Coated resin particles and method for producing coated resin particles

Abstract

The present invention relates to a coated resin particle that has a water-absorbing resin particle and a coating layer that coats at least a part of the surface of the water-absorbing resin particle. The coating layer is capable of disintegrating because of the expansion that accompanies absorption of water by the water-absorbing resin particle, or is capable of spreading with the expansion that accompanies absorption of water by the water-absorbing resin particle.

Description

[Technical Field]

[0001] The present invention relates to coated resin particles and a method for producing coated resin particles. [Background technology]

[0002] Water-absorbent resin particles are widely used in various fields, such as sanitary materials such as disposable diapers, sanitary products, and portable toilets; agricultural and horticultural materials such as water retention agents and soil conditioners; and industrial materials such as waterproofing agents and anti-condensation agents. In addition to high water absorption capacity and gel strength, water-absorbent resin particles are required to have controllable water absorption speed. The water absorption speed can be controlled, for example, by varying the specific surface area of ​​the water-absorbent resin particles or the amount of crosslinking agent used. For example, paragraph

[0062] of Patent Document 1 discloses that "by subjecting a hydrogel having an internal crosslinked structure to a post-crosslinking reaction, the crosslink density near the surface of the water-absorbent resin is increased, thereby increasing the water absorption speed." [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-28117 Summary of the Invention [Problem to be solved by the invention]

[0004] Conventional water-absorbent resin particles begin to absorb water and reach a swollen state (a state in which they can no longer absorb water) in a relatively short time after coming into contact with a liquid to be absorbed, such as water or urine (hereinafter simply referred to as "liquid"). When the water-absorbent resin particles swell, the gaps that originally existed between the water-absorbent resin particles are filled with the swollen gel-like water-absorbent resin particles, making it difficult for the liquid to pass through the gaps. This is generally referred to as the gel-blocking phenomenon. As a result, it becomes difficult for the liquid to diffuse through the gaps, which is one cause of liquid leakage. According to the findings of the present inventors, slowing the water-absorption rate of the water-absorbent resin (e.g., delaying the time it takes for the particles to reach a swollen state and / or the time it starts to absorb water) is effective in suppressing the gel-blocking phenomenon. For example, it is conceivable to delay the time it takes for the water-absorbent resin particles to reach a swollen state by changing the specific surface area of ​​the water-absorbent resin particles or the amount of crosslinking agent used. However, it is difficult to find the optimal conditions for these measures. Furthermore, water-absorbent resin particles usually start absorbing water quickly when they come into contact with a liquid, so it is difficult to delay the time at which the water-absorbent resin particles start absorbing water (water-absorption start time).

[0005] The present invention has been made in consideration of such problems, and aims to provide coated resin particles that have a controlled water absorption rate (delaying the time it takes for the particles to reach a swollen state and / or the time it starts to absorb water), and a method for producing the same. [Means for solving the problem]

[0006] One aspect of the present invention provides coated resin particles having water-absorbent resin particles and a coating layer covering at least a part of the surface of the water-absorbent resin particles, wherein the coating layer is disintegrable due to expansion of the water-absorbent resin particles as they absorb water, or is expandable in accordance with expansion of the water-absorbent resin particles as they absorb water.

[0007] Another aspect of the present invention provides a method for producing the above-mentioned coated resin particles, comprising a step of mixing water-absorbent resin particles with a coating material to form a coating layer on at least a part of the surface of the water-absorbent resin particles. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide coated resin particles in which the water absorption rate is controlled to be slow, and a method for producing the same. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a cross-sectional perspective view schematically illustrating one embodiment of coated resin particles. [Figure 2] 1 is a cross-sectional perspective view schematically illustrating one embodiment of coated resin particles. [Figure 3] 1 is a cross-sectional perspective view schematically illustrating one embodiment of coated resin particles. [Figure 4] 1 is a cross-sectional view schematically illustrating one embodiment of a coated resin particle. [Figure 5] 1 is a graph showing the water absorption behavior of water-absorbent resin particles and coated resin particles. [Figure 6] FIG. 1 is a schematic diagram showing a device for measuring the pressureless DW of water-absorbent resin particles and coated resin particles. [Figure 7] 3 is a photograph showing the state of the coated resin particles of Example 1 after absorbing water. [Figure 8] 1 is a photograph showing the state of the water-absorbent resin particles of Comparative Example 1 after absorbing water. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, several embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0011] In this specification, "acrylic" and "methacrylic" are collectively referred to as "(meth)acrylic." Similarly, "acrylate" and "methacrylate" are also referred to as "(meth)acrylate." "(Poly)" refers to both cases with and without the prefix "poly." In the numerical ranges described in this specification, the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of another numerical range. In the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the Examples. The materials exemplified in this specification may be used alone or in combination of two or more. When multiple substances corresponding to each component are present in the composition, the content of each component refers to the total amount of the multiple substances present in the composition, unless otherwise specified. "Room temperature" refers to 25±2°C. The term "layer" encompasses structures that are formed over the entire surface as well as structures that are formed only partially when observed in a plan view.

[0012] [Coated resin particles] (Basic structure of coated resin particles) The coated resin particles of the present invention have water-absorbent resin particles and a coating layer that covers at least a part of the surface of the water-absorbent resin particles, and the coating layer is disintegrable due to the expansion of the water-absorbent resin particles as they absorb water, or is expandable in accordance with the expansion of the water-absorbent resin particles as they absorb water.

[0013] The coating layer may be water-permeable or water-impermeable, but when the entire surface of the water-absorbent resin particle is covered with the coating layer, a water-permeable coating layer is used. Note that "the coating layer is water-permeable" means that a 0.9 mass % sodium chloride aqueous solution (hereinafter simply referred to as "physiological saline") can permeate the coating layer and can reach the opposite surface from the surface (i.e., the water-absorbent resin particle) after a predetermined time has elapsed. The time required for the physiological saline to permeate from the surface to the opposite surface is, for example, within 6 hours, preferably within 3 hours, and more preferably within 2 hours.

