Super absorbent polymer

Abstract

The present invention relates to a super absorbent polymer exhibiting improved absorption rate and absorption performance.

Description

superabsorbent resin

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2023-0165504, filed November 24, 2023, and U.S. Patent Application No. 18 / 922,670, filed October 22, 2024, the entire contents of which are incorporated herein by reference.

[0003] The present invention relates to a superabsorbent resin exhibiting improved absorption speed and absorption performance.

[0004] Super absorbent polymer (SAP) is a synthetic polymer material that can absorb 500 to 1,000 times its own weight in water. Different developers call it by different names, such as SAM (Super Absorbency Material) and AGM (Absorbent Gel Material). The above super absorbent polymer began to be put to practical use in products such as diapers and hygiene products, and is currently widely used as a soil conditioner for horticulture, a water-stopping material for civil engineering and construction, a sheet for nursery cultivation, and a freshness-preserving agent and material for steaming in the food distribution industry.

[0005] These superabsorbent polymers are widely used in sanitary products, such as diapers and sanitary napkins. Within these sanitary products, the superabsorbent polymers are typically dispersed within pulp. However, recent efforts to provide thinner sanitary products, such as diapers, are ongoing. As part of this effort, the development of so-called pulpless diapers, which contain reduced pulp content or even eliminate pulp altogether, is actively underway.

[0006] In this way, in the case of sanitary materials where the pulp content is reduced or no pulp is used, a relatively high proportion of superabsorbent resin is included, so superabsorbent resin particles are inevitably included in multiple layers within the sanitary material. In order for the entire superabsorbent resin particles included in multiple layers to more efficiently absorb a large amount of liquid such as urine, the superabsorbent resin needs to exhibit not only high absorption performance but also a fast absorption speed. Meanwhile, the most common method for improving such absorption properties is a method of forming a porous structure within the superabsorbent resin to increase the surface area of ​​the superabsorbent resin. In order to increase the surface area of ​​the superabsorbent resin, a method of forming a porous structure within the base resin powder by including a foaming agent in the monomer composition and performing crosslinking polymerization is generally adopted.

[0007] However, the use of a foaming agent has the disadvantage of lowering various properties of the superabsorbent resin, such as surface tension, permeability, or bulk density, and increasing the amount of fine particles generated. Accordingly, there is a continuous demand for the development of a technology that can improve the absorption properties of the superabsorbent resin without the use of a foaming agent.

[0008] Accordingly, there is a continuous demand for the development of technology that can manufacture superabsorbent polymers without generating fine particles to fundamentally solve these problems.

[0009] The present invention aims to provide a superabsorbent resin that can improve absorption speed and absorption performance such as water retention capacity and pressure absorption capacity by adjusting circularity and aspect ratio (A / R) to predetermined values, thereby enabling the resin to implement excellent quality when applied to an actual product.

[0010] In order to solve the above problem, the present invention,

[0011] As a polyacrylic acid (salt)-based superabsorbent resin,

[0012] The average value of circularity calculated by the following equation 1 for all particles is 0.90 or less, and the average value of aspect ratio (A / R), which means the ratio of the shortest diameter of the particle to the longest diameter of the particle, is 0.70 or more.

[0013] An absorbency under pressure (AUP) of 25 g / g or more as measured under 2.07 kPa (0.3 psi) in accordance with EDANA Act WSP 242.3;

[0014] We provide super absorbent resins:

[0015] [Formula 1]

[0016] Circularity = perimeter of CE particle / perimeter of actual particle

[0017] In the above equation 1,

[0018] The perimeter of a CE particle refers to the perimeter of a circle (Circle Equivalent) that has the same area as the 3D image of the 3D particle to be measured captured as a 2D image (CE Perimeter).

[0019] The actual particle perimeter refers to the actual perimeter length of the image captured as a 2D image of the 3D image of the 3D particle to be measured (Perimeter).

[0020] According to the superabsorbent resin of the present invention, it is possible to provide a superabsorbent resin having a circularity and an aspect ratio (A / R) of predetermined values, which can realize excellent quality when applied to an actual product.

[0021] In particular, it is possible to provide a superabsorbent resin with excellent property balance by simultaneously improving absorption performance such as water retention capacity and pressure absorption capacity while improving absorption speed.

[0022] In addition, when applied to sanitary materials such as diapers, it can absorb discharged body fluids at a fast rate and can also absorb relatively large amounts, thereby preventing problems such as body fluids accumulating inside the sanitary material or leaking out.

[0023] That is, it is possible to provide a superabsorbent resin that can quickly absorb body fluids when applied to a product and retain a large amount of body fluids without leaking them out.

[0024] Figure 1 shows the setting values ​​of the Sample Dispersion Unit in Malvern Panalytical's morphologi 4.

[0025] Figure 2 shows the illumination setting values ​​in Malvern Panalytical's morphologi 4.

[0026] Figure 3 shows the Optics Selection setting values ​​in Malvern Panalytical's morphologi 4.

[0027] Figure 4 shows the Scan Area setting values ​​in Malvern Panalytical's morphologi 4.

[0028] According to one embodiment of the present invention, as a polyacrylic acid (salt)-based superabsorbent resin,

[0029] The average value of circularity calculated by the following equation 1 for all particles is 0.90 or less, and the average value of aspect ratio (A / R), which means the ratio of the shortest diameter of the particle to the longest diameter of the particle, is 0.70 or more.

[0030] An absorbency under pressure (AUP) of 25 g / g or more as measured under 2.07 kPa (0.3 psi) in accordance with EDANA Act WSP 242.3;

[0031] Superabsorbent polymers may be provided:

[0032] [Formula 1]

[0033] Circularity = perimeter of CE particle / perimeter of actual particle

[0034] In the above equation 1,

[0035] The perimeter of a CE particle refers to the perimeter of a circle (Circle Equivalent) that has the same area as the 3D image of the 3D particle to be measured captured as a 2D image (CE Perimeter).

[0036] The actual particle perimeter refers to the actual perimeter length of the image captured as a 2D image of the 3D image of the 3D particle to be measured (Perimeter).

[0037] Unless otherwise defined herein, all technical and scientific terms used herein are used merely to describe exemplary embodiments and are not intended to be limiting of the present invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, it should be understood that the terms "comprises," "includes," or "has" indicate the presence of a feature, number, step, component, or combination thereof, but do not preclude the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0038] The present invention is susceptible to various modifications and takes various forms. Specific embodiments are illustrated and described in detail below. However, this is not intended to limit the present invention to specific disclosed forms, but rather to encompass all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

[0039] The technical terminology used herein is for the purpose of describing specific embodiments only and is not intended to limit the present invention. Furthermore, the singular forms "singular" and "in" also include plural forms, unless the context clearly dictates otherwise.

[0040] The term "polymer" or "high molecular weight polymer" as used in the specification of the present invention means a polymerized state of a water-soluble ethylenically unsaturated monomer, and may encompass any moisture content range or particle size range.

[0041] In addition, the term "superabsorbent resin" is used to mean, depending on the context, a base resin in powder form made of a crosslinked polymer or superabsorbent resin particles obtained by pulverizing the crosslinked polymer, or to encompass all of the crosslinked polymer or the base resin that have been subjected to additional processes, such as drying, pulverization, classification, surface crosslinking, etc., to make them suitable for commercialization.

[0042] Additionally, the term "fine particles" refers to particles having a particle size of less than 150 μm among superabsorbent resin particles. The particle size of such resin particles can be measured according to the European Disposables and Nonwovens Association (EDANA) standard EDANA WSP 220.3 method.

[0043] Additionally, the term "chopping" is used to refer to cutting the hydrogel polymer into small pieces on the order of millimeters to increase drying efficiency, as distinguished from grinding to the micrometer or normal particle level.

[0044] Additionally, the term "micronizing" is used to differentiate it from "chopping", as it refers to grinding a hydrogel polymer into particle sizes of tens to hundreds of micrometers.

[0045] Hereinafter, a superabsorbent resin and a method for manufacturing the same according to specific embodiments of the invention will be described in more detail.

[0046] Ⅰ. Polyacrylic acid (salt)-based superabsorbent resin

[0047] Hydrogel polymers obtained by polymerization of acrylic acid monomers undergo processes such as drying, grinding, classification, and surface crosslinking to produce superabsorbent resins in powder form, which are then commercially available. Recently, efforts have been continuously made to develop superabsorbent resins with even improved absorption rates.

[0048] The most common method for increasing the absorption rate is to form a porous structure inside the superabsorbent resin to increase the surface area of ​​the superabsorbent resin. In order to increase the surface area of ​​the superabsorbent resin, a method of forming a porous structure inside the base resin powder by including a foaming agent in the monomer composition and proceeding with crosslinking polymerization is generally adopted.

[0049] However, the conventional method has a problem in that it is difficult to form a sufficient surface area, and thus, during the actual urination time, body fluids that are not absorbed flow out from inside the sanitary material or leak out, causing discomfort to the user.

[0050] In order to solve the problems of the prior art as described above, the inventors of the present invention have confirmed that the resin can realize excellent quality when applied to an actual product by simultaneously improving absorption performance such as water retention capacity and pressure absorption capacity while improving absorption speed by adjusting the circularity and aspect ratio (A / R) to predetermined values, and completed the present invention.

[0051] According to one embodiment of the invention,

[0052] As a polyacrylic acid (salt)-based superabsorbent resin,

[0053] The average value of circularity calculated by the following equation 1 for all particles is 0.90 or less, and the average value of aspect ratio (A / R), which means the ratio of the shortest diameter of the particle to the longest diameter of the particle, is 0.70 or more.

[0054] An absorbency under pressure (AUP) of 25 g / g or more as measured under 2.07 kPa (0.3 psi) in accordance with EDANA Act WSP 242.3;

[0055] We provide super absorbent resins:

[0056] [Formula 1]

[0057] Circularity = perimeter of CE particle / perimeter of actual particle

[0058] In the above equation 1,

[0059] The perimeter of a CE particle refers to the perimeter of a circle (Circle Equivalent) that has the same area as the 3D image of the 3D particle to be measured captured as a 2D image (CE Perimeter).

[0060] The actual particle perimeter refers to the actual perimeter length of the image captured as a 2D image of the 3D image of the 3D particle to be measured (Perimeter).

[0061] The above total particles refer to superabsorbent resin particles with no limitation on particle size.

[0062] The present inventors have confirmed that when the circularity and aspect ratio of particles of a superabsorbent resin are each adjusted to a predetermined value, the specific surface area can be increased, thereby improving the absorption rate of the superabsorbent resin, while simultaneously improving other absorption performances such as water retention capacity and pressurized absorption capacity, thereby completing the present invention.

[0063] Specifically, by quantifying the shape of superabsorbent resin particles that affect absorption speed and absorption performance, the circularity is considered as a parameter that can determine how close the particle is to a perfect sphere, and the aspect ratio is considered as a parameter that can determine the symmetry of the particle, and it was confirmed that when each of these parameters has a certain level of value, the superabsorbent resin can exhibit a balance of fast absorption speed and improved water retention capacity and pressurized absorption capacity.

[0064] The above circularity is a parameter that can be used to determine how close the superabsorbent resin particles are to a perfect sphere, and is calculated by the following equation 1:

[0065] [Formula 1]

[0066] Circularity = perimeter of CE particle / perimeter of actual particle

[0067] In the above equation 1,

[0068] The perimeter of a CE particle refers to the perimeter of a circle (Circle Equivalent) that has the same area as the 3D image of the 3D particle to be measured captured as a 2D image (CE Perimeter).

[0069] The actual particle perimeter refers to the actual perimeter length of the image captured as a 2D image of the 3D image of the 3D particle to be measured (Perimeter).

[0070] The above circularity value has a value between 0 and 1, and in the case of a perfect sphere, the circularity is 1. The closer the circularity is to 1, the closer the particle is to a perfect sphere. The closer the circularity is to 0, the closer the particle is to a very pointed shape, for example, the shape of a very narrow rod.

[0071] At this time, the average value of the above circularity is measured after being randomly scattered on the stage by vacuum within the measuring device, and a statistical result is derived by securing n numbers of 200 or more and averaging them.

[0072] The above aspect ratio (A / R) is a parameter that can determine the symmetry of a particle, and means the ratio of the shortest diameter of the particle to the longest diameter of the particle.

[0073] The above aspect ratio value also has a value between 0 and 1. When all axes are symmetrical, such as a perfect sphere or square, the aspect ratio value is 1. The closer the aspect ratio is to 1, the more symmetrical the particle can be seen to be, and the closer the aspect ratio is to 0, the more asymmetrical the particle can be seen to be.

[0074] The average value of the above aspect ratio is similarly measured after randomly scattering the sample on the stage by vacuum within the measuring device, and a statistical result is derived by obtaining n of 200 or more and averaging them.

[0075] The above circularity and aspect ratio are similar in that they quantify the shape of superabsorbent resin particles, but they are parameters with different meanings.

[0076] That is, even if the circularity value is the same for particles, the aspect ratio value may be different depending on the symmetry of the particle and the degree of surface roughness, and if the shape of the particle changes, both the circularity and aspect ratio values ​​may be different or only some of them may be different.

[0077] Therefore, in order for a superabsorbent resin to exhibit a balance of fast absorption speed, improved water retention capacity, and pressurized absorption capacity, both circularity and aspect ratio need to satisfy specific levels of values.

[0078] These parameters can be measured using several commercial instruments that quantify and analyze particle morphology based on image analysis. For example, these parameters can be measured using Malvern Panalytical's Morphologi 4, which is specifically measured through the following four steps, which are described in more detail in the experimental examples below.

[0079] 1) Sample Preparation: Prepare the superabsorbent resin particles to be measured. When measuring the circularity and aspect ratio (A / R) of particles with a specific particle size range, prepare the sample by classifying the particles with the specific particle size using a Retsch classifier at 1.0 amplitude for 10 minutes.

[0080] At this time, the particle size of the superabsorbent resin particles can be measured according to the European Disposables and Nonwovens Association (EDANA) standard EDANA WSP 220.3 method.

[0081] 2) Image acquisition: After setting the prepared sample on the stage within the equipment, scan it at 2.5x magnification to acquire images of individual particles.

[0082] 3) Image processing: For the acquired images, the 3D image of the 3D particle for each particle is captured as a 2D image, and parameter values ​​such as CE diameter (Circle Equivalent diameter), shortest diameter, longest diameter, and actual particle circumference are measured.

[0083] 4) Based on the data analyzed for each particle, shape data values ​​for all particles included in the sample were obtained. The above-described superabsorbent resin has an average circularity value measured for all particles of 0.90 or less, and an average aspect ratio (A / R) value of 0.70 or more.

[0084] If the average circularity of all particles of the above-mentioned superabsorbent resin exceeds 0.90, the particles may become close to a perfect sphere, reducing the specific surface area and potentially lowering the absorption rate of the superabsorbent resin. If the average aspect ratio is less than 0.70, there may be a problem of lowered absorption performance.

[0085] Specifically, for example, the average value of the circularity of all particles of the superabsorbent resin may be 0.70 or more, 0.71 or more, 0.72 or more, or 0.73 or more, and 0.90 or less, 0.89 or less, 0.88 or less, 0.87 or less, or 0.86 or less.

[0086] As the average value of the above circularity decreases, that is, as the shape of the particle deviates from a perfect sphere and has a pointed shape, the specific surface area of ​​the particle can be seen to increase. However, if only the specific surface area is increased, a problem may arise in which absorption performance such as water retention capacity and pressurized absorption capacity deteriorates.

