sealed, it was immersed in physiological saline (0.9 wt%) at room temperature. After 30 minutes, the bag was drained for 3 minutes under the condition of 250G using a centrifuge, and the mass W ₂ (g) of the envelope was measured. Moreover, the mass W ₁ (g) at that time was measured after performing the same operation without using a resin. CRC (g/g) was calculated according to Equation 3 below using each mass obtained.

[Equation 3]

CRC (g/g) = {[W ₂ (g)-W ₁ (g)]/W ₀ (g)}-1

(4) Absorbency under pressure (AUP)

According to EDANA method WSP 242.3, the absorbency under pressure (AUP) was measured for the antimicrobial superabsorbent polymers prepared in Examples and Comparative Examples.

Specifically, a 400 mesh wire mesh made of stainless steel was mounted on a cylindrical bottom of a plastic having an inner diameter of 60 mm. Under conditions of normal temperature and humidity of 50%, the water absorbent resin W(g) (approximately 0.90 g) was uniformly spread on the wire mesh, and a piston capable of uniformly applying a load of 4.83 kPa (0.7 psi) on it was 60 mm in outer diameter. It is slightly smaller, has no gaps with the inner wall of the cylinder, and prevents vertical movement. At this time, the weight W _a (g) of the device was measured.

A glass filter having a diameter of 90 mm and a thickness of 5 mm was placed inside the petri dish having a diameter of 150 mm, and the physiological saline composed of 0.90% by weight sodium chloride was brought to the same level as the top surface of the glass filter. A sheet of filter paper having a diameter of 90 mm was placed thereon. The measuring device was mounted on a filter paper, and the liquid was absorbed for 1 hour under a load. After 1 hour, the measuring device was lifted, and the weight W _b (g) was measured.

Then, the pressure absorption capacity (g/g) was calculated according to the following Equation 4 from W _a and W _b .

[Equation 4]

AUP (g/g) = {W _b -W _a } / W

(5) Water content

The weight of the aluminum foil container was weighed and recorded (W0). The sample was floated to about 5.0±0.0001 g, poured into a container, and the total weight was weighed (W1). The container was placed in an infrared moisture meter preheated to 140±2°C, and after 10 minutes the container was taken out and immediately placed in a desiccator. After 10 minutes, the container in the desiccator was taken out and the weight was weighed to record the weight (W2). The water content was measured according to Equation 5 below using the measured weight values W0, W1, and W2.

[Equation 5]

Water content (%) = (W1-W2)/(W1-W0) x 100

(6) Anti-caking

Petri-dish weight of 9 cm in diameter was measured and recorded (W1). Sample 2±0.01g was uniformly sprayed onto Petri-dish, and placed in a constant temperature and humidity chamber set at a temperature of 40°C and a humidity of 80%RH, and allowed to stand for 10 minutes. After 10 minutes, the Petri-dish was taken out and turned over on A4 paper and left for 5 minutes. After 5 minutes, the weight of the sample dropped on the floor (S1) and the weight of the Petri-dish (S2) were accurately recorded. Anticaking efficiency (A/C efficiency) was calculated according to Equation 6 below using the measured values.

[Equation 6]

Anti-caking efficiency (%) = [S1/(S2-W1) + S1] Ⅹ 100

(7) Dust number

The dust value was analyzed using Dustview II (manufactured by Paras GmbH), which can measure the dust level of the antimicrobial superabsorbent polymer prepared in Examples and Comparative Examples with a laser.

The dust number was measured using the SAP sample prepared in the Example or Comparative Example of 30 g. Since the small particles and specific substances drop at a slower rate than the coarse grain, the dust number was calculated by Equation 7 below.

[Equation 7]

Dust number = Max value + 30 sec. value

In Equation 7, Max value represents the maximum dust value, and 30 sec. The value is the value measured 30 seconds after reaching the maximum dust value.