[0014] The coating layer is preferably chemically and / or physically bonded to the surface of the water-absorbent resin particle so as not to easily fall off from the water-absorbent resin particle before absorbing water. The physical bond is realized, for example, by an anchor effect caused by the coating layer penetrating into minute recesses present on the surface of the water-absorbent resin particle.

[0015] The water-absorbent resin particles are prevented from contacting liquids at the portions coated with the coating layer. Therefore, if the entire surface of the water-absorbent resin particles is coated with the coating layer, the water-absorbent resin particles cannot instantly absorb liquids. On the other hand, if only a portion of the surface of the water-absorbent resin particles is coated with the coating layer, the water-absorbent resin particles can instantly absorb liquids at the exposed surface portions (portions not coated with the coating layer), but the coating layer functions as a binder that inhibits the expansion of the water-absorbent resin particles. Therefore, if a coating layer is provided on at least a portion of the surface of the water-absorbent resin particles, the water-absorbent resin particles cannot exhibit their inherent water-absorbing ability. However, in the present invention, the coating layer is disintegrable due to the expansion of the water-absorbent resin particles as they absorb water, or is expandable in response to the expansion of the water-absorbent resin particles as they absorb water. Therefore, the water-absorbent resin particles gradually exhibit their inherent water-absorbent ability and eventually reach a swollen state.

[0016] Hereinafter, a presumed mechanism by which the water absorption rate can be controlled by the coated resin particles of the present invention will be described with reference to Figures 1 to 5. In this specification, in order to distinguish between "a coating layer that can be disintegrated by expansion caused by the water absorption of the water-absorbent resin particles" and "a coating layer that can be spread in accordance with expansion caused by the water absorption of the water-absorbent resin particles", for convenience, the former will be referred to as coating layer A and the latter as coating layer B, and both will be collectively referred to as coating layer.

[0017] <Coated resin particles having coating layer A> FIG. 1 is a cross-sectional perspective view schematically illustrating one embodiment of a coated resin particle. In the coated resin particle 1 shown in FIG. 1(a), the entire surface of a water-absorbent resin particle 10 is coated with a coating layer A12. Even if the coated resin particle 1 comes into contact with a liquid, the water-absorbent resin particle 10 cannot immediately absorb the liquid due to the presence of the coating layer A12. However, because the coating layer A12 is water-permeable, the liquid gradually permeates the coating layer A12 and reaches the water-absorbent resin particle 10, and at that moment, the water-absorbent resin particle 10 begins to expand as it absorbs the liquid. Then, as shown in FIG. 1(b), the coating layer A12 cracks (i.e., the coating layer A12 collapses) due to the internal pressure caused by the expansion of the water-absorbent resin particle 10 (hereinafter simply referred to as "expansion force"), and a part of the surface of the water-absorbent resin particle 10a is exposed. Thereafter, the expansion force of the water-absorbent resin particles 10 increases more and more, and accordingly the cracks in the coating layer A12 become larger and larger, and the water-absorbent resin particles 10a become more likely to come into contact with a liquid. When the coating layer A12 is sufficiently broken down, the expansion of the water-absorbent resin particles 10a is not substantially hindered, and finally, the water-absorbent resin particles 10a in a swollen state are obtained.

[0018] FIG. 2 is a cross-sectional perspective view schematically illustrating another embodiment of coated resin particles. In the coated resin particles 2 shown in FIG. 2(a), a portion of the surface of the water-absorbent resin particle 10 is coated with a coating layer A14. In this embodiment, a continuous band-like coating layer A14 is provided around the water-absorbent resin particle 10. When the coated resin particle 2 comes into contact with moisture, water absorption and expansion begin from the surface of the water-absorbent resin particle 10 that is not covered by the coating layer A14. However, in this embodiment, since the coating layer A14 is provided so as to wrap around the water-absorbent resin particle 10, even if water absorption occurs, the coating layer A14 functions as a binder, and expansion of the water-absorbent resin particle 10 is suppressed to some extent. Thereafter, when the expansion force of the water-absorbent resin particle 10 increases, the coating layer A14 collapses as shown in FIG. 2(b), and finally, a swollen water-absorbent resin particle 10a is obtained.

[0019] FIG. 3 is a cross-sectional perspective view schematically illustrating another embodiment of coated resin particles. In the coated resin particle 3 shown in FIG. 3(a), a coating layer A16 covers part of the surface of the water-absorbent resin particle 10 in an island-like (discontinuous) pattern. When the coated resin particle 3 comes into contact with moisture, water absorption and expansion begin from the surface of the water-absorbent resin particle 10 that is not covered with the coating layer A16. When the water-absorbent resin particle 10 absorbs water, the surface of the water-absorbent resin particle 10 tends to shift position relative to the lower surface of each corresponding island (coating layer A16) due to expansion (increase in surface area) caused by water absorption. In this embodiment, each island 16 is chemically and / or physically bonded to the surface of the water-absorbent resin particle 10 at its lower surface, and this bonded portion inhibits positional displacement (i.e., expansion of the water-absorbent resin particle 10). However, when the expansion force of the water-absorbent resin particle 10 increases further, the surface area of ​​the water-absorbent resin particle 10 also tends to increase accordingly, and strong tensile stress is applied to each island 16 bonded to the surface of the water-absorbent resin particle 10. As a result, the bond between the water-absorbent resin particle 10 and each island 16 cannot be maintained, and in some cases, as shown in Fig. 3(b), each island 16 cracks and collapses, and finally, a swollen water-absorbent resin particle 10a is obtained.

[0020] In the example shown in Fig. 3, the coating layer A16 collapses due to the generation of cracks, but the generation of cracks is not essential for the collapse of the coating layer A16. For example, if the bonding strength between the coating layer A16 and the surface of the water-absorbent resin particle 10 is weak, the bond between the coating layer A16 and the water-absorbent resin particle 10 can no longer be maintained before a tensile stress strong enough to cause cracks is applied to the coating layer A16, and the coating layer A16 may fall off from the water-absorbent resin particle 10 without causing cracks. In such a case, it can also be said that the coating layer A16 has collapsed. Furthermore, when the water-absorbent resin particle reaches a swollen state, a part or all of the coating layer A16 may fall off from the surface of the water-absorbent resin particle.