[0087] Therefore, in order to simultaneously improve absorption rate and absorption performance and have an excellent balance of physical properties, it is preferable that the average value of the circularity of all particles of the superabsorbent resin be 0.70 or more.

[0088] The average aspect ratio of all particles of the above superabsorbent resin may be 0.70 or more, 0.85 or less, 0.84 or less, 0.83 or less, 0.82 or less, 0.81 or less, or 0.80 or less.

[0089] As the average value of the above aspect ratio decreases, the asymmetry of the particles increases, which can be seen as increasing the specific surface area. However, similarly, if only the specific surface area is increased, a problem may arise in which absorption performance such as water retention capacity and pressurized absorption capacity deteriorates.

[0090] Therefore, in order to simultaneously improve absorption rate and absorption performance and have excellent physical property balance, it is preferable that the average value of the aspect ratio of all particles of the superabsorbent resin be 0.70 or more.

[0091] In addition, the superabsorbent resin particles of the present invention satisfy an average value of circularity measured for all particles of 0.90 or less and an average value of aspect ratio of 0.70 or more.

[0092] As described above, when the shape of the particle changes, both the circularity and aspect ratio values ​​may change, or only some of them may change, but when the two values ​​each satisfy a certain level of value, the specific surface area of ​​the particle increases and the asymmetry increases, so that the absorption rate and absorption performance of the superabsorbent resin can be improved at the same time, making it possible to implement a superabsorbent resin with excellent property balance.

[0093] Meanwhile, as described above, circularity is the ratio of the circumference of the CE particle to the circumference of the actual particle. In order to more sensitively represent the change in the relationship between the circumference of the actual particle and the circumference of the CE particle, the circularity value can be squared and represented as HS circularity (High Sensitivity circularity) as in Equation 2 below.

[0094] [Formula 2]

[0095] HS circularity = (perimeter of CE particle) 2 / (circumference of actual particle) 2

[0096] In the above equation 2, the perimeter of the CE particle and the perimeter of the actual particle are as described above.

[0097] The above HS circularity (High Sensitivity circularity) is a parameter that can be used to determine how close a particle is to a perfect sphere, similar to circularity. The HS circularity value also has a value between 0 and 1. The closer the HS circularity is to 1, the closer the particle is to a sphere, and the closer the HS circularity is to 0, the closer the particle is to a sharp shape.

[0098] However, the HS circularity is the square of the circularity value, and can be expressed by maximizing the calculated value according to the difference in particle shape.

[0099] Specifically, the average value of the HS circularity of all particles of the superabsorbent resin may be 0.50 or more, 0.51 or more, 0.52 or more, 0.53 or more, or 0.54 or more, and 0.80 or less, 0.79 or less, 0.78 or less, 0.77 or less, 0.76 or less, 0.75 or less, or 0.74 or less.

[0100] Meanwhile, the ratio of the circularity of particles having a particle size of 300 ㎛ to 600 ㎛ to the circularity of the entire particles may be 0.90 or more, 0.93 or more, or 0.95 or more.

[0101] The circularity of particles having a particle size of 300 ㎛ to 600 ㎛ in the above superabsorbent resin can be measured separately. At this time, the ratio of the circularity of particles having a particle size of 300 ㎛ to 600 ㎛ to the circularity of all particles can be calculated, and the closer the ratio of the circularity of particles having a particle size of 300 ㎛ to 600 ㎛ to the circularity of all particles is to 1, the more the superabsorbent resin has a similar degree of proximity to a perfect sphere regardless of the particle size.

[0102] The above superabsorbent resin may have an average CE diameter (Circle Equivalent diameter) of 220 ㎛ to 400 ㎛.

[0103] The above CE diameter refers to the diameter of a circle having the same area as an image captured as a 2D image of a 3D image of a particle, and the size of the particle can be expressed through the CE diameter.

[0104] However, since particles of different shapes may also have the same CE diameter value, it is desirable to represent the shape of the particle through the circularity and aspect ratio of the particle in addition to the CE diameter.

[0105] The average value of the CE diameter of the above superabsorbent resin may be 220 ㎛ or more, 230 ㎛ or more, or 240 ㎛ or more, and 400 ㎛ or less, 350 ㎛ or less, 330 ㎛ or less, 320 ㎛ or less, or 310 ㎛ or less.

[0106] If the average value of the CE diameter of the above-mentioned superabsorbent resin is less than 220 ㎛, there is a concern that the amount of fine particles will be high due to the large number of fine particles, and the absorption characteristics will be low. If it exceeds 400 ㎛, there may be a problem that the absorption speed will be low. Therefore, it is preferable that the average value of the CE diameter of the above-mentioned superabsorbent resin be within the above-mentioned range.

[0107] The average value of the above CE diameter is measured after randomly scattering the particles on the stage by vacuum within the measuring device, and a statistical result is derived by securing n numbers of 200 or more and averaging them.

[0108] In addition, the superabsorbent resin manufactured according to one embodiment of the present invention can have a uniform particle size distribution, and thus can provide a superabsorbent resin having excellent overall absorption properties such as water retention capacity and pressure absorption capacity, and rewet characteristics.

[0109] The superabsorbent resin according to one embodiment of the invention may have a fast absorption rate and a low fine particle content, and may have overall absorption properties such as water retention capacity (CRC) and absorbency under load (AUP) that are equivalent or higher than those of superabsorbent resins manufactured by conventional methods.

[0110] In addition, regardless of particle size, the circularity of the particles can have a similar value, and the content of water-soluble components (EC) can be reduced, thereby providing a superabsorbent resin having excellent liquid permeability and rewet properties.

[0111] Specifically, the superabsorbent resin of the present invention may have a water retention capacity (CRC) measured according to EDANA method WSP 241.3 of about 33 g / g or more, about 34 g / g or more, or about 35 g / g or more, and about 50 g / g or less, about 45 g / g or less, or about 40 g / g or less.

[0112] In addition, the superabsorbent polymer of the present invention may have an absorbency under pressure (AUP) of about 25 g / g or more, about 27 g / g or more, about 28 g / g or more, about 29 g / g or more, or about 30 g / g or more, and about 45 g / g or less, about 42 g / g or less, or about 40 g / g or less, at 2.07 kPa (0.3 psi) as measured according to EDANA method WSP 242.3.

[0113] In addition, the superabsorbent resin of the present invention may have an effective absorption capacity (EFFC) calculated by the following Equation 3 of 30 g / g or more, 31 g / g or more, 32 g / g or more, or 33 g / g or more, and 40 g / g or less, 39 g / g or less, 38 g / g or less, 37 g / g or less, or 36 g / g or less.

[0114] [Formula 3]

[0115] Effective Absorbent Capacity (EFFC) = {Water Retention Capacity (CRC) + Absorbent Capacity Under Pressure (AUP) of 2.07 kPa (0.3 psi)} / 2

[0116] The above effective absorption capacity (EFFC) is the arithmetic mean of the water retention capacity (CRC) and the 2.07 kPa (0.3 psi) absorbency under load (AUP), and can be calculated from the measured CRC and AUP.

[0117] In addition, the superabsorbent resin of the present invention may have a water-soluble component of 5 wt% or less, 4.8 wt% or less, 4.5 wt% or less, 4.3 wt% or less, 4 wt% or less, or 3.9 wt% or less, as measured after swelling for 1 hour according to the method of EDANA method WSP 270.3. The lower the value of the content of the water-soluble component, the better, and the lower limit is theoretically 0 wt%, but may be, for example, 0.1 wt% or more, or 1 wt% or more.

[0118] The superabsorbent resin of the present invention may have a vortex time of 40 seconds or less as measured by a vortex measurement method at 24.0°C.

[0119] More specifically, the vortex time may be 40 seconds or less, 35 seconds or less, 33 seconds or less, or 30 seconds or less. In addition, the vortex time is better the smaller the value, so the lower limit of the vortex time is theoretically 0 seconds, but may be, for example, 10 seconds or more, 15 seconds or more, or 20 seconds or more.

[0120] The method for measuring the water retention capacity, pressurized absorption capacity and absorption rate of the above superabsorbent resin is described in more detail in the experimental examples described below.

[0121] In addition, when 1 g of the superabsorbent resin of the present invention is swelled in water having an electrical conductivity of 110 μS / cm for 1 minute, the maximum capacity of water that the superabsorbent resin can hold (Free Swell Capacity) may be 170 g or more, 175 g or more, 180 g or more, or 185 g or more, and 230 g or less, 225 g or less, 220 g or less, or 215 g or less.

[0122] The method for measuring the absorption capacity in water having an electrical conductivity value of 110 μS / cm will be described in more detail in the experimental example section described below.

[0123] Meanwhile, the values ​​of circularity and aspect ratio according to the present invention can be implemented by adjusting the components / content of the superabsorbent resin, the manufacturing process conditions of the superabsorbent resin, etc.

[0124] For example, the circularity and aspect ratio can be controlled to have a specific range by adjusting the type and content of the monomer composition in the polymerization process, the type and content of the internal cross-linking agent, the type, amount and timing of introduction of the surfactant in the neutralization and atomization steps, the type, amount and timing of introduction of the neutralizing agent, the type of atomization device, the rotation speed, the hole size, the number of atomizations, etc.

[0125] This will be explained in more detail in Item II of the method for manufacturing superabsorbent resin.

[0126] Below, each component that makes up the superabsorbent resin will be explained in more detail.

[0127] A polyacrylic acid (salt)-based superabsorbent resin of one embodiment of the invention comprises a base resin comprising a crosslinked polymer of a water-soluble ethylenically unsaturated monomer having an acidic group and an internal crosslinking agent. The crosslinked polymer can preferably be formed by polymerizing a monomer composition comprising components such as a monomer, an internal crosslinking agent, and a polymerization initiator.

[0128] Here, the water-soluble ethylenically unsaturated monomer may be any monomer commonly used in the production of superabsorbent resins. As a non-limiting example, the water-soluble ethylenically unsaturated monomer may be a compound represented by the following chemical formula 1:

[0129] [Chemical Formula 1]

[0130] R-COOM'

[0131] In the above chemical formula 1,

[0132] R is an alkyl group having 2 to 5 carbon atoms containing an unsaturated bond,

[0133] M' is a hydrogen atom, a monovalent or divalent metal, an ammonium group, or an organic amine salt.

[0134] Preferably, the monomer may be at least one selected from the group consisting of (meth)acrylic acid, and monovalent (alkali) metal salts, divalent metal salts, ammonium salts, and organic amine salts of these acids.

[0135] In this way, when (meth)acrylic acid and / or its salt is used as a water-soluble ethylenically unsaturated monomer, a superabsorbent resin with improved absorbency can be obtained, which is advantageous. In addition, as the monomers, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethane sulfonic acid, 2-methacryloylethane sulfonic acid, 2-(meth)acryloylpropanesulfonic acid or 2-(meth)acrylamide-2-methyl propane sulfonic acid, (meth)acrylamide, N-substituted (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, (N,N)-dimethylaminoethyl (meth)acrylate, (N,N)-dimethylaminopropyl (meth)acrylamide, etc. can be used.

[0136] The above-mentioned water-soluble ethylenically unsaturated monomer has acidic groups. Meanwhile, in the production of superabsorbent resins, a monomer in which at least a portion of the acidic groups are neutralized by a neutralizing agent is crosslinked and polymerized to form a polymer. However, in the present invention, the acidic groups are preferably not neutralized during polymerization, but can be neutralized after the polymer is formed. More specific details regarding this will be described in the section on the production method of superabsorbent resins.

[0137] The concentration of the water-soluble ethylenically unsaturated monomer in the monomer composition may be appropriately adjusted in consideration of polymerization time, reaction conditions, etc., and may be about 20 to about 60 wt%, or about 20 to about 40 wt%.

[0138] The term 'internal crosslinking agent' used in this specification is a term used to distinguish it from a surface crosslinking agent for performing a crosslinking reaction on the surface of superabsorbent resin particles described below, and it serves to form a polymer including a crosslinked structure by introducing crosslinking bonds between unsaturated bonds of the water-soluble ethylenically unsaturated monomers described above.

[0139] The crosslinking in the above step is carried out without distinction between the surface and the interior, but when the surface crosslinking process of the superabsorbent resin particles described later is carried out, the surface of the finally manufactured superabsorbent resin particles may include a structure newly crosslinked by the surface crosslinking agent, and the interior of the superabsorbent resin particles may maintain the structure crosslinked by the internal crosslinking agent.

[0140] According to one embodiment of the present invention, the internal crosslinking agent may include at least one of a multifunctional acrylate compound, a multifunctional allyl compound, or a multifunctional vinyl compound.

[0141] Non-limiting examples of multifunctional acrylate compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol Examples thereof include tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, and glycerin tri(meth)acrylate, and these may be used alone or in combination of two or more.

[0142] Non-limiting examples of polyfunctional allyl compounds include ethylene glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, tetraethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, tripropylene glycol diallyl ether, polypropylene glycol diallyl ether, butanediol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol diallyl ether, dipentaerythritol triallyl ether, dipentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, trimethylolpropane diallyl ether, Examples include trimethylolpropane triallyl ether, glycerin diallyl ether, and glycerin triallyl ether, and they can be used alone or in combination of two or more.

[0143] Non-limiting examples of polyfunctional vinyl compounds include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol divinyl ether, butanediol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol divinyl ether, dipentaerythritol trivinyl ether, dipentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, trimethylolpropane divinyl ether, trimethylolpropane Examples thereof include trivinyl ether, glycerin divinyl ether, and glycerin trivinyl ether, and these may be used singly or in combination of two or more. Preferably, pentaerythritol triallyl ether may be used.

[0144] The above-described multifunctional allyl compound or multifunctional vinyl compound can form a cross-linked structure during the polymerization process by having two or more unsaturated groups included in the molecule bond with the unsaturated bonds of water-soluble ethylenically unsaturated monomers or the unsaturated bonds of other internal cross-linking agents, and unlike an acrylate compound including an ester bond (-(C=O)O-) in the molecule, the cross-linked bond can be more stably maintained even during the neutralization process after the polymerization reaction described below.

[0145] Accordingly, the gel strength of the superabsorbent resin being manufactured can be increased, process stability can be improved during the discharging process after polymerization, and the amount of water-soluble components can be minimized.

[0146] Crosslinking polymerization of the water-soluble ethylenically unsaturated monomer in the presence of such an internal crosslinking agent can be carried out in the presence of a polymerization initiator, a thickener if necessary, a plasticizer, a preservative stabilizer, an antioxidant, etc.

[0147] In the monomer composition, the internal cross-linking agent may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer. For example, the internal cross-linking agent may be used in an amount of 0.01 parts by weight or more, 0.05 parts by weight or more, or 0.1 parts by weight or more, and 5 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, 1 part by weight or less, or 0.7 parts by weight or less, based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer. If the content of the internal cross-linking agent is too low, cross-linking may not sufficiently occur, making it difficult to achieve a strength higher than an appropriate level, and if the content of the internal cross-linking agent is too high, the internal cross-linking density may increase, making it difficult to achieve a desired water retention capacity. In particular, it is suitable for achieving the circularity and aspect ratio of the present invention within the intended range within the above range.