CRC
(g/g) AUP
(g/g) GPUP
(Ⅹ10E ^-13 m ² ) A/C efficiency
(%) Dust number Water content
(%) Example 1 27.4 20.6 19.1 90 1.1 1.68 Example 2 27.0 20.1 19.8 90 0.8 2.44 Comparative Example 1 28.5 19.7 19.8 20 6 0.64 Comparative Example 2 28.2 19.0 19.5 10 11 0.73 Comparative Example 3 28.2 21.0 20.1 90 0.9 1.75 Comparative Example 4 27.8 20.6 19.8 90 0.6 2.41 Comparative Example 5 27.9 20.9 19.5 90 One 1.79 Comparative Example 6 27.4 20.5 20.1 90 0.8 2.34 Comparative Example 7 27.2 18.1 19.0 90 1.2 2.28 Comparative Example 8 26.4 18.4 19.1 20 0.6 3.94 Comparative Example 9 27.1 18.2 19.1 20 1.1 2.34

As a result of the experiment, the antimicrobial superabsorbent polymers of Examples 1 and 2, and Comparative Examples 3 to 6, prepared through wet mixing of an aqueous solution containing an antimicrobial agent, were equivalent to those of Comparative Examples 1 and 2, prepared through dry mixing of an antimicrobial agent. While showing CRC, AUP, and GPUP above the level, the Hush rate increased, the dust number decreased significantly, and the anti-caking efficiency increased.

Test Example 2

Antibacterial properties were evaluated in the following manner, and the results are shown in Table 3 below.

Proteus mirabilis (ATCC29906) was added to 1 g of the sample of the antimicrobial superabsorbent polymer prepared in the above Examples or Comparative Examples in 50 ml of artificial urine inoculated with 2,700 CFU/ml, and mixed evenly by shaking for 1 minute. After incubation in an oven at 35° C. for 12 hours, well washed with 150 ml of brine to measure CFU (colony forming unit). It was commissioned and analyzed by the Korea Research Institute of Standards and Science (KSTR).

In addition, only the bacteria were inoculated into artificial urine without the introduction of antibacterial superabsorbent resin, and used as a control.

Incubation time (h) CFU/ml Log[CFU/ml] Control 0
(Initial inoculation bacteria) 2,700 3.43 12 5,200,000,000 9.72 Example 1 12 1,370,000 6.14 Example 2 12 1,350,000 6.13 Comparative Example 1 12 5,700,000 6.76 Comparative Example 2 12 3,000,000 6.48 Comparative Example 3 12 6,000,000 6.78 Comparative Example 4 12 4,800,000 6.68 Comparative Example 5 12 2,700,000 6.43 Comparative Example 6 12 2,300,000 6.36 Comparative Example 7 12 1,100,000 6.04 Comparative Example 8 12 4,100,000,000 9.61 Comparative Example 9 12 8,800,000 6.94

As a result of the experiment, Examples 1 and 2 and Comparative Examples 3 to 6 prepared through wet mixing showed better antimicrobial properties compared to Comparative Examples 1 and 2 prepared through dry mixing during the treatment of the antibacterial agent. From this, it can be seen that the wet mixing method during the treatment of the antibacterial agent exhibits a more excellent effect on improving the antibacterial property.

In addition, from the results of Comparative Examples 3 and 5, and Comparative Examples 4 and 6, it was confirmed that the antimicrobial properties improved as the amount of the antimicrobial agent increased, and also the results of Comparative Examples 3 and 4 and Comparative Examples 5 and 6 From it can be seen that as the water content in the hydrolysis solution increases, that is, as the concentration of the antimicrobial agent in the hydrolysis solution decreases, the antimicrobial improvement effect increases.

In addition, from the results of Comparative Examples 5 and 1, and Comparative Examples 6 and 2, when citric acid was added together during the treatment of the antibacterial agent, it was confirmed that it exhibited better antibacterial properties, and from the results of Examples 1 and 2, citric acid It can be seen that the antibacterial properties are further improved as the content is increased. However, in the absorption performance results of Table 2, Example 2, which has a high content of citric acid, shows relatively reduced absorption performance compared to Example 1, and citric acid is used to exhibit improved antimicrobial properties while maintaining excellent absorption performance and liquid permeability. It can be seen that the amount of input should be optimized.