[0021] <Coated resin particles having coating layer B> FIG. 4 is a cross-sectional view schematically illustrating another embodiment of coated resin particles. In the coated resin particle 4 shown in FIG. 4(a), the entire surface of the water-absorbent resin particle 10 is coated with a coating layer B18. Even if the coated resin particle 4 comes into contact with a liquid, the water-absorbent resin particle 10 cannot immediately absorb the liquid due to the presence of the coating layer B18. However, because the coating layer B18 is water-permeable, the liquid gradually permeates the coating layer B18 and reaches the water-absorbent resin particle 10, at which point the water-absorbent resin particle 10 begins to expand as it absorbs the liquid. Although an expansion force is applied to the coating layer B18 in association with the expansion of the water-absorbent resin particle 10, the coating layer B18 can be spread in response to the expansion of the water-absorbent resin particle 10. Therefore, as shown in FIG. 4(b), the coating layer B18 remains in close contact with the surface of the expanded water-absorbent resin particle 10a even as its thickness decreases. In other words, the coating layer B18 does not substantially collapse due to the expansion of the water-absorbent resin particle 10. Therefore, even if the water-absorbent resin particles 10a in a swollen state are finally obtained, the surfaces thereof are covered with the coating layer B18. In the present embodiment, the coating layer B18 does not substantially collapse, and therefore the effect of suppressing the expansion of the water-absorbent resin particles 10 can continue until just before the water-absorbent resin particles 10 reach a swollen state.

[0022] As described above, the coated resin particles of the present invention have a specific coating layer on the water-absorbent resin particles, so that the water-absorbent resin particles have a suppressed water-absorption capacity. In other words, the coated resin particles take longer to reach a swollen state than when only the water-absorbent resin particles constituting the coated resin particles are used. The change in the amount of water absorption that the coated resin particles can exhibit will be described below with reference to FIG. 5.

[0023] Fig. 5 is a graph showing the change in water absorption over time after contact with a liquid for each of coated resin particles and water-absorbent resin particles constituting the coated resin particles (hereinafter simply referred to as "water absorption behavior"). Note that Fig. 5 is not a graph obtained by actually measuring specific coated resin particles and water-absorbent resin particles, but a conceptual diagram showing the concept of the present invention.

[0024] The water absorption behavior of the coated resin particles may be, for example, as shown in (a) of Figure 5, "compared to water-absorbent resin particles, the time at which they start absorbing water (the moment the coated resin particles come into contact with a liquid) is the same, but the amount of water absorbed is generally consistently small, so the time until they reach a swollen state is slower," or as shown in (b) of Figure 5, "compared to water-absorbent resin particles, the time at which they start absorbing water and the time until they reach a swollen state are both slower," or as shown in (c) of Figure 5, "compared to water-absorbent resin particles, the time at which they start absorbing water is the same (the moment the coated resin particles come into contact with a liquid), but the amount of water absorbed in the initial stage is significantly smaller, so the time until they reach a swollen state is slower."

[0025] As described above, the coated resin particles have a slower water absorption rate than when only water-absorbent resin particles are used. Therefore, by using the coated resin particles of the present invention, the occurrence of gel-blocking can be more effectively suppressed than when only water-absorbent resin particles are used. The coated resin particles are preferably those whose water absorption amount increases significantly after a certain period of time has passed, as shown in Figure 5(b) or (c), and more preferably those that do not absorb liquid until a certain period of time has passed, as shown in Figure 5(b). In particular, coated resin particles that exhibit water-absorbing behavior such as that shown in Figure 5(b) do not absorb liquid until a certain period of time has passed, and therefore can more effectively suppress the occurrence of gel-blocking.

[0026] When the coated resin particles exhibit water absorption behavior as shown in Figure 5(b), the time it takes for the coated resin particles to start absorbing water after contact with saline may be, for example, 3 to 120 minutes, 5 to 90 minutes, or 10 to 60 minutes. When the coated resin particles exhibit water absorption behavior as shown in Figure 5(c), the time it takes for the coated resin particles to exhibit 10% of their water absorption capacity after contact with saline may be, for example, 3 to 120 minutes, 5 to 90 minutes, or 10 to 60 minutes. Note that "exhibiting 10% of their water absorption capacity" means absorbing saline equivalent to 10% by mass of the total amount of water absorbed in the swollen state.

[0027] The water absorption behavior that can be easily achieved will be explained for each aspect of the coating layer. When the coating layer A or the coating layer B covers the entire surface of the water-absorbent resin particle, even if the coated resin particle comes into contact with a liquid, water absorption does not substantially start until the liquid that has permeated the coating layer reaches the water-absorbent resin particle, and as a result, the coated resin particle is likely to exhibit the water absorption behavior as shown in (b) of Figure 5. In this case, the time until the coated resin particle starts to absorb water can be appropriately controlled by the forming material and / or thickness of the coating layer A or the coating layer B.

[0028] On the other hand, when the coating layer A or the coating layer B covers a part of the surface of the water-absorbent resin particle, water absorption starts the moment the coated resin particle comes into contact with a liquid, but the expansion of the water-absorbent resin particle is suppressed by the coating layer A or the coating layer B. Therefore, the coated resin particle cannot exhibit sufficient water absorption ability until the coating layer A is sufficiently disintegrated or the coating layer B is spread, and as a result, the coated resin particle is likely to exhibit water absorption behavior such as that shown in (a) or (c) of Figure 5. Whether the coated resin particle exhibits water absorption behavior such as that shown in (a) of Figure 5 (the amount of water absorption per unit time is relatively constant until the coated resin particle reaches a swollen state) or water absorption behavior such as that shown in (c) of Figure 5 (the amount of water absorption increases sharply after a certain time has passed) can be appropriately controlled by the forming materials, thicknesses, and / or coverage rates of the coating layers A and B.