[0148] Meanwhile, when a low content of internal cross-linking agent is used to ensure that the base resin has a high water retention capacity (CRC), the gel strength of the formed polymer may be reduced, and the low gel strength may make it difficult to operate a shredder or the like when cutting the hydrogel polymer. In this case, by mixing two or more types of internal cross-linking agents and using them to operate a high-speed rotary shredder or the like, the gel strength can be increased, thereby improving the operational stability of the shredder or the like.

[0149] Meanwhile, when a low content of internal cross-linking agent is used to ensure that the base resin has a high water retention capacity (CRC), the gel strength of the formed polymer may be reduced, and the low gel strength may make it difficult to operate a shredder or the like when cutting the hydrogel polymer. In this case, by mixing two or more types of internal cross-linking agents and using them to operate a high-speed rotary shredder or the like, the gel strength can be increased, thereby improving the operational stability of the shredder or the like.

[0150] In this way, when the polymer has a three-dimensional network structure, the overall properties of the superabsorbent resin, such as water retention capacity and pressure absorption capacity, can be significantly improved compared to the case of a two-dimensional linear structure that is not further crosslinked by an internal crosslinking agent.

[0151] The above polymer is a polymer in which a monomer and an internal crosslinking agent are polymerized in the presence of a polymerization initiator. The type of the polymerization initiator is not particularly limited, but preferably, the polymerization can be performed using a thermal polymerization method in a batch reactor, and accordingly, a thermal polymerization initiator can be used as the polymerization initiator.

[0152] As the above thermal polymerization initiator, one or more selected from the group of initiators consisting of persulfate initiators, azo initiators, hydrogen peroxide, and ascorbic acid can be used. Specifically, examples of persulfate initiators include sodium persulfate (Na2S2O8), potassium persulfate (K2S2O8), and ammonium persulfate ((NH4)2S2O8), and examples of azo initiators include 2,2-azobis-(2-amidinopropane) dihydrochloride, 2,2-azobis-(N,N-dimethylene)isobutyramidine dihydrochloride, 2-(carbamoylazo)isobutylonitril, Examples include 2,2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 4,4-azobis-(4-cyanovaleric acid), etc. A more diverse range of thermal polymerization initiators is well described in Odian's book, 'Principle of Polymerization (Wiley, 1981), p203, and is not limited to the examples described above.

[0153] Such polymerization initiator may be used in an amount of 2 parts by weight or less relative to 100 parts by weight of the water-soluble ethylenically unsaturated monomer. That is, if the concentration of the polymerization initiator is excessively low, the polymerization rate may be slowed and a large amount of residual monomer may be extracted from the final product, which is not preferable. Conversely, if the concentration of the polymerization initiator is higher than the above range, the polymer chains forming the network may become shorter, which may increase the content of water-soluble components and lower the pressure absorbency, thereby deteriorating the physical properties of the resin, which is not preferable.

[0154] Meanwhile, in one embodiment of the present invention, polymerization can be initiated by adding the aforementioned polymerization initiator and a reducing agent forming a redox couple together to the monomer composition.

[0155] Specifically, the initiator and reducing agent react with each other to form radicals when introduced into a polymer solution.

[0156] The formed radicals react with the monomer, and since the oxidation-reduction reaction between the initiator and reducing agent is highly reactive, polymerization is initiated even when only a small amount of initiator and reducing agent is added, so there is no need to increase the process temperature, low-temperature polymerization is possible, and changes in the physical properties of the polymer solution can be minimized.

[0157] The polymerization reaction utilizing the above oxidation-reduction reaction can occur smoothly even at temperatures near room temperature (25°C) or lower. For example, the polymerization reaction can be performed at a temperature of 5°C or higher and 25°C or lower, or 5°C or higher and 20°C or lower.

[0158] In one embodiment of the present invention, when a persulfate-based initiator is used as the initiator, the reducing agent may be at least one selected from the group consisting of sodium metabisulfite (Na2S2O5); tetramethyl ethylenediamine (TMEDA); a mixture of iron (II) sulfate and EDTA (FeSO4 / EDTA); sodium formaldehyde sulfoxylate; and disodium 2-hydroxy-2-sulfinoacetate.

[0159] For example, potassium persulfate may be used as the initiator and disodium 2-hydroxy-2-sulfinoacetate may be used as the reducing agent; ammonium persulfate may be used as the initiator and tetramethylethylenediamine may be used as the reducing agent; or sodium persulfate may be used as the initiator and sodium formaldehyde sulfoxylate may be used as the reducing agent.

[0160] In another embodiment of the present invention, when a hydrogen peroxide-based initiator is used as the initiator, the reducing agent may be at least one selected from the group consisting of ascorbic acid; sucrose; sodium sulfite (Na2SO3), sodium metabisulfite (Na2S2O5); tetramethyl ethylenediamine (TMEDA); a mixture of iron (II) sulfate and EDTA (FeSO4 / EDTA); sodium formaldehyde sulfoxylate; disodium 2-hydroxy-2-sulfinoacteate; and disodium 2-hydroxy-2-sulfoacteate.

[0161] The above monomer composition may further include additives such as a thickener, a plasticizer, a preservative stabilizer, and an antioxidant, as needed.

[0162] And, the monomer composition including the monomer may be in a solution state dissolved in a solvent such as water, for example, and the solid content in the monomer composition in the solution state, i.e., the concentration of the monomer, internal crosslinking agent, and polymerization initiator, may be appropriately adjusted in consideration of the polymerization time, reaction conditions, etc. For example, the solid content in the monomer composition may be 10 to 80 wt%, 15 to 60 wt%, or 30 to 50 wt%.

[0163] The solvent that can be used at this time can be used without limitation in its composition as long as it can dissolve the above-mentioned components, and for example, one or more selected from 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 ether, toluene, xylene, butyrolactone, carbitol, methyl cellosolve acetate, and N,N-dimethylacetamide can be used in combination.

[0164] The polymer obtained in this way can form a polymer having a high molecular weight and a uniform molecular weight distribution by polymerizing using an ethylenically unsaturated monomer in an unsaturated state, and is suitable for implementing the desired circularity and aspect ratio within an appropriate range by reducing the content of the water-soluble component.

[0165] Additionally, the polymer may have a moisture content of 30 to 80 wt%. For example, the moisture content of the polymer may be at least 30 wt%, at least 45 wt%, or at least 50 wt%, but at most 80 wt%, at most 70 wt%, or at most 60 wt%.

[0166] If the moisture content of the polymer is too low, it may be difficult to secure an appropriate surface area in the subsequent grinding step, and thus the polymer may not be effectively ground. If the moisture content of the polymer is too high, the pressure applied in the subsequent grinding step may increase, making it difficult to grind to the desired particle size.

[0167] Meanwhile, throughout this specification, "moisture content" refers to the moisture content in relation to the total polymer weight, which is the value obtained by subtracting the weight of the polymer in a dry state from the weight of the polymer. Specifically, the moisture content is defined as a value calculated by measuring the weight loss due to moisture evaporation in the polymer during the drying process by raising the temperature of the polymer in a crumbly state through infrared heating. At this time, the drying conditions are such that the temperature is raised from room temperature to about 180°C and then maintained at 180°C, and the total drying time is set to 40 minutes, including 5 minutes for the temperature rising step, to measure the moisture content.

[0168] A superabsorbent resin according to one embodiment of the invention comprises a base resin powder comprising a crosslinked polymer of a water-soluble ethylenically unsaturated monomer having an acidic group as described above and an internal crosslinking agent; and a surface crosslinked layer formed on the base resin powder by further crosslinking the crosslinked polymer via a surface crosslinking agent.

[0169] The above surface cross-linking layer is formed on at least a portion of the surface of the base resin powder, and may be formed by additional cross-linking of a cross-linking polymer included in the base resin powder via a surface cross-linking agent.

[0170] As the surface cross-linking agent, any surface cross-linking agent that has been conventionally used in the production of superabsorbent resins can be used without particular limitation. For example, the surface cross-linking agent may be at least one polyol selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-hexanediol, 1,3-hexanediol, 2-methyl-1,3-propanediol, 2,5-hexanediol, 2-methyl-1,3-pentanediol, 2-methyl-2,4-pentanediol, tripropylene glycol, and glycerol; at least one carbonate compound selected from the group consisting of ethylene carbonate, propylene carbonate, and glycerol carbonate; an epoxy compound such as ethylene glycol diglycidyl ether; an oxazoline compound such as oxazolidinone; a polyamine compound; mono-, di- or polyoxazolidinone compounds; or cyclic urea compounds; etc.

[0171] Specifically, one or more, two or more, or three or more of the surface cross-linking agents described above may be used as the surface cross-linking agent, for example, ethylene carbonate-propylene carbonate (ECPC), propylene glycol, and / or glycerol carbonate may be used.

[0172] Such a surface cross-linking agent may be used in an amount of about 0.001 to about 5 parts by weight based on 100 parts by weight of the superabsorbent resin particles. For example, the surface cross-linking agent may be used in an amount of 0.005 parts by weight or more, 0.01 parts by weight or more, or 0.05 parts by weight or more, and 5 parts by weight or less, 4 parts by weight or less, or 3 parts by weight or less based on 100 parts by weight of the superabsorbent resin particles. By adjusting the content range of the surface cross-linking agent within the above-described range, a superabsorbent resin exhibiting excellent overall absorption properties can be manufactured. In particular, it is suitable for implementing the circularity and aspect ratio of the present invention within the target range within the above range.

[0173] Additionally, the surface cross-linking layer can be formed by adding an inorganic substance to the surface cross-linking agent. That is, in the presence of the surface cross-linking agent and the inorganic substance, the surface of the base resin powder can be further cross-linked to form a surface cross-linking layer.

[0174] As such inorganic materials, one or more inorganic materials selected from the group consisting of silica, clay, alumina, silica-alumina composites, titania, zinc oxide, and aluminum sulfate can be used. The inorganic material can be used in powder or liquid form, and in particular, can be used as alumina powder, silica-alumina powder, titania powder, or nano silica solution. In addition, the inorganic material can be used in an amount of about 0.001 to about 1 part by weight based on 100 parts by weight of superabsorbent resin particles.

[0175] As described above, the superabsorbent resin including the base resin powder and the surface cross-linking layer formed on the base resin powder can absorb discharged body fluid at a high speed when applied to sanitary materials such as diapers by adjusting the circularity and aspect ratio, which are the parameters of the present invention, to a specific range, and can also absorb a relatively large amount initially, thereby preventing problems such as body fluid accumulating inside the sanitary material or leaking out.

[0176] Ⅱ. Manufacturing method of superabsorbent resin

[0177] Meanwhile, conventional superabsorbent polymers are manufactured by crosslinking and polymerizing a water-soluble ethylenically unsaturated monomer having at least partially neutralized acidic groups in the presence of an internal crosslinking agent and a polymerization initiator to form a hydrogel polymer, drying the hydrogel polymer formed in this manner, and then pulverizing it to a desired particle size. In this case, a chopping process is typically performed before the drying process to cut the hydrogel polymer into particles several millimeters in size in order to facilitate drying of the hydrogel polymer and increase the efficiency of the pulverization process. However, in this chopping process, due to the adhesiveness of the hydrogel polymer, the hydrogel polymer cannot be pulverized to a micro-sized particle level, but instead becomes an aggregated gel. When this aggregated gel-type hydrogel polymer is dried, a plate-shaped dried body is formed, and in order to pulverize it to a micro-sized particle level, it must go through a multi-stage pulverization process that lowers the adhesiveness of the polymer. This process has been problematic in that a lot of fine dust is generated.

[0178] Specifically, conventional superabsorbent resins have been manufactured by including the following steps.

[0179] (Neutralization) A step of neutralizing at least a portion of the acidic groups of a water-soluble ethylenically unsaturated monomer;

[0180] (Polymerization) A step of forming a hydrogel polymer by crosslinking and polymerizing a water-soluble ethylenically unsaturated monomer having at least a portion of neutralized acidic groups in the presence of an internal crosslinking agent and a polymerization initiator;

[0181] (Chopping) A step of chopping the above functional gel polymer;

[0182] (dry) drying the chopped functional gel polymer; and

[0183] (Crushing / classification) A step of crushing the dried polymer and then classifying it into normal particles and fine powder;

[0184] As described above, the chopped hydrogel polymer has a coagulated gel form with a size of about 1 cm to 10 cm, and the chopped hydrogel polymer is laminated on a belt having a perforated bottom and dried by hot air supplied from the bottom or the top. Since the polymer dried by the drying method has a plate shape rather than a particle shape, the step of classifying after grinding has been performed by coarsely grinding and then classifying, and then finely grinding and then classifying again so that the manufactured particles become normal particles, that is, particles having a particle size of 150 ㎛ to 850 ㎛. Since the amount of fine powder separated in the final classification step by this manufacturing method is large, about 20 wt% to about 30 wt% based on the total weight of the finally manufactured superabsorbent resin, the separated fine powder is mixed with an appropriate amount of water, reassembled into fine powder, and then reused by adding it to the chopping step or the step before drying.

[0185] However, when the fine powder reassembly mixed with water is re-introduced into the crushing or drying process for reuse of such fine powder, problems such as increased device load and / or energy consumption have occurred, and the fine powder remaining without being classified has caused a deterioration in the properties of the superabsorbent resin.

[0186] To solve this problem, as a result of repeated research, it was confirmed that, instead of performing polymerization in a state where the acidic groups of a water-soluble ethylenically unsaturated monomer are neutralized, as in the conventional method for producing superabsorbent resins, polymerization is first performed in a state where the acidic groups are not neutralized to form a polymer, and then the hydrogel polymer is micronized in the presence of a surfactant and then the acidic groups of the polymer are neutralized, or the hydrogel polymer is formed by neutralizing the acidic groups of the polymer and then the hydrogel polymer is micronized in the presence of a surfactant, or the acidic groups present in the polymer are neutralized simultaneously with the micronization, so that the surfactant is present in a large amount on the surface of the polymer and can sufficiently play a role in lowering the high adhesiveness of the polymer, preventing the polymer from excessively agglomerating, and controlling the agglomeration state to a desired level.

[0187] At this time, when a high-intensity mechanical shear force is applied to the above-mentioned micro-pulverization step to perform ultra-fine grinding, coagulated functional gel particles having finer pores can be formed.

[0188] The functional gel polymer manufactured by applying the above high-intensity mechanical shear force and ultra-fine grinding is manufactured in the form of particles having stable micropores of 100㎛ or less, and as the grinding and drying process is carried out under milder conditions thereafter, the amount of fine powder generated during the process can be further reduced.

[0189] In addition, the absorption rate can also be improved by forming micropores in the hydrogel polymer through the ultra-fine grinding process using the high-intensity mechanical shear force without using a separate foaming agent in the polymerization step, and accordingly, the circularity and aspect ratio (A / R) of the superabsorbent resin of the present invention described above can be easily controlled within the desired range.

[0190] Meanwhile, preferably, the above-mentioned functional gel micronization process can be conducted in the presence of a surfactant. By using a surfactant in the micronization step, particle aggregation can be effectively controlled, thereby reducing the load on the device and further improving productivity.

[0191] In addition, by first performing polymerization in an uncrosslinked state to form a polymer and then neutralizing the acidic groups present in the polymer, it is possible to form a polymer with a longer chain, and thus achieve the effect of reducing the content of water-soluble components that exist in an uncrosslinked state due to incomplete crosslinking.