Claims (11)

A base resin powder comprising a crosslinked polymer of a water-soluble ethylenically unsaturated monomer having an acidic group at least partially neutralized; And a surface crosslinking layer formed on the base resin powder and additionally crosslinked through a non-epoxy watch surface crosslinking agent; based on 100 parts by weight of the super absorbent polymer, 0.3 to 1.2 parts by weight of the antibacterial agent, and 0.1 to 1.5 parts by weight of citric acid. Part, and comprising the step of spraying, and mixing the superabsorbent resin, an antibacterial agent hydrolysis solution containing 0.5 to 5 parts by weight of water,
Method for producing antibacterial superabsorbent resin.
According to claim 1,
The antibacterial agent comprises ethylenediamine-N,N,N',N'-tetraacetic acid (EDTA) or a salt thereof, a method for producing an antimicrobial superabsorbent polymer.
According to claim 1,
The antibacterial agent comprises ethylenediamine-N,N,N',N'-tetraacetic acid, tetrasodium salt (EDTA-4Na), a method for producing an antimicrobial superabsorbent polymer.
According to claim 1,
The antimicrobial hydrolysis solution comprises 0.5 to 1 part by weight of an antibacterial agent, 0.5 to 1 part by weight of citric acid, and 1 to 3 parts by weight of water with respect to 100 parts by weight of a superabsorbent polymer.
According to claim 1,
The spraying is carried out at a temperature of 50 to 70 ℃, a method for producing an antimicrobial superabsorbent polymer.
According to claim 1,
The spray is performed while stirring the superabsorbent polymer under the conditions of 200 to 600rpm, a method for producing an antimicrobial superabsorbent polymer.
According to claim 1,
The mixing is carried out for 10 to 30 minutes, a method for producing an antimicrobial superabsorbent polymer.
According to claim 1,
The super absorbent polymer is
Crosslinking polymerization of a water-soluble ethylenically unsaturated monomer having an acidic group at least partially neutralized in the presence of an internal crosslinking agent to form a hydrogel polymer comprising a crosslinked polymer;
Drying, grinding and classifying the hydrogel polymer to form a base resin powder; And
Method for producing an antimicrobial superabsorbent polymer prepared by a method comprising the step of surface-crosslinking the base resin powder with a surface crosslinking solution containing a non-epoxy watch surface crosslinking agent.
The method of claim 8,
The non-epoxy watch surface crosslinking agent has a polyhydric alcohol compound having 3 to 20 carbon atoms, a polyamine compound, a halo epoxy compound and a condensation product thereof, an oxazoline-based compound, a mono-, di- and poly-oxazolidinone compound, a cyclic urea compound, a polyvalent Method of producing an antimicrobial superabsorbent polymer comprising at least one compound selected from the group consisting of a metal salt and an alkylene carbonate compound having 2 to 5 carbon atoms.
The method of claim 8,
The water-soluble ethylenically unsaturated monomers are acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethane sulfonic acid, 2-methacryloylethanesulfonic acid, 2-(meth)acryloyl Propanesulfonic acid, or anionic monomers of 2-(meth)acrylamide-2-methyl propane sulfonic acid and salts thereof; (Meth)acrylamide, N-substituted (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate or polyethylene glycol ( Nonionic hydrophilic containing monomers of meth)acrylates; And an amino group-containing unsaturated monomer of (N,N)-dimethylaminoethyl (meth)acrylate or (N,N)-dimethylaminopropyl (meth)acrylamide and a quaternary product thereof. A method for producing an antimicrobial superabsorbent polymer comprising:
According to claim 1,
The antimicrobial superabsorbent polymer is Proteus mirabilis (Proteus mirabilis) inhibits the growth of bacteria, antibacterial superabsorbent polymer production method.