[0029] (Water-absorbing resin particles) The water-absorbent resin particles are not particularly limited as long as they are made of a resin having water absorption properties. The water-absorbent resin particles may contain, for example, a crosslinked polymer formed by polymerization of a monomer containing an ethylenically unsaturated monomer. The crosslinked polymer may have a monomer unit derived from the ethylenically unsaturated monomer. The water-absorbent resin particles can be produced, for example, by a method including a step of polymerizing a monomer containing an ethylenically unsaturated monomer. Examples of the polymerization method include reverse-phase suspension polymerization, aqueous solution polymerization, bulk polymerization, and precipitation polymerization.

[0030] The ethylenically unsaturated monomer may be a water-soluble ethylenically unsaturated monomer (an ethylenically unsaturated monomer having a solubility of 1.0 g or more in 100 g of water at 25°C). Examples of water-soluble ethylenically unsaturated monomers include (meth)acrylic acid and its salts, 2-(meth)acrylamido-2-methylpropanesulfonic acid and its salts, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, N-methylol(meth)acrylamide, polyethylene glycol mono(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N-diethylaminopropyl(meth)acrylate, and diethylaminopropyl(meth)acrylamide. When the ethylenically unsaturated monomer has an amino group, the amino group may be quaternized. The ethylenically unsaturated monomer may be used alone or in combination of two or more.

[0031] When the ethylenically unsaturated monomer has an acid group, the acid group may be neutralized with an alkaline neutralizing agent before the polymerization reaction. The degree of neutralization of the ethylenically unsaturated monomer with the alkaline neutralizing agent may be, for example, 10 to 100 mol %, 50 to 90 mol %, or 60 to 80 mol % of the acid group in the ethylenically unsaturated monomer.

[0032] From the viewpoint of industrial ease of availability, the ethylenically unsaturated monomer may include at least one compound selected from the group consisting of (meth)acrylic acid and its salts, acrylamide, methacrylamide, and N,N-dimethylacrylamide. The ethylenically unsaturated monomer may include at least one compound selected from the group consisting of (meth)acrylic acid and its salts, and acrylamide.

[0033] As a monomer for obtaining water-absorbing resin particles, a monomer other than the above-mentioned ethylenically unsaturated monomer may be used. Such a monomer may be used, for example, by mixing with an aqueous solution containing the above-mentioned ethylenically unsaturated monomer. The amount of the ethylenically unsaturated monomer used may be 70 to 100 mol% based on the total amount of monomers. The proportion of (meth)acrylic acid and its salts may be 70 to 100 mol% based on the total amount of monomers.

[0034] During polymerization, crosslinking occurs due to self-crosslinking, but crosslinking may be promoted by using an internal crosslinking agent. The use of an internal crosslinking agent makes it easy to control the water absorption properties (water retention capacity, etc.) of the water-absorbent resin particles. The internal crosslinking agent is usually added to the reaction solution during the polymerization reaction.

[0035] The water-absorbent resin particles may be crosslinked near the surface (surface crosslinked). The water-absorbent resin particles may be composed of polymer particles (crosslinked polymers) alone, or may further contain various additional components selected from, for example, gel stabilizers, metal chelating agents, and flow improvers (lubricants). The additional components may be located inside the polymer particles, on the surfaces of the polymer particles, or both. The additional component may be a flow improver (lubricant). The flow improver may contain inorganic particles. Examples of inorganic particles include silica particles such as amorphous silica.

[0036] The shape of the water-absorbent resin particles is not particularly limited, and may be, for example, substantially spherical, crushed or granular, or may be an aggregate of primary particles having these shapes.

[0037] The water-absorbent resin particles may have a median particle diameter of 100 to 800 μm, 150 to 700 μm, 200 to 600 μm, or 250 to 500 μm. The median particle diameter is measured by the method described in the examples.

[0038] The water absorption amount of the water-absorbent resin particles in physiological saline may be, for example, 10 to 100 g / g, 20 to 90 g / g, or 30 to 80 g / g at 25° C. The water absorption amount is measured by the method described in the examples.

[0039] The swelling force of the water-absorbent resin particles may be, for example, 1 to 100 N, 5 to 80 N, 10 to 70 N, or 15 to 60 N. The swelling force of the water-absorbent resin particles in this specification is equal to the swelling force (60-second value) of the water-absorbent resin particles measured by the procedure described in

[0085] to

[0089] of WO 2018 / 181548.

[0040] (coating layer) The coating layer preferably contains a water-insoluble component. In this specification, the water-insoluble component may include not only a completely water-insoluble substance but also a substance that is slightly soluble in water (a poorly water-soluble substance). The solubility of the water-insoluble component in 100 g of water at 25°C is, for example, less than 1.0 g, preferably less than 0.8 g, more preferably less than 0.6 g, and even more preferably less than 0.4 g. The solubility is measured by the method described in the Examples. Below, the water-insoluble component will be explained separately for coating layer A and coating layer B.

[0041] (Coating layer A) The water-insoluble component that can be contained in the coating layer A may be an organic compound (hereinafter simply referred to as an "organic water-insoluble component") or an inorganic compound (hereinafter simply referred to as an "inorganic water-insoluble component").

[0042] The organic water-insoluble component is preferably solid or waxy at room temperature, and is preferably plastic when hot (120°C) or at room temperature (25°C). Examples of organic water-insoluble components include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate; polyamides such as nylon 6 and nylon 66; polyolefins such as polyethylene, polypropylene, ethylene-butene copolymer, and ethylene-propylene copolymer; polyurethanes such as ether-based polyurethanes, ester-based polyurethanes, and carbonate-based polyurethanes; polystyrenes such as poly-α-methylstyrene and syndiotactic polystyrene; polycarbonates such as bisphenol A and polyhexamethylene carbonate; polyacrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; polyacetals such as polyoxymethylene, polyacetaldehyde, polypropionaldehyde, and polybutyraldehyde; halogen-based polymers such as polyvinyl chloride, polyvinyl fluoride, and polyvinylidene fluoride; sucrose fatty acid esters; and polysiloxanes. These organic water-insoluble components may be used alone or in combination of two or more. In addition, the organic water-insoluble component may be acid-modified, since this makes it easier to control the water absorption behavior of the coated resin particles.