[0192] Since the above-mentioned water-soluble component has the property of easily dissolving when the superabsorbent resin comes into contact with a liquid, when the content of the water-soluble component is high, most of the dissolved water-soluble component remains on the surface of the superabsorbent resin, making the superabsorbent resin sticky and causing a decrease in liquid permeability. Therefore, from the perspective of liquid permeability, it is important to keep the content of the water-soluble component low.

[0193] According to one embodiment of the present invention, by performing polymerization in an unsaturated state, the content of water-soluble components is reduced, thereby improving the permeability of the superabsorbent resin, and accordingly, it was confirmed that it is easy to control the circularity and aspect ratio within a desired range.

[0194] Hereinafter, each step of the method for manufacturing a superabsorbent resin according to an embodiment will be described in more detail.

[0195] Step 1: Polymerization Step

[0196] First, polymerization is performed on a monomer composition including a water-soluble ethylenically unsaturated monomer having an acidic group and an internal crosslinking agent, thereby producing a base resin powder including a polymer in which the water-soluble ethylenically unsaturated monomer having an acidic group and the internal crosslinking agent are crosslinked.

[0197] The above step may be comprised of a step of preparing a monomer composition by mixing the water-soluble ethylenically unsaturated monomer having the acidic group, an internal crosslinking agent, and a polymerization initiator, and a step of polymerizing the monomer composition to form a polymer.

[0198] Here, the same content as described in the superabsorbent resin of the above-mentioned item ° can be applied to each component.

[0199] Meanwhile, the water-soluble ethylenically unsaturated monomer has an acidic group. As explained above, in the production of conventional superabsorbent resins, a monomer in which at least a portion of the acidic groups are neutralized by a neutralizing agent is crosslinked and polymerized to form a polymer. Specifically, in the step of mixing the water-soluble ethylenically unsaturated monomer having the acidic group, an internal crosslinking agent, a polymerization initiator, and a neutralizing agent, at least a portion of the acidic groups of the water-soluble ethylenically unsaturated monomer are neutralized.

[0200] However, according to one embodiment of the present invention, polymerization is first performed in a state where the acidic group of the water-soluble ethylenically unsaturated monomer is not neutralized to form a polymer.

[0201] Water-soluble ethylenically unsaturated monomers (e.g., acrylic acid) whose acid groups are not neutralized are liquid at room temperature and have high miscibility with the solvent (water), so they exist as a mixed solution in the monomer composition. However, water-soluble ethylenically unsaturated monomers whose acid groups are neutralized are solid at room temperature and have different solubility depending on the temperature of the solvent (water), with the solubility decreasing at lower temperatures.

[0202] In this way, a water-soluble ethylenically unsaturated monomer in which the acidic groups are not neutralized has a higher solubility or miscibility in a solvent (water) than a monomer in which the acidic groups are neutralized, and thus does not precipitate even at low temperatures, and is therefore advantageous for long-term polymerization at low temperatures. Accordingly, a water-soluble ethylenically unsaturated monomer in which the acidic groups are not neutralized can be used for long-term polymerization to stably form a polymer having a higher molecular weight and a uniform molecular weight distribution.

[0203] In addition, since it is possible to form a polymer of a longer chain, it is possible to achieve the effect of reducing the content of water-soluble components that exist in a non-crosslinked state due to incomplete polymerization or crosslinking, and accordingly, it is suitable for implementing the circularity and aspect ratio of the superabsorbent resin of the present invention described above within the desired range.

[0204] In addition, if polymerization is first performed in a state where the acidic groups of the monomer are not neutralized to form a polymer, and then the polymer is micronized in the presence of a surfactant after neutralization, or the polymer is micronized in the presence of a surfactant and then neutralized, or the acidic groups present in the polymer are neutralized simultaneously with the micronization, the surfactant can sufficiently play a role in reducing the adhesiveness of the polymer by being present in large quantities on the surface of the polymer.

[0205] According to one embodiment of the present invention, the step of performing polymerization on the monomer composition to form a polymer can be performed for 1 hour or more in a batch type reactor.

[0206] In the manufacturing method of a typical superabsorbent resin, the polymerization method is largely divided into thermal polymerization and photopolymerization depending on the polymerization energy source. When thermal polymerization is performed, it can be performed in a reactor with a stirring shaft such as a kneader, and when photopolymerization is performed, it can be performed in a flat-bottomed container.

[0207] Meanwhile, when the polymerization is performed as a continuous polymerization, for example, when the polymerization is performed in a reactor equipped with a conveyor belt, a new monomer composition is supplied to the reactor as the polymerization product moves, so that polymerization is performed continuously, and thus polymers having different polymerization rates are mixed, and accordingly, it is difficult to achieve even polymerization throughout the entire monomer composition, which may result in a deterioration of the overall physical properties.

[0208] However, according to one embodiment of the present invention, since polymerization is carried out in a static manner in a batch reactor, there is less concern that polymers with different polymerization rates will be mixed, and thus a polymer with consistent quality can be obtained.

[0209] In addition, the polymerization step is performed in a batch reactor having a predetermined volume, and the polymerization reaction is performed for a longer period of time, for example, 1 hour or more, 3 hours or more, or 6 hours or more, than when polymerization is performed continuously in a reactor equipped with a conveyor belt. Despite the long polymerization reaction time as described above, since the polymerization is performed on a water-soluble ethylenically unsaturated monomer in an unneutralized state, the monomer does not precipitate easily even if the polymerization is performed for a long period of time, and therefore, it is advantageous for long-term polymerization.

[0210] Meanwhile, since polymerization in the batch reactor of the present invention utilizes a thermal polymerization method, the polymerization initiator uses a thermal polymerization initiator, and the description of the corresponding component is as described above.

[0211] Steps 2 and 3: Atomization and neutralization steps

[0212] Next, a step (step 2) is included in which the functional gel polymer is micronized in the presence of a surfactant to prepare a mixture including the micronized functional gel polymer.

[0213] The above-mentioned micronization step is a step of micronizing the polymer in the presence of a surfactant, and is a step in which micronization and agglomeration into sizes of tens to hundreds of micrometers occur simultaneously, rather than chopping the polymer into sizes of millimeters.

[0214] That is, this is a step for manufacturing secondary aggregated particles in the form of aggregated primary particles that are finely divided into tens to hundreds of micrometers in size by imparting appropriate adhesiveness to the polymer. The secondary aggregated particles, which are hydrophilic superabsorbent resin particles manufactured through this step, have a normal particle size distribution while significantly increasing their surface area, which can significantly improve their absorption rate.

[0215] Meanwhile, when a high-intensity mechanical shear force is applied in the above-mentioned micronization step to perform ultra-fine grinding at a rotation speed of 500 rpm to 4,000 rpm, coagulated functional gel particles having finer pores can be formed.

[0216] At this time, when ultra-fine grinding is performed at a rotation speed of 500 rpm to 4,000 rpm, a high-strength mechanical shear force is applied, so that micropores of 100 μm or less are easily formed in the polymer, thereby increasing the surface roughness, and significantly increasing the total surface area of ​​the polymer due to the pores formed inside and outside the polymer particles. Since the micropores are formed in a stable form compared to the pores formed using a foaming agent in the polymerization step, the degree of fine powder generation due to the pores in the subsequent process can be significantly reduced. The superabsorbent resin particles manufactured by this step have a significantly increased surface area, so that the absorption rate can be significantly improved, and thus are suitable for implementing the circularity and aspect ratio of the superabsorbent resin of the present invention described above within the desired range.

[0217] The above ultra-fine grinding process is performed at a rotation speed of 500 rpm to 4,000 rpm. If the rotation speed of the process is less than 500 rpm, it is difficult to form sufficient pores to the desired degree, making it difficult to expect a fast absorption speed and securing the desired level of productivity. In addition, if it exceeds 4,000 rpm, the polymer chains may be damaged due to excessive shear force, and accordingly, the water-soluble component may increase, which may slightly deteriorate the overall physical properties of the manufactured superabsorbent resin. Preferably, the above ultra-fine grinding process can be performed at 1,000 rpm to 3,500 rpm, or 2,000 rpm to 3,000 rpm. Within this range, it is easy to form the desired micropores without the aforementioned problems.

[0218] According to one embodiment of the present invention, the atomization step is performed by an atomization device, and the atomization device may include a body part including a transport space into which a polymer is transported; a screw member rotatably installed inside the transport space to move the polymer; a driving motor providing a rotational driving force to the screw member; a cutter member installed in the body part to pulverize the polymer; and a porous plate having a plurality of holes formed therein, which discharges the polymer pulverized by the cutter member to the outside of the body part.

[0219] At this time, the hole size provided in the porous plate of the atomization device may be 1 mm to 25 mm, 5 mm to 20 mm, or 5 mm to 15 mm.

[0220] In this way, when the polymer mixed with the surfactant is atomized while controlling agglomeration using a micronizing device, a smaller particle size distribution is realized, so that subsequent drying and grinding processes can be performed under milder conditions, thereby preventing the generation of fine particles and improving the properties of the superabsorbent resin. In addition, if ultra-fine grinding is performed, the absorption rate can be improved by simultaneously forming appropriate micropores on the surface of the polymer and increasing the surface area.

[0221] The above atomization step may be performed one or more times, preferably one to six times, one to four times, or one to three times. This may be performed using a plurality of atomization devices, a single atomization device comprising a plurality of porous plates and / or a plurality of cutter elements, or some of the plurality of atomization devices may comprise a plurality of porous plates and / or a plurality of cutter elements.

[0222] According to one embodiment of the present invention, a surfactant may be additionally used in the atomization step, whereby agglomeration between polymer particles can be effectively controlled, thereby reducing the load on the equipment used in the pulverization process and further improving productivity.

[0223] Preferably, the surfactant may be a compound represented by the following chemical formula 2 or a salt thereof, but the present invention is not limited thereto:

[0224] [Chemical Formula 2]

[0225]

[0226] In the above chemical formula 2,

[0227] A1, A2 and A3 are each independently a single bond, carbonyl, , or and, provided that at least one of these is carbonyl or , wherein, m1, m2 and m3 are each independently an integer from 1 to 8, are each connected to an adjacent oxygen atom, are connected to adjacent R1, R2 and R3 respectively,

[0228] R1, R2 and R3 are each independently hydrogen, straight or branched chain alkyl having 6 to 18 carbon atoms or straight or branched chain alkenyl having 6 to 18 carbon atoms,

[0229] n is an integer from 1 to 9.

[0230] The above surfactant is added so that the atomization step can be easily achieved without agglomeration by mixing with the polymer.

[0231] The surfactant represented by the above chemical formula 2 is a nonionic surfactant, and has excellent surface adsorption performance by hydrogen bonding even with a polymer that is not neutralized, and is therefore suitable for implementing the desired coagulation control effect. On the other hand, in the case of anionic surfactants, not nonionic surfactants, when mixed with a polymer that has been neutralized with a neutralizing agent such as NaOH or Na2SO4, the Na ionized in the carboxyl group substituent of the polymer + It is adsorbed through ions, and when mixed with an unsaturated polymer, there is a problem that the adsorption efficiency for the polymer is relatively reduced due to competition with the anion of the carboxyl group substituent of the polymer.

[0232] Specifically, in the surfactant represented by the above chemical formula 2, the hydrophobic functional group is the terminal functional group R1, R2, R3 portion (if not hydrogen), and the hydrophilic functional group is the glycerol-derived portion in the chain and the terminal hydroxyl group (A n is a single bond, and at the same time R nWhen hydrogen is present, n=1~3) is further included, and the glycerol-derived portion and the terminal hydroxyl group serve as hydrophilic functional groups to improve the adsorption performance on the polymer surface. Accordingly, the aggregation of superabsorbent resin particles can be effectively suppressed.

[0233] In the above chemical formula 2, the hydrophobic functional groups R1, R2, and R3 (if not hydrogen) are each independently a straight-chain or branched alkyl having 6 to 18 carbon atoms or a straight-chain or branched alkenyl having 6 to 18 carbon atoms. In this case, if the R1, R2, and R3 portions (if not hydrogen) are alkyl or alkenyl having less than 6 carbon atoms, there is a problem that the agglomeration control of the pulverized particles is not effectively performed due to the short chain length, and if the R1, R2, and R3 portions (if not hydrogen) are alkyl or alkenyl having more than 18 carbon atoms, the mobility of the surfactant may be reduced so that it may not be effectively mixed with the polymer, and there may be a problem that the unit price of the composition increases due to the increase in the cost of the surfactant.

[0234] Preferably, R1, R2, R3 may be hydrogen, or, if it is a straight-chain or branched alkyl having 6 to 18 carbon atoms, 2-methylhexyl, n-heptyl, 2-methylheptyl, n-octyl, n-nonyl, n-decanyl, n-undecanyl, n-dodecanyl, n-tridecanyl, n-tetradecanyl, n-pentadecanyl, n-hexadecanyl, n-heptadecanyl, or n-octadecanyl, or, if it is a straight-chain or branched alkenyl having 6 to 18 carbon atoms, 2-hexenyl, 2-heptenyl, 2-octenyl, 2-nonenyl, n-dekenyl, 2-undekenyl, 2-dodekenyl, 2-tridekenyl, 2-tetradekenyl, 2-pentadekenyl, 2-hexadekenyl, It can be 2-heptadekenyl or 2-octadekenyl.

[0235] The above surfactant may be selected from compounds represented by the following chemical formulas 2-1 to 2-14:

[0236] [Chemical Formula 2-1]

[0237]

[0238] [Chemical Formula 2-2]

[0239]

[0240] [Chemical Formula 2-3]

[0241]

[0242] [Chemical Formula 2-4]

[0243]

[0244] [Chemical Formula 2-5]

[0245]

[0246] [Chemical Formula 2-6]

[0247]

[0248] [Chemical Formula 2-7]

[0249]

[0250] [Chemical Formula 2-8]

[0251]

[0252] [Chemical Formula 2-9]

[0253]

[0254] [Chemical Formula 2-10]

[0255]

[0256] [Chemical Formula 2-11]

[0257]

[0258] [Chemical Formula 2-12]

[0259]

[0260] [Chemical Formula 2-13]

[0261]

[0262] [Chemical Formula 2-14]

[0263] .

[0264] Meanwhile, the amount of the surfactant used is not particularly limited, but may be used in an amount of 0.06 g to 0.48 g per 1,000 g of the functional gel polymer depending on the need for securing productivity or the load condition of the device.

[0265] If the surfactant is used in an excessively small amount, the surfactant may not be evenly adsorbed on the polymer surface, resulting in re-agglomeration of particles after grinding, or absorption performance, such as water retention capacity and absorbency under pressure, may deteriorate due to the surfactant sharing a large amount with the polymer. On the other hand, if the surfactant is used in an excessive amount, the overall physical properties of the final superabsorbent resin may deteriorate due to a decrease in surface tension.

[0266] Therefore, for example, the surfactant may be used in an amount of 0.06 g or more, 0.1 g or more, or 0.2 g or more, and 0.48 g or less, 0.45 g or less, or 0.4 g or less per 1,000 g of the functional gel polymer, and accordingly, it is easy to control the circularity and aspect ratio of the superabsorbent resin of the present invention described above within the desired range.

[0267] The method for mixing these surfactants into the polymer is not particularly limited, and any method capable of evenly mixing them into the polymer may be appropriately employed. Specifically, the surfactants may be mixed dry, dissolved in a solvent and then mixed in a solution state, or melted and then mixed.