[0043] Polyurethane is a reaction product of a polyol and a polyisocyanate. Examples of polyols include polyether polyols, polyester polyols, polybutadiene polyols, and hydrogenated polybutadiene polyols. Examples of polyisocyanates include aromatic isocyanates such as diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and p-phenylene diisocyanate; alicyclic isocyanates such as dicyclohexylmethane diisocyanate and isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate.

[0044] As the organic water-insoluble component that can be contained in the water-insoluble component, it is preferable to use at least one selected from the group consisting of polyurethane, polyolefin, polyester, polyamide, polystyrene, polycarbonate, polyacrylate, polyacetal, polyvinyl chloride, sucrose fatty acid ester, and acid-modified products thereof, because this makes it easier to control the water absorption behavior of the coated resin particles. It is more preferable to use at least one selected from the group consisting of polyolefin, polyurethane, polyester, polyvinyl chloride, sucrose fatty acid ester, and acid-modified products thereof. It is even more preferable to use at least one selected from the group consisting of polyolefin, polyurethane, polyvinyl chloride, and acid-modified products thereof. It is particularly preferable to use polyvinyl chloride, acid-modified polyolefin and / or polyurethane.

[0045] When the organic water-insoluble component is acid-modified, the organic water-insoluble component may be modified with at least one acid anhydride selected from the group consisting of maleic anhydride, succinic anhydride, and phthalic anhydride. The material to be modified with the acid anhydride is preferably a polyolefin, more preferably polyethylene, polypropylene, and / or an ethylene-propylene copolymer, and even more preferably an ethylene-propylene copolymer. Furthermore, the acid anhydride used for modification is preferably maleic anhydride.

[0046] Examples of inorganic water-insoluble components include light anhydrous silicic acid, calcium silicate, silicon dioxide, talc, silicon oxide, and synthetic hydrotalcite. These inorganic water-insoluble components may be used alone or in combination. Preferably, at least one of silicon dioxide and talc is used because they can exhibit relatively high water permeability when a coating layer is formed.

[0047] The coating layer A needs to withstand the expansion force of the water-absorbent resin particles to a certain extent, while easily collapsing when the expansion force exceeds a certain level. In consideration of this, the organic insoluble component may have a tensile strength of 0.1 to 200 MPa, 0.5 to 150 MPa, 1 to 100 MPa, or 2 to 80 MPa. The tensile strength is measured in accordance with JIS K7161 (Testing methods for tensile properties of plastics).

[0048] (Coating layer B) The water-insoluble component that can be contained in the coating layer B is a water-insoluble component that can be spread as the water-absorbent resin particles expand. The water-insoluble component that can be contained in the coating layer B includes, for example, at least one selected from the group consisting of rubber latex and a water-absorbent resin, and preferably includes a water-absorbent resin.

[0049] Examples of rubber latex include styrene-butadiene rubber latex, nitrile rubber latex, acrylic rubber latex, polybutadiene rubber latex, butyl rubber latex, CR latex, IR latex, and polysulfide rubber latex. One type of rubber latex may be used alone, or multiple types may be used in combination.

[0050] When a water-absorbent resin is used as the water-insoluble component, the material for forming the water-absorbent resin (hereinafter referred to as "coated water-absorbent resin" to distinguish it from water-absorbent resin particles) may be, for example, the same monomer as the material for forming the water-absorbent resin particles described above, or may be a precursor of the water-absorbent resin (a polymer that is not sufficiently cross-linked to the extent that it can function as a water-absorbent resin; hereinafter simply referred to as "precursor").

[0051] Specifically, the monomer used to form the coated water-absorbent resin is preferably a water-soluble ethylenically unsaturated monomer, more preferably an ethylenically unsaturated monomer other than (meth)acrylic acid and its salts, and even more preferably (meth)acrylamide, because this makes it easier to control the water absorption behavior of the coated resin particles. A water-insoluble component (crosslinked polymer) that can be contained in the coating layer B can be prepared by polymerizing this monomer. Furthermore, the precursor used to form the coated water-absorbent resin is preferably at least one selected from polyacrylic acid and polyacrylamide. It is preferable that the coated water-absorbent resin absorbs less saline than the water-absorbent resin particles.

[0052] Coating layer A and coating layer B are preferably composed essentially of water-insoluble components, but may contain small amounts of components other than the water-insoluble components (hereinafter simply referred to as "other components"). When other components are contained, the proportion of the water-insoluble components in the entire coating layer is, for example, 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more. By including other components in the coating layer, the water absorption behavior of the coated resin particles can be appropriately controlled. Examples of other components include water-soluble components such as polyethylene glycol and polyvinyl alcohol, each of which has a solubility of 1.0 g or more in 100 g of water at 25°C.

[0053] Coating layer A or coating layer B may also contain a crosslinked water-soluble component such as polyethylene glycol or polyvinyl alcohol as a coating material.

[0054] Coating layer A or coating layer B may have a single-layer structure or a multilayer structure having two or more layers. For example, coating layer A may have a first layer containing an organic water-insoluble component and a second layer containing an inorganic water-insoluble component that covers at least a portion of the surface of the first layer, or the reverse layer structure. Coating layer B may have a first layer containing rubber latex and a second layer containing a coated water-absorbent resin that covers at least a portion of the surface of the first layer, or the reverse layer structure. By making coating layer A or coating layer B a multilayer structure, coated resin particles that exhibit more complex water absorption behavior can be produced.