[0268] For example, the surfactant may be mixed in a solution state dissolved in a solvent. Any type of solvent, whether inorganic or organic, may be used, but water is most suitable considering the ease of the drying process and the cost of the solvent recovery system. Furthermore, the solution may be prepared by mixing the surfactant and polymer in a reactor, placing the polymer in a mixer and spraying the solution, or continuously supplying the polymer and solution to a continuously operating mixer for mixing.

[0269] Meanwhile, when the surfactant is mixed in a solution state dissolved in water, it can be used by diluting it into an aqueous solution having a concentration of about 0.01% to 90%.

[0270] For example, if the surfactant is to be used at 0.1 g per 1,000 g of the hydrogel polymer, 100 g of an aqueous solution having a concentration of 0.1%, in which 0.1 g of the surfactant is dissolved in 99.9 g of water, may be used. Alternatively, 10 g of an aqueous solution having a concentration of 1%, in which 0.1 g of the surfactant is dissolved in 9.9 g of water, may be used.

[0271] That is, when using the same amount of surfactant, the water content can be increased or decreased to create an aqueous solution having a desired concentration, and the concentration can be appropriately adjusted in consideration of the properties of the superabsorbent resin to be ultimately manufactured.

[0272] According to one embodiment of the invention, a step of neutralizing at least a portion of the acidic groups of the polymer (step 3) is performed, wherein the atomizing step of step 2 and the neutralizing step of step 3 described above may be performed sequentially, alternately, or simultaneously.

[0273] That is, a neutralizing agent may be added to the polymer to first neutralize the acidic groups, and then a surfactant may be added to the neutralized polymer to micronize the polymer mixed with the surfactant (performed in the order of Step 3->Step 2), or the neutralizing agent and the surfactant may be added to the polymer simultaneously to neutralize and micronize the polymer (perform Steps 2 and 3 simultaneously). Alternatively, the surfactant may be added first and the neutralizing agent may be added later (performed in the order of Step 2->Step 3). Alternatively, the neutralizing agent and the surfactant may be added alternately in a cross-sectional manner. Alternatively, the surfactant may be added first to micronize, the neutralizing agent may be added to neutralize, and then an additional surfactant may be added to the neutralized hydrogel polymer to further perform the micronization process.

[0274] Here, if the neutralization step is performed independently from the atomization step of step 2, it can be performed in a manner in which the additive is added while pulverizing the polymer at the same time. More specifically, a screw-type extruder including a porous plate having a plurality of holes formed therein can be used. The screw-type extruder is a device that performs pulverization under milder conditions compared to the atomization device used in the atomization step described above, and the rotation speed can be about 150 rpm to 500 rpm, and the holes of the porous plate can be about 3 mm to 25 mm, but are not limited thereto.

[0275] The rotation speed of the screw-type extruder and the size of the perforated plate holes affect the discharge state of the superabsorbent resin discharged from the extruder, and the particle shape of the superabsorbent resin may change depending on the discharge state.

[0276] In particular, by adjusting the rotation speed of the screw-type extruder to 150 rpm to 500 rpm, the circularity and aspect ratio of the superabsorbent resin of the present invention can be controlled within the desired range.

[0277] At this time, a basic substance such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide that can neutralize acid groups can be used as a neutralizing agent.

[0278] In addition, the degree of neutralization, which refers to the degree of neutralization of acidic groups contained in the polymer by the neutralizing agent, may be 50 to 90 mol%, 60 to 85 mol%, 65 to 85 mol%, or 65 to 80 mol%. The range of the degree of neutralization may vary depending on the final physical properties, and the absorption rate and absorption performance may be controlled by controlling the degree of neutralization.

[0279] At this time, if the degree of neutralization is excessively high, the absorption capacity of the superabsorbent resin may decrease, and if the concentration of carboxyl groups on the particle surface is excessively low, it may be difficult to properly perform surface cross-linking in subsequent processes, which may reduce the pressure-absorbent properties or liquid permeability. Conversely, if the degree of neutralization is excessively low, not only will the polymer's absorption capacity significantly decrease, but it may also exhibit properties similar to elastic rubber that are difficult to handle.

[0280] Meanwhile, it may be desirable to leave a certain time gap between the introduction of the neutralizing agent and the atomization process to ensure even neutralization of the entire polymer.

[0281] Step 4: Drying

[0282] Next, a step (step 4) is performed to dry the above-mentioned micronized and neutralized polymer to prepare a base resin powder.

[0283] The above step is a step of drying the moisture in the base resin powder, which is a polymer obtained by neutralizing at least a portion of the acidic groups of the polymer and pulverizing the polymer.

[0284] In a conventional method for producing a superabsorbent resin, the drying step is performed so that the moisture content of the base resin powder is about 4 to 20 wt%, about 4 to about 15 wt%, or about 6 to about 13 wt%. However, the present invention is not limited thereto.

[0285] The above step 4 can be performed by a fixed-bed type drying method, a moving type drying method, or a combination thereof.

[0286] According to one embodiment of the invention, step 4 can be performed by static drying.

[0287] The above-mentioned static drying method refers to a method in which the material to be dried is placed on a perforated iron plate or other permeable floor, and hot air is passed through the material from below to dry it.

[0288] Since static drying dries in a plate-like shape without particle movement, it is difficult to achieve uniform drying with a simple flow of hot air. Therefore, static drying requires delicate control of hot air and temperature to obtain a uniform, high-moisture content dried body. In the present invention, by changing the hot air direction from downward to upward, warping of the plate-like dried body during drying was prevented, thereby preventing hot air from escaping. In addition, the drying temperature was changed section by section so that the upper, middle, and lower layers within the dried body could be uniformly dried with a moisture content deviation of less than 5%.

[0289] As a device capable of drying using the above-mentioned political drying method, a belt-type dryer may be used, but is not limited thereto.

[0290] In the above-described static drying step, the drying process may be performed at a temperature of about 80°C to 200°C, preferably 90°C to 190°C or 100°C to 180°C. If the drying temperature is lower than 80°C, the drying time may be excessively long, and if the drying temperature is excessively high, exceeding 200°C, a superabsorbent resin having a moisture content lower than the desired moisture content may be obtained. Meanwhile, the drying temperature may refer to the temperature of the hot air used or the internal temperature of the device during the drying process.

[0291] According to one embodiment of the invention, step 4 may be performed by fluid drying.

[0292] The fluidized drying method described above refers to a method of drying in which the material is mechanically stirred during the drying process. The direction in which the hot air passes through the material may be the same as or different from the direction in which the material circulates. Alternatively, the material can be dried by circulating the heat-generating fluid (heat-generating oil) within the dryer and passing it through a separate pipe outside the dryer.

[0293] Devices capable of drying using this fluid drying method include a horizontal-type mixer, a rotary kiln, a paddle dryer, a steam tube dryer, or a generally used fluid dryer.

[0294] In the case of the above-mentioned fluid drying step, the drying process can be performed at a temperature of about 100°C to 300°C, preferably 120°C to 280°C or 150°C to 250°C. If the drying temperature is too low, such as below 100°C, the drying time may be too long, and if the drying temperature is too high, such as exceeding 300°C, the superabsorbent resin polymer chain may be damaged, resulting in a decline in overall physical properties and a superabsorbent resin having a moisture content lower than the desired moisture content may be obtained.

[0295] Step 5: Grinding Stage

[0296] Next, a step of grinding the dried base resin powder is performed.

[0297] Specifically, the above grinding step can be performed by grinding the dry base resin powder to have a particle size of a normal particle level, i.e., a particle size of 150 μm to 850 μm.

[0298] The crusher used for this purpose may be, specifically, a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, a cutter mill, a disc mill, a shred crusher, a crusher, a chopper, or a disc cutter, but is not limited to the examples described above.

[0299] Alternatively, a grinder such as a pin mill, hammer mill, screw mill, roll mill, disc mill or jog mill may be used, but is not limited to the examples described above.

[0300] Meanwhile, in the manufacturing method of the present invention, superabsorbent resin particles having a smaller particle size distribution than in the conventional chopping step can be realized in the micronization step, and since the moisture content after drying is maintained relatively high, even if the pulverization is performed under mild conditions with less pulverization force, a superabsorbent resin having a very high content of normal particle size of 150 ㎛ to 850 ㎛ can be formed, and the fine powder generation ratio can be greatly reduced.

[0301] The superabsorbent resin particles manufactured as described above may contain superabsorbent resin particles having a particle size of 150 ㎛ to 850 ㎛, i.e., normal particles, in an amount of 80 wt% or more, 85 wt% or more, 89 wt% or more, 90 wt% or more, 92 wt% or more, 93 wt% or more, 94 wt% or more, or 95 wt% or more, based on the total weight. The particle size of these resin particles may be measured according to the European Disposables and Nonwovens Association (EDANA) standard EDANA WSP 220.3 method.

[0302] In addition, the superabsorbent resin particles may include fine particles having a particle size of less than 150 μm in an amount of about 20 wt% or less, about 18 wt% or less, about 15 wt% or less, about 13 wt% or less, about 12 wt% or less, about 11 wt% or less, about 10 wt% or less, about 9 wt% or less, about 8 wt% or less, or about 5 wt% or less, relative to the total weight. This is in contrast to having fine particles in an amount of more than about 20 wt% to about 30 wt% when producing a superabsorbent resin according to a conventional production method.

[0303] Additive injection stage

[0304] Meanwhile, according to one embodiment of the invention, a step of adding an additive to the atomized and neutralized polymer may be further included before the drying step (step 4).

[0305] The above additive injection process is a process for improving properties by using additional additives within a range that does not impede the desired effect, and the types of the additives are not particularly limited, and examples thereof include, but are not limited to, a polymerization initiator for removing residual monomers, a permeability improver for improving absorption properties, a fine powder anti-caking agent for recycling the generated fine powder, a fluidity improver, an antioxidant, a neutralizer, a surfactant, etc.

[0306] The above additive injection step may be performed simultaneously with step 2, simultaneously with step 3, after steps 2 and 3, or in at least one or more of these steps. The above additive injection step may be performed multiple times as needed, and may also be performed at least once in each step.

[0307] If the above additive injection step is performed independently from steps 2 and 3, i.e., after steps 2 and 3 and before step 4, it can be performed in such a way that the additive is injected simultaneously with the polymer being crushed.

[0308] The above grinding can be applied in the same manner as the grinding step of step 5 described above, and the additive can be added once or multiple times in the grinding step and mixed with the polymer.

[0309] Classification stage

[0310] Next, after the step of crushing the base resin powder (step 5), a step of classifying the crushed superabsorbent resin particles according to particle size may be further included.

[0311] Surface cross-linking step

[0312] In addition, a step of forming a surface cross-linking layer on at least a portion of the surface of the base resin particles may be further included in the presence of a surface cross-linking agent after the base resin powder has been pulverized (step 5) and / or classified. By this step, the cross-linking polymer contained in the base resin powder may be further cross-linked via the surface cross-linking agent, thereby forming a surface cross-linking layer on at least a portion of the surface of the base resin powder.

[0313] The description of the above surface cross-linking agent can be applied equally to all of the above.

[0314] In addition, there is no limitation on the composition of the method for mixing the surface cross-linking agent with the base resin powder. For example, a method of mixing a composition containing the surface cross-linking agent and the base resin powder by placing them in a reaction tank, a method of spraying the surface cross-linking agent onto the composition, a method of continuously supplying the resin composition and the surface cross-linking agent to a continuously operating mixer, and the like can be used.

[0315] When mixing the surface crosslinking agent and base resin powder, water and methanol may be additionally mixed and added. Adding water and methanol has the advantage of ensuring that the surface crosslinking agent is evenly dispersed throughout the resin composition. The amount of water and methanol added can be appropriately adjusted to ensure even dispersion of the surface crosslinking agent, prevent clumping of the resin composition, and optimize the depth of surface penetration of the crosslinking agent.

[0316] The above surface cross-linking process may be performed at a temperature of about 80° C. to about 250° C. More specifically, the surface cross-linking process may be performed at a temperature of about 100° C. to about 220° C., or about 120° C. to about 200° C., for about 20 minutes to about 2 hours, or about 40 minutes to about 80 minutes. When the above-described surface cross-linking process conditions are met, the surface of the superabsorbent resin particles may be sufficiently cross-linked, thereby increasing the absorbency under pressure.

[0317] The temperature raising means for the above surface crosslinking reaction is not particularly limited.

[0318] Heating can be achieved by supplying a heat medium or directly supplying a heat source. At this time, available heat mediums include, but are not limited to, heated fluids such as steam, hot air, and hot oil. Furthermore, the temperature of the supplied heat medium can be appropriately selected considering the heat medium source, heating rate, and target temperature. Meanwhile, directly supplied heat sources include, but are not limited to, heating via electricity or gas.

[0319] Post-processing step

[0320] According to one embodiment of the present invention, after the step of forming a surface cross-linking layer on at least a portion of the surface of the base resin powder, the method may further include at least one of a cooling step of cooling the superabsorbent resin particles on which the surface cross-linking layer has been formed, a watering step of adding water to the superabsorbent resin particles on which the surface cross-linking layer has been formed, and a post-treatment step of adding an additive to the superabsorbent resin particles on which the surface cross-linking layer has been formed. In this case, the cooling step, the watering step, and the post-treatment step may be performed sequentially or simultaneously.

[0321] In the above-described water step, water or brine can be used, thereby controlling the amount of water generated, etc. The amount of water used can be appropriately adjusted in consideration of the moisture content of the desired final product, etc., and preferably, 0.1 to 10 wt%, 0.5 to 8 wt%, or 1 to 5 wt% can be used relative to the absorbent resin, but is not limited thereto.

[0322] Additionally, after the above-mentioned singer step, a further maturation step can be performed.

[0323] When using brine in the above-mentioned water step, the solution absorption rate is relatively low due to the conductivity of the brine, so that the brine is evenly distributed in the maturation step, enabling even absorption into the absorbent resin. The maturation step may be performed using a commonly used method without any particular limitation, and may be performed, for example, using a rotary stirring device, at a temperature of 100°C or lower, 80°C or lower, and preferably 50°C or lower for 10 minutes to 1 hour.

[0324] The additives added in the above post-processing step may include surfactants, inorganic salts, permeability improvers, anti-caking agents, fluidity improvers, and antioxidants, but the present invention is not limited thereto.

[0325] By selectively performing the above cooling step, water step, and post-treatment step, the moisture content of the final superabsorbent resin can be improved by controlling the occurrence of moisture, etc., and a higher quality superabsorbent resin product can be manufactured.

[0326] Hereinafter, the functions and effects of the invention will be described in more detail through specific examples. However, these examples are provided merely as examples of the invention and do not define the scope of the invention.

[0327] <Example>

[0328] Example 1

[0329] (Step 1: Polymer manufacturing step)

[0330] In a 5 L glass vessel equipped with a stirrer and a thermometer, 1500 g of acrylic acid, 3.75 g of pentaerythritol triallyl ether (PETTAE) as an internal cross-linking agent, and 3401 g of water were stirred and mixed, and reacted while maintaining the temperature at 5°C. The glass vessel containing the mixture was replaced with nitrogen conditions by introducing 1,000 cc / min of nitrogen for 1 hour. Next, 30.0 g of a 0.3% aqueous hydrogen peroxide solution as a polymerization initiator, 15.0 g of a 1% aqueous ascorbic acid solution, and 45.0 g of a 2% aqueous 2,2'-azobis-(2-amidinopropane)dihydrochloric acid solution were added, and at the same time, 22.5 g of a 0.01% aqueous iron sulfate solution as a reducing agent was added to initiate polymerization. After the temperature of the above mixture reached 85°C, a polymer was obtained by polymerizing at 90±2°C for about 6 hours.

[0331] (Steps 2 and 3: Atomization and Neutralization Steps)

[0332] 100 g of a 0.45 wt% aqueous solution of Glycerol Monolaurate (GML) was added to 5,000 g of the polymer obtained in the above step 1. Thereafter, a high-speed rotary shredder (F-150 / Karl Schnell) mounted inside a cylindrical crusher was used to push the polymer through a porous plate having multiple 10 mm holes at a rotation speed of 2,000 rpm, thereby carrying out a particle formation process.

[0333] After this, the recovered hydrogel polymer was extruded three times through a perforated plate having multiple 10 mm holes at a rotation speed of 250 rpm using a screw extruder mounted inside a cylindrical crusher to perform an additional crushing process. 1383 g of a 50% NaOH aqueous solution (Step 3: Neutralization Step) was added to each step of the screw extruder to neutralize some of the acidic groups of the polymer, and then 100 g of fine powder (additional additive addition step) and 157 g of a 10% Na2SO4 aqueous solution (additional additive addition step) were added, respectively, to manufacture hydrogel superabsorbent resin particles (=micronized and neutralized polymer).

[0334] (Step 4: Drying Stage)

[0335] 1,000 g of the above-described superabsorbent resin particles were placed in a dryer containing a porous plate capable of vertical airflow transfer. Hot air of 200°C and 100°C was sequentially flowed from top to bottom for 5 minutes and 10 minutes, respectively, so that the moisture content of the dried superabsorbent resin was approximately 10%, and then hot air of 100°C was flowed from bottom to top for 15 minutes to uniformly dry the polymer.

[0336] (Step 5: Crushing and Classification Stage)

[0337] The above dried body is crushed by a grinder (GRAN-U-LIZER) TM , MPE) and then sieved through a standard mesh sieve of ASTM standards to obtain base resin powder with a size of 150 to 850 μm.

[0338] (Surface cross-linking step)

[0339] Next, a surface cross-linking agent aqueous solution containing 4 g of water, 6 g of methanol, 0.05 g of ethylene glycol diglycidyl ether (EJ-1030S), 0.1 g of propylene glycol, and 0.2 g of aluminum sulfate per 100 g of the base resin powder was sprayed and stirred at room temperature to evenly distribute the surface cross-linking agent on the superabsorbent resin powder. Subsequently, the base resin powder mixed with the surface cross-linking agent was placed in a surface cross-linking reactor to perform a surface cross-linking reaction. Within this surface cross-linking reactor, the base resin powder underwent a surface cross-linking reaction at about 140°C for 40 minutes to obtain a surface-cross-linked superabsorbent resin.

[0340] After the surface cross-linking step, the surface-cross-linked superabsorbent resin was classified through a standard mesh sieve according to ASTM standards to produce a superabsorbent resin (moisture content 1.8%) having a particle size of 150 ㎛ to 850 ㎛.

[0341] Example 2

[0342] (Step 1: Polymer manufacturing step)

[0343] A polymer was obtained in the same manner as in Example 1, except that 3.0 g of pentaerythritol triallyl ether (PETTAE) and 0.75 g of trimethylolpropane triacrylate (TMPTA) (Miramer M3190 product from Miwon) were used instead of 3.75 g of pentaerythritol triallyl ether (PETTAE) as an internal crosslinking agent.

[0344] (Steps 2 and 3: Atomization and Neutralization Steps)

[0345] A water-absorbent polymer particle (=micronized and neutralized polymer) was manufactured in the same manner as in Example 1, except that the rotation speed of the high-speed rotary cutter was set to 2,500 rpm.

[0346] Thereafter, drying, grinding, classification, and surface cross-linking steps were performed in the same manner as in Example 1 to manufacture a superabsorbent resin (moisture content 1.6%).

[0347] Example 3

[0348] (Post-processing stage)

[0349] For the superabsorbent resin manufactured in Example 2 above, an additional step of adding water was performed as follows.

[0350] An aqueous solution containing 4 g of water and about 0.4 g of polycarboxylic acid copolymer per 100 g of the superabsorbent resin manufactured in Example 2 was sprayed and stirred to evenly distribute the aqueous solution over the introduced superabsorbent resin powder. Subsequently, the mixture was evenly mixed for 20 minutes in a reactor at about 50°C to manufacture a superabsorbent resin (water content 4.6%).

[0351] Example 4

[0352] (Step 1: Polymer manufacturing step)

[0353] A polymer was obtained in the same manner as in Example 1 above.

[0354] (Steps 2 and 3: Atomization and Neutralization Steps)

[0355] 299 g of a 0.45 wt% aqueous solution of Glycerol Monolaurate (GML) was added to 5,000 g of the polymer obtained in the above step 1. Thereafter, a high-speed rotary shredder (F-150 / Karl Schnell) installed inside a cylindrical crusher was used to push the polymer through a perforated plate having multiple 10 mm holes at a rotation speed of 2,000 rpm, thereby carrying out a particle formation process.

[0356] After this, the recovered hydrogel polymer was extruded three times through a perforated plate having multiple 10 mm holes at a rotation speed of 150 rpm using a screw extruder mounted inside a cylindrical crusher to perform an additional crushing process. 1383 g of a 50% NaOH aqueous solution (Step 3: Neutralization Step) was added to each step of the screw extruder to neutralize some of the acidic groups of the polymer, and then 100 g of fine powder (additional additive addition step) and 157 g of a 10% Na2SO4 aqueous solution (additional additive addition step) were added, respectively, to manufacture hydrogel superabsorbent resin particles (=micronized and neutralized polymer).

[0357] Thereafter, drying, grinding, classification, and surface cross-linking steps were performed in the same manner as in Example 1 to manufacture a superabsorbent resin (moisture content 1.9%).

[0358] Example 5

[0359] (Step 1: Polymer manufacturing step)

[0360] In a 5 L glass vessel equipped with a stirrer and a thermometer, 1500 g of acrylic acid, 3.75 g of pentaerythritol triallyl ether (PETTAE) as an internal cross-linking agent, and 3401 g of water were stirred and mixed, and the reaction was carried out while maintaining the temperature at 5 ℃. The glass vessel containing the mixture was replaced with nitrogen conditions by introducing 1,000 cc / min of nitrogen for 1 hour. Next, 30.0 g of a 0.3% aqueous hydrogen peroxide solution as a polymerization initiator, 15.0 g of a 1% aqueous ascorbic acid solution, and 45.0 g of a 2% aqueous 2,2'-azobis-(2-amidinopropane)dihydrochloric acid solution were added, and at the same time, 22.5 g of a 0.01% aqueous iron sulfate solution as a reducing agent was added to initiate polymerization. After the temperature of the above mixture reached 85°C, a polymer was obtained by polymerizing at 85±2°C for about 8 hours.

[0361] (Steps 2 and 3: Atomization and Neutralization Steps)

[0362] 100 g of a 0.45 wt% aqueous solution of Glycerol Monolaurate (GML) was added to 5,000 g of the polymer obtained in the above step 1. Thereafter, a high-speed rotary shredder (F-150 / Karl Schnell) installed inside a cylindrical crusher was used to push the polymer through a perforated plate having multiple 15 mm holes at a rotation speed of 1,500 rpm, thereby carrying out a particle formation process.

[0363] After this, the recovered hydrogel polymer was extruded three times through a perforated plate having multiple 6 mm holes at a rotation speed of 500 rpm using a screw extruder mounted inside a cylindrical crusher to perform an additional crushing process. 1383 g of a 50% NaOH aqueous solution (Step 3: Neutralization Step) was added to each step of the screw extruder to neutralize some of the acidic groups of the polymer, and then 100 g of fine powder (additional additive addition step) and 157 g of a 10% Na2SO4 aqueous solution (additional additive addition step) were added, respectively, to manufacture hydrogel superabsorbent resin particles (=micronized and neutralized polymer).

[0364] Thereafter, drying, grinding, classification, and surface cross-linking steps were performed in the same manner as in Example 1 to manufacture a superabsorbent resin (moisture content 1.7%).

[0365] Example 6

[0366] (Step 1: Polymer manufacturing step)

[0367] A polymer was obtained in the same manner as in Example 1, except that 3.0 g of pentaerythritol triallyl ether (PETTAE) and 0.75 g of trimethylolpropane triacrylate (TMPTA) (Miramer M3190 product from Miwon) were used instead of 3.75 g of pentaerythritol triallyl ether (PETTAE) as an internal crosslinking agent.

[0368] (Steps 2 and 3: Atomization and Neutralization Steps)

[0369] 150 g of a 0.45 wt% aqueous solution of Glycerol Monolaurate (GML) was added to 5,000 g of the polymer obtained in the above step 1. Thereafter, a high-speed rotary shredder (F-150 / Karl Schnell) installed inside a cylindrical crusher was used to push the polymer through a perforated plate having multiple 10 mm holes at a rotation speed of 3,000 rpm, thereby carrying out a particle formation process.

[0370] After this, the recovered hydrogel polymer was extruded three times through a perforated plate having multiple 10 mm holes at a rotation speed of 250 rpm using a screw extruder mounted inside a cylindrical crusher to perform an additional crushing process. 1383 g of a 50% NaOH aqueous solution (Step 3: Neutralization Step) was added to each step of the screw extruder to neutralize some of the acidic groups of the polymer, and then 100 g of fine powder (additional additive addition step) and 157 g of a 10% Na2SO4 aqueous solution (additional additive addition step) were added, respectively, to manufacture hydrogel superabsorbent resin particles (=micronized and neutralized polymer).

[0371] Thereafter, drying, grinding, classification, and surface cross-linking steps were performed in the same manner as in Example 1 to manufacture a superabsorbent resin (moisture content 1.8%).

[0372] Comparative Example 1

[0373] (Step 1: Polymer manufacturing step)

[0374] In a 5 L glass vessel equipped with a stirrer and a thermometer, 1500 g of acrylic acid, 5.25 g of pentaerythritol triallyl ether (PETTAE) as an internal cross-linking agent, and 3404 g of water were stirred and mixed, and the reaction was carried out while maintaining the temperature at 5 ° C. The glass vessel containing the mixture was replaced with nitrogen conditions by introducing 1,000 cc / min of nitrogen for 1 hour. Next, 30.0 g of a 0.3% aqueous hydrogen peroxide solution as a polymerization initiator, 15.0 g of a 1% aqueous ascorbic acid solution, and 45.0 g of a 2% aqueous 2,2'-azobis-(2-amidinopropane)dihydrochloric acid solution were added, and at the same time, 22.5 g of a 0.01% aqueous iron sulfate solution as a reducing agent was added to initiate polymerization. After the temperature of the above mixture reached 85°C, a polymer was obtained by polymerizing at 90±2°C for about 6 hours.

[0375] (Steps 2 and 3: Atomization and Neutralization Steps)

[0376] 5,000 g of the polymer obtained in the above step 1 was pushed through a porous plate having multiple 10 mm holes at a rotation speed of 2,000 rpm using a high-speed rotary shredder (F-150 / Karl Schnell) mounted inside a cylindrical crusher to carry out a particle formation process.

[0377] Afterwards, the recovered hydrogel polymer was extruded three times through a perforated plate having multiple 10 mm holes at a rotation speed of 250 rpm using a screw extruder mounted inside a cylindrical crusher to perform an additional crushing process. 1161 g of a 50% NaOH aqueous solution (Step 3: Neutralization Step) was added to each step of the screw extruder to neutralize some of the acidic groups of the polymer, and then 100 g of fine powder (additional additive addition step) and 165 g of a 10% Na2SO4 aqueous solution (additional additive addition step) were added, respectively, to manufacture hydrogel superabsorbent resin particles (=micronized and neutralized polymer).

[0378] (Step 4: Drying Stage)

[0379] 1,000 g of the above-described superabsorbent resin particles were placed in a dryer containing a porous plate capable of vertical airflow transfer. Hot air of 200°C and 100°C was sequentially flowed from top to bottom for 5 minutes and 10 minutes, respectively, so that the moisture content of the dried superabsorbent resin was approximately 10%, and then hot air of 100°C was flowed from bottom to top for 15 minutes to uniformly dry the polymer.

[0380] (Step 5: Crushing and Classification Stage)

[0381] The above dried body is crushed by a grinder (GRAN-U-LIZER) TM , MPE) and then sieved through a standard mesh sieve of ASTM standards to obtain base resin powder with a size of 150 to 850 μm.

[0382] (Surface cross-linking step)

[0383] Next, a surface cross-linking agent aqueous solution containing 5.5 g of water, 6 g of methanol, 0.15 g of ethylene glycol diglycidyl ether (EJ-1030S), and 0.3 g of aluminum sulfate per 100 g of the base resin powder was sprayed and stirred at room temperature to evenly distribute the surface cross-linking agent on the superabsorbent resin powder. Subsequently, the base resin powder mixed with the surface cross-linking agent was placed in a surface cross-linking reactor to perform a surface cross-linking reaction. Within this surface cross-linking reactor, the base resin powder underwent a surface cross-linking reaction at about 140°C for 40 minutes to obtain a surface-cross-linked superabsorbent resin.

[0384] After the surface cross-linking step, the surface-cross-linked superabsorbent resin was classified through a standard mesh sieve according to ASTM standards to produce a superabsorbent resin having a particle size of 150 μm to 850 μm.

[0385] Comparative Example 2

[0386] (Step 1: Polymer manufacturing step)

[0387] In a 5 L glass vessel equipped with a stirrer and a thermometer, 1500 g of acrylic acid, 5.25 g of pentaerythritol triallyl ether (PETTAE) as an internal cross-linking agent, and 3404 g of water were stirred and mixed, and the reaction was carried out while maintaining the temperature at 5 ° C. The glass vessel containing the mixture was replaced with nitrogen conditions by introducing 1,000 cc / min of nitrogen for 1 hour. Next, 30.0 g of a 0.3% aqueous hydrogen peroxide solution as a polymerization initiator, 15.0 g of a 1% aqueous ascorbic acid solution, and 45.0 g of a 2% aqueous 2,2'-azobis-(2-amidinopropane)dihydrochloric acid solution were added, and at the same time, 22.5 g of a 0.01% aqueous iron sulfate solution as a reducing agent was added to initiate polymerization. After the temperature of the above mixture reached 85°C, a polymer was obtained by polymerizing at 90±2°C for about 6 hours.

[0388] (Steps 2 and 3: Atomization and Neutralization Steps)

[0389] 597 g of a 0.45 wt% aqueous solution of Glycerol Monolaurate (GML) was added to 5,000 g of the polymer obtained in the above step 1. Thereafter, a high-speed rotary shredder (F-150 / Karl Schnell) mounted inside a cylindrical crusher was used to push the polymer through a perforated plate having multiple 10 mm holes at a rotation speed of 2,000 rpm, thereby carrying out a particle formation process.

[0390] Afterwards, the recovered hydrogel polymer was extruded three times through a perforated plate having multiple 10 mm holes at a rotation speed of 250 rpm using a screw extruder mounted inside a cylindrical crusher to perform an additional crushing process. 1037 g of a 50% NaOH aqueous solution (Step 3: Neutralization Step) was added to each step of the screw extruder to neutralize some of the acidic groups of the polymer, and then 100 g of fine powder (additional additive addition step) and 150 g of a 10% Na2SO4 aqueous solution (additional additive addition step) were added, respectively, to manufacture hydrogel superabsorbent resin particles (=micronized and neutralized polymer).