[0055] From the viewpoint of controlling the water absorption behavior of the coated resin particles, the thickness of the coating layer (when the coating layer has a multilayer structure, this refers to the total thickness obtained by adding up the thicknesses of the individual layers) may be 0.001 to 100 μm, 0.01 to 50 μm, or 0.1 to 30 μm. The thickness of the coating layer can be calculated by observing the cross-section of the coated resin particle using an optical microscope. Specifically, the thickness is calculated by processing the cross-section of the coated resin particle using an ultramicrotome, and then observing the cross-section using an optical microscope "SZX16" (manufactured by Olympus) and a confocal microscope OPTELEICS HYBRID (manufactured by Lasertec).

[0056] The coating layer only needs to cover at least a part of the surface of the water-absorbent resin particle, and the water absorption behavior of the coated resin particle can be controlled depending on the coverage rate. The coverage rate of the surface of the water-absorbent resin particle by the coating layer may be 30% or more, 40% or more, or 50% or more, or may be 100% or less, 90% or less, or 80% or less. The coverage rate is calculated using RAMAN touch (manufactured by Nanophoton Inc.).

[0057] In the coated resin particles of the present invention, at least a portion of the surface of the water-absorbent resin particle is coated with coating layer A or coating layer B. Therefore, the water-absorbent resin particle cannot exhibit its inherent water-absorbing ability until the coating layer collapses due to the swelling of the water-absorbent resin particle as it absorbs water, or until the coating layer expands in response to the swelling of the water-absorbent resin particle as it absorbs water. Therefore, the coated resin particle takes longer to reach a swollen state than when the water-absorbent resin particle, which is its constituent material, is used alone, and as a result, the occurrence of the gel-blocking phenomenon can be suppressed. In particular, the coated resin particle of the present invention can be easily produced by providing a coating layer on the surface of the water-absorbent resin particle.

[0058] The coated resin particles of the present invention can be used alone, or can be used as mixed particles by mixing with water-absorbent resin particles other than the coated resin particles (hereinafter simply referred to as "other water-absorbent resin particles"). By using mixed particles, the time required to reach a swollen state can be delayed compared to when the other water-absorbent resin particles are used alone, and as a result, the occurrence of gel blocking can be suppressed. Furthermore, when mixed particles are used, any water absorption behavior can be achieved by appropriately changing the type of coated resin particles, the type of other water-absorbent resin particles, the mixing ratio of the coated resin particles and the other water-absorbent resin particles, etc.

[0059] [Method of manufacturing coated resin particles] The method for producing coated resin particles of the present invention comprises a step of mixing water-absorbent resin particles with a coating material to form a coating layer on at least a part of the surface of the water-absorbent resin particles.

[0060] The proportion of the coating material mixed with the water-absorbent resin particles (proportion of the coating material) may be 0.1% by mass or more, 0.2% by mass or more, 0.5% by mass or more, 1.0% by mass or more, 1.5% by mass or more, or 2.0% by mass or more. The proportion may be 50% by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less. The water absorption rate of the coated resin particles can be changed by appropriately changing this proportion. The proportion of the coating material is calculated based on the formula described in the Examples of this specification.

[0061] The coating material is, for example, a compound containing a water-insoluble component capable of forming the above-mentioned coating layer. When the water-insoluble component contains a polymer, the coating material may include not only the polymer itself but also a material that forms the polymer.

[0062] For example, when the coating layer contains polyurethane as a water-insoluble component, the coating material may contain polyurethane itself, or may contain polyol and polyisocyanate, which are materials for forming the polyurethane. Also, when the coating layer contains a coated water-absorbent resin as a water-insoluble component, the coating material may contain the coated water-absorbent resin itself, or may contain a monomer, which is a material for forming the coated water-absorbent resin, or may contain a precursor, which is a material for forming the coated water-absorbent resin.

[0063] When the coating material contains a polymer-forming material (other than a precursor), the method for producing coated resin particles of the present invention preferably further comprises a step of mixing the water-absorbent resin particles with the coating material and then polymerizing the coating material.When the coating material contains a precursor of the coated water-absorbent resin, the method for producing coated resin particles of the present invention preferably further comprises a step of mixing the water-absorbent resin particles with the coating material and then crosslinking the coating material with a crosslinking agent.Specific methods for producing coated resin particles will be described below for each state of the coating material.

[0064] <When using solid coating materials> In this case, a particle compositing device can be used to pressure-bond a coating material onto the surfaces of water-absorbent resin particles to form a coating layer. Specifically, a predetermined amount of water-absorbent resin particles and a solid (e.g., powder) coating material are charged into the particle compositing device. Thereafter, stress (compressive stress and shear stress) is applied to the water-absorbent resin particles and the coating material by rotation of an agitator blade provided in the device, and the coating material is pressure-bonded onto the surfaces of the water-absorbent resin particles by the stress, thereby producing coated resin particles.

[0065] In this case, the thickness and coverage of the coating layer can be adjusted as desired by appropriately adjusting the amounts of water-absorbent resin particles and coating material added to the particle compositing device. While the water-absorbent resin particles and coating material may be added separately to the particle compositing device, it is preferable to add the water-absorbent resin particles and coating material mixed together in advance to the particle compositing device, as this is expected to result in a more uniform coating. When a particle compositing device is used, coated resin particles in which a coating layer is applied to a portion of the surface of the water-absorbent resin particles are likely to be obtained, and therefore, the coated resin particles are likely to exhibit the water absorption behavior shown in Figure 5(a) or (c). For example, the particle compositing device Nobilta MINI (manufactured by Sugino Machine Co., Ltd.) can be used as the particle compositing device.

[0066] <When using liquid coating materials> A liquid coating material (hereinafter simply referred to as a "coating liquid") can be obtained, for example, by melting the coating material, or by dissolving or dispersing the coating material in any solvent or dispersion medium. Since this makes it easier to form a coating layer of uniform thickness, it is preferable to obtain a coating liquid by dissolving or dispersing the coating material in any solvent or dispersion medium. Whether the coating liquid is a solution or a dispersion depends on the properties of the coating material and the medium used.