[0391] (Step 4: Drying Stage)

[0392] 1,000 g of the above-described superabsorbent resin particles were placed in a dryer containing a porous plate capable of vertical airflow transfer. Hot air of 200°C and 100°C was sequentially flowed from top to bottom for 5 minutes and 10 minutes, respectively, so that the moisture content of the dried superabsorbent resin was approximately 10%, and then hot air of 100°C was flowed from bottom to top for 15 minutes to uniformly dry the polymer.

[0393] (Step 5: Crushing and Classification Stage)

[0394] The above dried body is crushed by a grinder (GRAN-U-LIZER) TM , MPE) and then sieved through a standard mesh sieve of ASTM standards to obtain base resin powder with a size of 150 to 850 μm.

[0395] (Surface cross-linking step)

[0396] Next, a surface cross-linking agent aqueous solution containing 5.5 g of water, 5 g of methanol, and 0.07 g of ethylene glycol diglycidyl ether (EJ-1030S) per 100 g of the base resin powder was sprayed and stirred at room temperature to evenly distribute the surface cross-linking agent on the superabsorbent resin powder. Subsequently, the base resin powder mixed with the surface cross-linking agent was placed in a surface cross-linking reactor to perform a surface cross-linking reaction. Within this surface cross-linking reactor, the base resin powder underwent a surface cross-linking reaction at about 140°C for 40 minutes to obtain a surface-cross-linked superabsorbent resin.

[0397] After the surface cross-linking step, the surface-cross-linked superabsorbent resin was classified through a standard mesh sieve according to ASTM standards to produce a superabsorbent resin having a particle size of 150 μm to 850 μm.

[0398] Comparative Example 3

[0399] (Step 1: Polymer manufacturing step)

[0400] In a 5 L glass vessel equipped with a stirrer and a thermometer, 1500 g of acrylic acid, 3.75 g of pentaerythritol triallyl ether (PETTAE) as an internal cross-linking agent, and 3400 g of water were stirred and mixed, and the reaction was carried out while maintaining the temperature at 5 ° C. The glass vessel containing the mixture was replaced with nitrogen conditions by introducing 1,000 cc / min of nitrogen for 1 hour. Next, 30.0 g of a 0.3% aqueous hydrogen peroxide solution as a polymerization initiator, 15.0 g of a 1% aqueous ascorbic acid solution, and 45.0 g of a 2% aqueous 2,2'-azobis-(2-amidinopropane)dihydrochloric acid solution were added, and at the same time, 22.5 g of a 0.01% aqueous iron sulfate solution as a reducing agent was added to initiate polymerization. After the temperature of the above mixture reached 85°C, a polymer was obtained by polymerizing at 90±2°C for about 6 hours.

[0401] (Steps 2 and 3: Atomization and Neutralization Steps)

[0402] In the above step 1, 100 g of a 0.45 wt% aqueous solution of Glycerol Monolaurate (GML) was added to 5,000 g of the polymer obtained. Thereafter, the hydrogel polymer was extruded three times through a perforated plate having multiple 10 mm holes at a rotation speed of 250 rpm using a screw extruder mounted inside a cylindrical crusher to perform an additional pulverization process. 1,383 g of a 50% NaOH aqueous solution (step 3: neutralization step) was added to each step of the screw extruder to neutralize some of the acidic groups of the polymer, and then 100 g of fine powder (additional additive addition step) and 162 g of a 10% Na2SO4 aqueous solution (additional additive addition step) were added, respectively, to manufacture hydrogel superabsorbent resin particles (=micronized and neutralized polymer).

[0403] (Step 4: Drying Stage)

[0404] 1,000 g of the above-described superabsorbent resin particles were placed in a dryer containing a porous plate capable of vertical airflow transfer. Hot air of 200°C and 100°C was sequentially flowed from top to bottom for 5 minutes and 10 minutes, respectively, so that the moisture content of the dried superabsorbent resin was approximately 10%, and then hot air of 100°C was flowed from bottom to top for 15 minutes to uniformly dry the polymer.

[0405] (Step 5: Crushing and Classification Stage)

[0406] The above dried body is crushed by a grinder (GRAN-U-LIZER) TM , MPE) and then sieved through a standard mesh sieve of ASTM standards to obtain base resin powder with a size of 150 to 850 μm.

[0407] (Surface cross-linking step)

[0408] Next, a surface cross-linking agent aqueous solution containing 3.5 g of water, 5 g of methanol, and 0.12 g of ethylene glycol diglycidyl ether (EJ-1030S) per 100 g of the base resin powder was sprayed and stirred at room temperature to evenly distribute the surface cross-linking agent on the superabsorbent resin powder. Subsequently, the base resin powder mixed with the surface cross-linking agent was placed in a surface cross-linking reactor to perform a surface cross-linking reaction. Within this surface cross-linking reactor, the base resin powder underwent a surface cross-linking reaction at about 140°C for 40 minutes to obtain a surface-cross-linked superabsorbent resin.

[0409] After the surface cross-linking step, the surface-cross-linked superabsorbent resin was classified through a standard mesh sieve according to ASTM standards to produce a superabsorbent resin having a particle size of 150 μm to 850 μm.

[0410] Comparative Example 4

[0411] (Step 1: Polymer manufacturing step)

[0412] In a 5 L glass vessel equipped with a stirrer and a thermometer, 1500 g of acrylic acid, 3.0 g of pentaerythritol triallyl ether (PETTAE) as an internal cross-linking agent, and 3399 g of water were stirred and mixed, and the reaction was carried out while maintaining the temperature at 5 ° C. The glass vessel containing the mixture was replaced with nitrogen conditions by introducing 1,000 cc / min of nitrogen for 1 hour. Next, 30.0 g of a 0.3% aqueous hydrogen peroxide solution as a polymerization initiator, 15.0 g of a 1% aqueous ascorbic acid solution, and 45.0 g of a 2% aqueous 2,2'-azobis-(2-amidinopropane)dihydrochloric acid solution were added, and at the same time, 22.5 g of a 0.01% aqueous iron sulfate solution as a reducing agent was added to initiate polymerization. After the temperature of the above mixture reached 85°C, a polymer was obtained by polymerizing at 90±2°C for about 6 hours.

[0413] (Steps 2 and 3: Atomization and Neutralization Steps)

[0414] In the above step 1, 100 g of a 0.45 wt% aqueous solution of Glycerol Monolaurate (GML) was added to 5,000 g of the polymer obtained. Thereafter, the hydrogel polymer was extruded three times through a perforated plate having multiple 10 mm holes at a rotation speed of 250 rpm using a screw extruder mounted inside a cylindrical crusher to perform an additional pulverization process. 1,140 g of a 50% NaOH aqueous solution (step 3: neutralization step) was added to each step of the screw extruder to neutralize some of the acidic groups of the polymer, and then 100 g of fine powder (additional additive addition step) and 162 g of a 10% Na2SO4 aqueous solution (additional additive addition step) were added, respectively, to manufacture hydrogel superabsorbent resin particles (=micronized and neutralized polymer).

[0415] (Step 4: Drying Stage)

[0416] 1,000 g of the above-described superabsorbent resin particles were placed in a dryer containing a porous plate capable of vertical airflow transfer. Hot air of 200°C and 100°C was sequentially flowed from top to bottom for 5 minutes and 10 minutes, respectively, so that the moisture content of the dried superabsorbent resin was approximately 10%, and then hot air of 100°C was flowed from bottom to top for 15 minutes to uniformly dry the polymer.

[0417] (Step 5: Crushing and Classification Stage)

[0418] The above dried body is crushed by a grinder (GRAN-U-LIZER) TM , MPE) and then sieved through a standard mesh sieve of ASTM standards to obtain base resin powder with a size of 150 to 850 μm.

[0419] (Surface cross-linking step)

[0420] Next, a surface cross-linking agent aqueous solution containing 5 g of water, 6 g of methanol, 0.15 g of ethylene carbonate, and 0.38 g of aluminum sulfate per 100 g of the base resin powder was sprayed and stirred at room temperature to evenly distribute the surface cross-linking agent on the superabsorbent resin powder. Subsequently, the base resin powder mixed with the surface cross-linking agent was placed in a surface cross-linking reactor to perform a surface cross-linking reaction. Within this surface cross-linking reactor, the base resin powder underwent a surface cross-linking reaction at about 185°C for 50 minutes to obtain a surface-cross-linked superabsorbent resin.

[0421] After the surface cross-linking step, the surface-cross-linked superabsorbent resin was classified through a standard mesh sieve according to ASTM standards to produce a superabsorbent resin having a particle size of 150 μm to 850 μm.

[0422] Comparative Example 5

[0423] (Step 1: Polymer manufacturing step)

[0424] In a 5 L glass vessel equipped with a stirrer and a thermometer, 1450 g of acrylic acid, 3.63 g of pentaerythritol triallyl ether (PETTAE) as an internal cross-linking agent, and 3454 g of water were stirred and mixed, and reacted while maintaining the temperature at 5 ° C. The glass vessel containing the mixture was replaced with nitrogen conditions by introducing 1,000 cc / min of nitrogen for 1 hour. Next, 29.0 g of a 0.3% aqueous hydrogen peroxide solution as a polymerization initiator, 14.5 g of a 1% aqueous ascorbic acid solution, and 43.5 g of a 2% aqueous 2,2'-azobis-(2-amidinopropane)dihydrochloric acid solution were added, and at the same time, 21.75 g of a 0.01% aqueous iron sulfate solution as a reducing agent was added to initiate polymerization. After the temperature of the above mixture reached 85°C, a polymer was obtained by polymerizing at 90±2°C for about 6 hours.

[0425] (Steps 2 and 3: Atomization and Neutralization Steps)

[0426] In the above step 1, 96 g of a 0.45 wt% aqueous solution of Glycerol Monolaurate (GML) was added to 5,000 g of the polymer obtained. Thereafter, the hydrogel polymer was extruded three times through a perforated plate having multiple 10 mm holes at a rotation speed of 250 rpm using a screw extruder mounted inside a cylindrical crusher to perform an additional pulverization process. 1,417 g of a 50% NaOH aqueous solution (step 3: neutralization step) was added to each step of the screw extruder to neutralize some of the acidic groups of the polymer, and then 100 g of fine powder (additional additive addition step) and 159 g of a 10% Na2SO4 aqueous solution (additional additive addition step) were added, respectively, to manufacture hydrogel superabsorbent resin particles (=micronized and neutralized polymer).

[0427] (Step 4: Drying Stage)

[0428] 1,000 g of the above-described superabsorbent resin particles were placed in a dryer containing a porous plate capable of vertical airflow transfer. Hot air of 200°C and 100°C was sequentially flowed from top to bottom for 5 minutes and 10 minutes, respectively, so that the moisture content of the dried superabsorbent resin was approximately 10%, and then hot air of 100°C was flowed from bottom to top for 15 minutes to uniformly dry the polymer.

[0429] (Step 5: Crushing and Classification Stage)

[0430] The above dried body is crushed by a grinder (GRAN-U-LIZER) TM , MPE) and then sieved through a standard mesh sieve of ASTM standards to obtain base resin powder with a size of 150 to 850 μm.

[0431] (Surface cross-linking step)

[0432] Next, a surface cross-linking agent aqueous solution containing 3.5 g of water, 5 g of methanol, and 0.1 g of ethylene glycol diglycidyl ether (EJ-1030S) per 100 g of the base resin powder was sprayed and stirred at room temperature to evenly distribute the surface cross-linking agent on the superabsorbent resin powder. Subsequently, the base resin powder mixed with the surface cross-linking agent was placed in a surface cross-linking reactor to perform a surface cross-linking reaction. Within this surface cross-linking reactor, the base resin powder underwent a surface cross-linking reaction at about 140°C for 40 minutes to obtain a surface-cross-linked superabsorbent resin.

[0433] After the surface cross-linking step, the surface-cross-linked superabsorbent resin was classified through a standard mesh sieve according to ASTM standards to produce a superabsorbent resin having a particle size of 150 μm to 850 μm.

[0434] Comparative Example 6

[0435] (Step 1: Polymer manufacturing step)

[0436] In a 5 L glass vessel equipped with a stirrer and a thermometer, 1400 g of acrylic acid, 2.8 g of pentaerythritol triallyl ether (PETTAE) as an internal cross-linking agent, and 3506 g of water were stirred and mixed, and the reaction was carried out while maintaining the temperature at 5 ℃. The glass vessel containing the mixture was replaced with nitrogen conditions by introducing 1,000 cc / min of nitrogen for 1 hour. Next, 28.0 g of a 0.3% aqueous hydrogen peroxide solution as a polymerization initiator, 14.0 g of a 1% aqueous ascorbic acid solution, and 42.0 g of a 2% aqueous 2,2'-azobis-(2-amidinopropane)dihydrochloric acid solution were added, and at the same time, 21.0 g of a 0.01% aqueous iron sulfate solution as a reducing agent was added to initiate polymerization. After the temperature of the above mixture reached 85°C, a polymer was obtained by polymerizing at 90±2°C for about 6 hours.

[0437] (Steps 2 and 3: Atomization and Neutralization Steps)

[0438] In the above step 1, 279 g of a 0.45 wt% aqueous solution of Glycerol Monolaurate (GML) was added to 5,000 g of the polymer obtained. Thereafter, the hydrogel polymer was extruded three times through a perforated plate having multiple 10 mm holes at a rotation speed of 250 rpm using a screw extruder mounted inside a cylindrical crusher to perform an additional pulverization process. 1,027 g of a 50% NaOH aqueous solution (step 3: neutralization step) was added to each step of the screw extruder to neutralize some of the acidic groups of the polymer, and then 100 g of fine powder (additional additive addition step) and 149 g of a 10% Na2SO4 aqueous solution (additional additive addition step) were added, respectively, to manufacture hydrogel superabsorbent resin particles (=micronized and neutralized polymer).

[0439] (Step 4: Drying Stage)

[0440] 1,000 g of the above-described superabsorbent resin particles were placed in a dryer containing a porous plate capable of vertical airflow transfer. Hot air of 200°C and 100°C was sequentially flowed from top to bottom for 5 minutes and 10 minutes, respectively, so that the moisture content of the dried superabsorbent resin was approximately 10%, and then hot air of 100°C was flowed from bottom to top for 15 minutes to uniformly dry the polymer.

[0441] (Step 5: Crushing and Classification Stage)

[0442] The above dried body is crushed by a grinder (GRAN-U-LIZER) TM , MPE) and then sieved through a standard mesh sieve of ASTM standards to obtain base resin powder with a size of 150 to 850 μm.

[0443] (Surface cross-linking step)

[0444] Next, a surface cross-linking agent aqueous solution containing 3.5 g of water, 5 g of methanol, 0.15 g of ethylene carbonate, and 0.2 g of aluminum sulfate per 100 g of the base resin powder was sprayed and stirred at room temperature to evenly distribute the surface cross-linking agent on the superabsorbent resin powder. Subsequently, the base resin powder mixed with the surface cross-linking agent was placed in a surface cross-linking reactor to perform a surface cross-linking reaction. Within this surface cross-linking reactor, the base resin powder underwent a surface cross-linking reaction at about 185°C for 50 minutes to obtain a surface-cross-linked superabsorbent resin.