[0067] Examples of solvents or dispersion media include water, hydrophilic compounds, mixtures of water and hydrophilic compounds, and hydrocarbon compounds. Hydrophilic compounds are compounds that dissolve substantially uniformly in water. Examples of hydrophilic compounds include alcohols such as methanol and isopropyl alcohol; glycols such as ethylene glycol; cellosolves such as methyl cellosolve and ethyl cellosolve; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; and ethers such as tetrahydrofuran. Examples of hydrocarbon compounds include chain aliphatic hydrocarbons such as n-hexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 3-ethylpentane, and n-octane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, trans-1,2-dimethylcyclopentane, cis-1,3-dimethylcyclopentane, and trans-1,3-dimethylcyclopentane; and aromatic hydrocarbons such as benzene, toluene, and xylene. These compounds may be used alone or in combination of two or more.

[0068] The concentration of the coating material in the coating liquid is not particularly limited, and can be appropriately adjusted in consideration of the amount of the water-absorbent resin particles to be coated in order to obtain a coating layer of a desired thickness, and may be, for example, 1 to 50 mass %, 3 to 30 mass %, or 5 to 20 mass %.

[0069] When a coating liquid is used, the coating layer can be formed by, for example, (1) a method of adding the coating liquid to a hydrocarbon dispersion medium in which water-absorbent resin particles are dispersed, (2) a method of adding the coating liquid and water-absorbent resin particles to a hydrocarbon dispersion medium at approximately the same time, (3) a method of bringing the coating liquid into contact with water-absorbent resin particles in a dry state, (4) a method of polymerizing the coating material in the presence of water-absorbent resin particles, or (5) a method of crosslinking the coating material (including a precursor) using a crosslinking agent in the presence of water-absorbent resin particles. Each method will be specifically described below.

[0070] An example of the above method (1) will be described. First, a separable flask equipped with a reflux condenser, a dropping funnel, a nitrogen gas inlet tube, and a stirrer is prepared. Subsequently, a hydrocarbon dispersion medium and water-absorbent resin particles are charged into the separable flask, and the mixture is thoroughly stirred while maintaining a high temperature (for example, 60 to 80°C). Meanwhile, a solvent or dispersion medium and a coating material are added to a beaker and mixed to prepare a coating liquid. After the coating liquid is added to the separable flask and thoroughly stirred, the separable flask is immersed in an oil bath set at a high temperature (for example, 100 to 125°C), and water that may be contained in the reaction system is extracted from the system by azeotropic distillation of the hydrocarbon dispersion medium and water while refluxing the hydrocarbon dispersion medium. Thereafter, the hydrocarbon dispersion medium is evaporated to obtain coated resin particles in which the surfaces of water-absorbent resin particles are coated with a coating material.

[0071] An example of the above method (2) will be described. First, a separable flask equipped with a reflux condenser, a dropping funnel, a nitrogen gas inlet pipe, and a stirrer is prepared. Subsequently, a hydrocarbon dispersion medium, water-absorbent resin particles, and a coating liquid are charged into the separable flask, and the mixture is thoroughly stirred while maintaining a high temperature (for example, 60 to 80°C). Thereafter, the hydrocarbon dispersion medium is evaporated, thereby obtaining coated resin particles in which the surfaces of the water-absorbent resin particles are coated with a coating material.

[0072] There are various methods for (3) above, but the following will explain representative examples: (3-1) a method using an eggplant flask, (3-2) a method using a sprayer, and (3-3) a method using various granulators.

[0073] (3-1) The coating liquid is poured into an eggplant flask, followed by the addition of water-absorbent resin particles. The eggplant flask is attached to an evaporator, and heated while being rotated, to distill off the solvent or dispersion medium contained in the coating liquid under reduced pressure conditions. This yields coated resin particles in which the surfaces of the water-absorbent resin particles are coated with the coating material.

[0074] (3-2) Water-absorbent resin particles are added to a separable flask equipped with a stirring blade and stirred. The coating liquid is sprayed onto the water-absorbent resin particles that have been stirred up by the stirring blade. The coating liquid can be sprayed using, for example, a two-fluid nozzle. Since uniform coating can be expected, it is desirable to spray the coating liquid in the form of a mist using a current of inert gas such as nitrogen. Thereafter, the content of the separable flask is removed, heated in a hot air dryer, and then cooled to room temperature to obtain coated resin particles.

[0075] (3-3) Examples of granulators used for producing coated resin particles include tumbling granulators, stirring granulators, and fluidized bed granulators. When a tumbling granulator is used, an inclined shallow circular container attached to the tumbling granulator is rotated, and water-absorbent resin particles are supplied to the circular container, and an appropriate amount of coating liquid is added. Then, a coating layer is formed on the surface of the water-absorbent resin particles while they are being tumbling, while a part of the water-absorbent resin particles aggregates due to the solvent or dispersion medium contained in the coating liquid. The step of adding the water-absorbent resin particles and the coating liquid can be carried out multiple times as necessary. When an agitation granulator is used, water-absorbent resin particles are charged into a mixer attached to the agitation granulator, and the coating liquid is added while mixing by agitation. Then, a coating layer is formed on the surface of the water-absorbent resin particles while a part of the water-absorbent resin particles is aggregated by the solvent or dispersion medium contained in the coating liquid during agitation. The step of adding the water-absorbent resin particles and the coating liquid can be carried out multiple times as necessary. Note that excessive aggregation of the water-absorbent resin particles can be suppressed by controlling the shear force of the mixer. When a fluidized bed granulator is used, first, water-absorbent resin particles are placed in a container attached to the fluidized bed granulator and capable of blowing hot air from the bottom, and the water-absorbent resin particles are fluidized in advance. Thereafter, when a coating liquid is sprayed from a nozzle attached to the container, a coating layer is formed on the surface of the water-absorbent resin particles while some of the particles are agglomerated by the solvent or dispersion medium contained in the coating liquid during stirring. The coating liquid can be sprayed multiple times as necessary. Note that excessive agglomeration of the water-absorbent resin particles can be suppressed by adjusting the amount and frequency of spraying of the coating liquid. As the fluidized bed granulator, for example, a fluidized bed granulator FBD / SG (manufactured by Mutual Corporation) can be used.