[0445] After the surface cross-linking step, the surface-cross-linked superabsorbent resin was classified through a standard mesh sieve according to ASTM standards to produce a superabsorbent resin having a particle size of 150 μm to 850 μm.

[0446] Comparative Example 7

[0447] (Step 1: Polymer manufacturing step)

[0448] In a 5 L glass vessel equipped with a stirrer and a thermometer, 1400 g of acrylic acid, 2.8 g of pentaerythritol triallyl ether (PETTAE) as an internal cross-linking agent, and 3506 g of water were stirred and mixed, and the reaction was carried out while maintaining the temperature at 5 ℃. The glass vessel containing the mixture was replaced with nitrogen conditions by introducing 1,000 cc / min of nitrogen for 1 hour. Next, 28.0 g of a 0.3% aqueous hydrogen peroxide solution as a polymerization initiator, 14.0 g of a 1% aqueous ascorbic acid solution, and 42.0 g of a 2% aqueous 2,2'-azobis-(2-amidinopropane)dihydrochloric acid solution were added, and at the same time, 21.0 g of a 0.01% aqueous iron sulfate solution as a reducing agent was added to initiate polymerization. After the temperature of the above mixture reached 85°C, a polymer was obtained by polymerizing at 90±2°C for about 6 hours.

[0449] (Steps 2 and 3: Atomization and Neutralization Steps)

[0450] In the above step 1, 279 g of a 0.45 wt% aqueous solution of Glycerol Monolaurate (GML) was added to 5,000 g of the polymer obtained. Thereafter, the hydrogel polymer was extruded three times through a perforated plate having multiple 10 mm holes at a rotation speed of 250 rpm using a screw extruder mounted inside a cylindrical crusher to perform an additional pulverization process. 1,027 g of a 50% NaOH aqueous solution (step 3: neutralization step) was added to each step of the screw extruder to neutralize some of the acidic groups of the polymer, and then 100 g of fine powder (additional additive addition step) and 149 g of a 10% Na2SO4 aqueous solution (additional additive addition step) were added, respectively, to manufacture hydrogel superabsorbent resin particles (=micronized and neutralized polymer).

[0451] (Step 4: Drying Stage)

[0452] 1,000 g of the above-described superabsorbent resin particles were placed in a dryer containing a porous plate capable of vertical airflow transfer. Hot air of 200°C and 100°C was sequentially flowed from top to bottom for 5 minutes and 10 minutes, respectively, so that the moisture content of the dried superabsorbent resin was approximately 10%, and then hot air of 100°C was flowed from bottom to top for 15 minutes to uniformly dry the polymer.

[0453] (Step 5: Crushing and Classification Stage)

[0454] The above dried body is crushed by a grinder (GRAN-U-LIZER) TM , MPE) and then sieved through a standard mesh sieve of ASTM standards to obtain base resin powder with a size of 150 to 850 μm.

[0455] (Surface cross-linking step)

[0456] Next, a surface cross-linking agent aqueous solution containing 4.5 g of water, 5 g of methanol, 0.1 g of ethylene glycol diglycidyl ether (EJ-1030S), and 0.4 g of aluminum sulfate per 100 g of the base resin powder was sprayed and stirred at room temperature to evenly distribute the surface cross-linking agent on the superabsorbent resin powder. Subsequently, the base resin powder mixed with the surface cross-linking agent was placed in a surface cross-linking reactor to perform a surface cross-linking reaction. Within this surface cross-linking reactor, the base resin powder underwent a surface cross-linking reaction at about 140°C for 40 minutes to obtain a surface-cross-linked superabsorbent resin.

[0457] After the surface cross-linking step, the surface-cross-linked superabsorbent resin was classified through a standard mesh sieve according to ASTM standards to produce a superabsorbent resin having a particle size of 150 μm to 850 μm.

[0458] <Experimental Example>

[0459] The properties of the superabsorbent resins manufactured in the above examples and comparative examples were evaluated using the following methods and are listed in Table 1 below.

[0460] Unless otherwise specified, all of the following property evaluations were conducted under constant temperature and humidity (23±1℃, relative humidity 50±10%), and saline solution or saline refers to a 0.9 wt% sodium chloride (NaCl) aqueous solution.

[0461] After the sample to be measured was left under constant temperature and humidity conditions for 24 hours, each property was evaluated.

[0462] Additionally, unless otherwise noted, the property evaluations for the surface-crosslinked final superabsorbent resin were performed on resins having particle sizes of 150 μm to 850 μm classified through an ASTM standard sieve.

[0463] (1) Measurement of circularity and aspect ratio of superabsorbent resin particles

[0464] For the superabsorbent resins of the above examples and comparative examples, the circularity and aspect ratio were measured using Malvern Panalytical's Morphologi 4 by the following method.

[0465] ① Sample Preparation: A 1 g particle sample of the superabsorbent resin to be measured was prepared. In order to measure the circularity and aspect ratio of particles having a particle size of 300 ㎛ to 600 ㎛, the superabsorbent resin was classified using a particle classifier from Retsch at 1.0 amplitude for 10 minutes to separate individual particles having a particle size of 300 ㎛ to 600 ㎛ without damaging the particles, thereby preparing a 1 g sample. The setting values ​​of the Sample Dispersion Unit at this time are as shown in Fig. 1.

[0466] ② Image acquisition: The prepared sample was placed on the stage within the equipment and scanned at 2.5x magnification to acquire images of individual particles. The Illumination Setting and Optics Selection Setting values ​​are shown in Figures 2 and 3, respectively.

[0467] ③ Image processing: For the acquired images, the parameter values ​​such as the 3D image of the 3D particle for each particle was captured as a 2D image, the CE diameter (Circle Equivalent diameter), the shortest diameter, the longest diameter, the actual particle perimeter, and the convex hull perimeter were measured. At this time, the Scan Area setting value is as shown in Fig. 4, and the measurement was performed without setting the Filtering value for the particle.

[0468] ④ Based on the data analyzed for each particle, shape data values ​​for all particles included in the sample were obtained.

[0469] Circularity average HS Circularity average Aspect ratio average CE Diameter average (㎛) Example 10.73 0.54 0.70 245 Example 20.77 0.59 0.71 312 Example 30.77 0.60 0.73 301 Example 40.86 0.74 0.80 301 Example 50.74 0.55 0.70 284 Example 60.77 0.58 0.71 309 Comparative Example 10.82 0.68 0.78 422 Comparative Example 20.85 0.72 0.80 445 Comparative Example 30.91 0.82 0.79 521 Comparative Example 40.92 0.83 0.82 481 Comparative Example 50.91 0.82 0.80 444 Comparative Example 60.930.850.81475Comparative example 70.920.830.81463

[0470] Example 1 Example 4 Circularity Average 300-600 ㎛ particles 0.71 0.82 Total particles 0.73 0.86 Ratio of circularity of particles having a diameter of 300 ㎛ to 600 ㎛ to the circularity of all particles 0.97 0.95

[0471] (2) Centrifuge Retention Capacity (CRC, g / g) The retention capacity by the absorption rate under no-load of the superabsorbent resins of the above examples and comparative examples was measured according to the European Disposables and Nonwovens Association (EDANA) standard EDANA WSP 241.3.

[0472] Measurements were performed at a temperature of 23±2℃ and a relative humidity of 45±15% as described in EDANA WSP 241.0.

[0473] Specifically, the superabsorbent resin W0(g) (approximately 0.2 g) obtained through each of the examples and comparative examples was uniformly placed in a nonwoven bag, sealed, and then immersed in a physiological saline solution (0.9 wt%) at room temperature. After 30 minutes, water was removed from the bag for 3 minutes using a centrifuge at 250 G, and the mass W2(g) of the bag was measured. In addition, the same operation was performed without using the resin, and the mass W1(g) at that time was measured.

[0474] Using each mass obtained, CRC (g / g) was calculated according to the following mathematical formula 1.

[0475] [Mathematical Formula 1]

[0476] CRC (g / g) = {[W2(g) - W1(g)] / W0(g)} - 1

[0477] The above measurement was repeated five times, and the average value and standard deviation were calculated.

[0478] (3) Absorbency under Pressure (AUP: Absorbency under Pressure, g / g)

[0479] The pressurized absorption capacity of 2.07 kPa (0.3 psi) of the superabsorbent resins of the above examples and comparative examples was measured according to EDANA method WSP 242.3.

[0480] Measurements were performed at a temperature of 23±2℃ and a relative humidity of 45±15% as described in EDANA WSP 242.0.

[0481] Specifically, a 400-mesh stainless steel wire mesh was installed on the bottom of a plastic cylinder with an inner diameter of 25 mm. Under conditions of room temperature and 50% humidity, superabsorbent resin W0 (g) (0.9 g) was uniformly sprayed on the wire mesh, and a piston capable of uniformly applying a load of 2.07 kPa (0.3 psi) was installed thereon, with an outer diameter slightly smaller than 25 mm, without a gap with the inner wall of the cylinder, and without impeding up-and-down movement. At this time, the weight W3 (g) of the device was measured.

[0482] A glass filter with a diameter of 90 mm and a thickness of 5 mm was placed inside a petri dish with a diameter of 150 mm, and a saline solution consisting of 0.9 wt% sodium chloride was placed so that it was level with the upper surface of the glass filter. A sheet of filter paper with a diameter of 90 mm was placed on top of it. The measuring device was placed on the filter paper, and the liquid was absorbed under a load for 1 hour. After 1 hour, the measuring device was lifted, and its weight W4 (g) was measured.

[0483] Using each mass obtained, the pressurized absorbency (g / g) was calculated according to the following mathematical formula 2.

[0484] [Equation 2]

[0485] AUP(g / g) = [W4(g) - W3(g)] / W0(g)

[0486] The above measurement was repeated five times, and the average value and standard deviation were calculated.

[0487] (4) Vortex time

[0488] The vortex time of the superabsorbent resins of the above examples and comparative examples was measured by the following method.

[0489] ① First, 50 mL of 0.9% saline solution was added to a 100 mL beaker with a flat bottom using a 100 mL mass cylinder.

[0490] ② Next, the beaker was placed in the center of the magnetic stirrer, and a circular magnetic bar (diameter 30 mm) was placed inside the beaker.

[0491] ③ Afterwards, the stirrer was operated so that the magnetic bar stirred at 600 rpm, and the lowest part of the vortex created by stirring was made to touch the top of the magnetic bar.

[0492] ④ After confirming that the temperature of the brine in the beaker reached 24.0℃, 2±0.01 g of superabsorbent resin sample was added while simultaneously operating the stopwatch, and the time until the vortex disappeared and the liquid surface became completely horizontal was measured in seconds, which was designated as the vortex time.

[0493] (5) 1-minute absorption capacity in water with an electrical conductivity value of 110 μS / cm (EC 110 μS / cm 1-minute absorption capacity)

[0494] 1.0 g (W5) of the superabsorbent resins of the examples and comparative examples were placed in a nonwoven bag (18 cm Х 28 cm) and immersed in 1000 mL of water having an electrical conductivity of 110 μS / cm at 24°C for 1 minute. After 1 minute, the bag was taken out of the distilled water, hung, and left for 1 minute. Thereafter, the mass (W7) of the bag was measured. In addition, the same operation was performed without using the superabsorbent resin, and the mass at that time (W6) was measured. Using each mass thus obtained, the absorbency (g / g) in water having an electrical conductivity of 110 μS / cm was calculated according to the following mathematical equation 3.

[0495] [Equation 3]

[0496] Absorption capacity in water with an electrical conductivity of 110 μS / cm = {[W7(g) - W6(g) - W5(g)] / W5(g)}

[0497] CRC(g / g)AUP(g / g)EFFCvortex time (sec)110μS / cm1 min Absorption capacity (g / g)Example 138.631.535.114212Example 237.431.434.419204Example 336.829.833.319217Example 435.333.334.327186Example 537.032.134.620201Example 638.430.534.513217Comparative Example 128.527.528.042118Comparative Example 232.628.230.545105Comparative Example 336.128.932.575124Comparative Example 437.029.933.59081Comparison Example 537.724.731.270115Comparison Example 638.841.735.310291Comparison Example 744.225.234.792100

[0498] As can be seen in Table 3 above, in the case of the present invention, it was confirmed that by controlling the circularity and aspect ratio within a specific range, the absorption speed can be improved while simultaneously improving absorption performance such as centrifugal retention capacity and pressurized absorption capacity, thereby exhibiting an excellent balance of physical properties.

[0499] The present invention can be applied to superabsorbent resins.

Claims

1. As a polyacrylic acid (salt) type super absorbent resin, The average value of circularity calculated by the following equation 1 for all particles is 0.90 or less, and the average value of aspect ratio (A / R), which means the ratio of the shortest diameter of the particle to the longest diameter of the particle, is 0.70 or more. An absorbency under pressure (AUP) of 25 g / g or more as measured at 2.07 kPa (0.3 psi) in accordance with EDANA Law WSP 242.

3. Superabsorbent resin: [Formula 1] Circularity = perimeter of CE particle / perimeter of actual particle In the above equation 1, The perimeter of a CE particle refers to the perimeter of a circle (Circle Equivalent) that has the same area as the image captured as a 2D image of the 3D image of the 3D particle to be measured (CE Perimeter). The actual particle perimeter refers to the actual perimeter length of the image captured as a 2D image of the 3D image of the 3D particle to be measured (Perimeter).

2. In paragraph 1, A superabsorbent resin having an average circularity value of 0.70 to 0.90 for all particles.

3. In paragraph 1, A superabsorbent resin having an average aspect ratio of the entire particles of 0.70 to 0.

85.

4. In paragraph 1, A superabsorbent resin having an average value of HS circularity (HS circularity) calculated by the following equation 2 for all particles of 0.80 or less: [Formula 2] HS circularity = (circumference of CE particle) 2 / (circumference of actual particle) 2 In the above equation 2, The perimeter of the CE particle and the perimeter of the actual particle are as defined in Article 1.

5. In paragraph 1, A superabsorbent resin having an average HS circularity of 0.50 to 0.80 for all particles.

6. In paragraph 1, A superabsorbent resin, wherein the ratio of the circularity of particles having a particle size of 300 ㎛ to 600 ㎛ to the circularity of all particles of the superabsorbent resin is 0.9 to 1.

1.

7. In paragraph 1, A superabsorbent resin having an average CE diameter of 220 ㎛ to 400 ㎛.

8. In paragraph 1, The above superabsorbent resin is a superabsorbent resin having a water retention capacity (CRC) of 33 g / g or more as measured according to the method of EDANA method WSP 241.

3.

9. In paragraph 1, The above superabsorbent resin is a superabsorbent resin having an effective absorbency (EFFC) of 30 g / g or more, calculated by the following Equation 3; [Formula 3] Effective absorbency (EFFC) = {Conservative Retention Capacity (CRC) + Absorbency under Pressure (AUP) of 2.07 kPa (0.3 psi)} / 2.

10. In paragraph 1, A superabsorbent resin having a vortex time of 40 seconds or less as measured by a vortex measurement method at 24.0°C.

11. In paragraph 1, A superabsorbent resin, wherein when 1 g of the superabsorbent resin is swelled in water having an electrical conductivity value of 110 μS / cm for 1 minute, the maximum capacity of water that the superabsorbent resin can hold (Free Swell Capacity) is 170 g or more.

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