[0076] An example of the above method (4) will be described. First, hydrated gel-like water-absorbent resin particles are prepared in a separable flask by a conventionally known reverse phase suspension polymerization method. The water-absorbent resin particles may be obtained by one-stage polymerization or by multi-stage polymerization of two or more stages. On the other hand, a monomer aqueous solution containing a coating material, a polymerization initiator, and, if necessary, an internal crosslinking agent is prepared. For example, when the coating layer contains polyurethane, the coating material contains a polyol and a polyisocyanate, and when the coating layer contains a coated water-absorbent resin, the coating material contains a monomer (for example, a water-soluble ethylenically unsaturated monomer) that can be polymerized to become a water-absorbent resin. Subsequently, a certain amount of water is removed from the separable flask by azeotropic distillation while refluxing the hydrocarbon dispersion medium, and then the above-mentioned aqueous monomer solution is charged into the separable flask to initiate a polymerization reaction. Thereafter, the hydrocarbon dispersion medium in the separable flask is evaporated to obtain coated resin particles in which the surfaces of the water-absorbent resin particles are coated with a coating layer (polymer of the coating material).

[0077] (5-1) An example of the above method (5) will be described. First, hydrated gel-like water-absorbent resin particles are prepared in a separable flask by a conventionally known reverse phase suspension polymerization method (these water-absorbent resin particles may be obtained by one-stage polymerization or by multi-stage polymerization of two or more stages). On the other hand, a precursor aqueous solution containing a coating material (including a precursor) and a crosslinking agent is prepared. For example, when the coating layer contains a crosslinked polymer of polyacrylamide as the coating water-absorbent resin, the precursor contains polyacrylamide. Subsequently, a certain amount of water is removed from the separable flask by azeotropic distillation while refluxing the hydrocarbon dispersion medium, and then the above-mentioned aqueous precursor solution is introduced into the separable flask to initiate a crosslinking reaction. Thereafter, the hydrocarbon dispersion medium in the separable flask is evaporated, thereby obtaining coated resin particles in which the surfaces of the water-absorbent resin particles are coated with a coating layer (coated water-absorbent resin which is a crosslinked product of the coating material).

[0078] (5-2) Another example of the method (5) above will be described. First, hydrated gel-like water-absorbent resin particles are prepared in the same manner as in 5-1 above. Subsequently, these particles are dehydrated to obtain dried water-absorbent resin particles. The dried water-absorbent resin particles are dispersed in an appropriate dispersion medium (e.g., n-heptane, etc.), and in this state, a coating material A (e.g., polyol) and a coating material B (e.g., polyisocyanate) are added in this order, and heated as necessary, thereby obtaining coated resin particles in which the surface of the water-absorbent resin is coated with a polymerization reaction product (coating layer) produced by a polymerization reaction of the coating material A and the coating material B.

[0079] When a coating layer is formed using a coating liquid, the coating material is likely to come into contact with the water-absorbent resin particles evenly, and therefore, it is thought that a coating layer is likely to be formed on the entire surface. In particular, it is thought that the above-mentioned methods (1), (2), and (3) using a fluidized bed granulator, and methods (4) and (5) are likely to provide a coating layer with a more uniform thickness than other methods. [Example]

[0080] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to these examples.

[0081] (Preparation of water-absorbent resin particles) A round-bottom, cylindrical, separable flask with an inner diameter of 11 cm and a volume of 2 L was prepared. It was equipped with a reflux condenser, a dropping funnel, a nitrogen gas inlet, and a stirrer (a two-stage stirrer with four inclined paddle blades, each 5 cm in diameter). 293 g of n-heptane and 0.736 g of maleic anhydride-modified ethylene-propylene copolymer (dispersant, Mitsui Chemicals, Inc., Hiwax 1105A) were added to the flask to obtain a mixture. The mixture was heated to 80 °C with stirring to dissolve the dispersant in the n-heptane, and then cooled to 50 °C.

[0082] Next, 92.0 g of an 80.5% by weight aqueous solution of acrylic acid (1.03 mol of acrylic acid) was placed in a 300 mL beaker. Subsequently, while cooling from the outside, 147.7 g of a 20.9% by weight aqueous solution of sodium hydroxide was added dropwise to the beaker to neutralize the 75 mol% acrylic acid. Next, 0.092 g of hydroxyethyl cellulose (Sumitomo Seika Chemicals Co., Ltd., HEC AW-15F) was added as a thickener, 0.0736 g (0.272 mmol) of potassium persulfate as a water-soluble radical polymerization initiator, and 0.010 g (0.057 mmol) of ethylene glycol diglycidyl ether as an internal crosslinking agent were added and dissolved to prepare the first aqueous solution.

[0083] The first-stage aqueous solution was added to the separable flask and stirred for 10 minutes. A surfactant solution was then added to the separable flask, obtained by dissolving 0.736 g of sucrose stearate (surfactant, manufactured by Mitsubishi Chemical Foods Corporation, Ryoto Sugar Ester S-370, HLB: 3) in 6.62 g of n-heptane, to obtain a reaction solution. The system was then thoroughly purged with nitrogen while stirring the reaction solution at a stirrer speed of 550 rpm. The separable flask was then immersed in a 70°C water bath to raise the temperature of the reaction solution, and the polymerization reaction was allowed to proceed for 60 minutes to obtain a first-stage polymerization slurry.

[0084] Next, 128.8 g of an 80.5% by weight aqueous solution of acrylic acid (1.43 mol of acrylic acid) was placed in a separate 500 mL beaker. Subsequently, while cooling from the outside, 159.0 g of a 27% by weight aqueous solution of sodium hydroxide was added dropwise to the beaker to neutralize the 75 mol% acrylic acid. Subsequently, 0.103 g (0.381 mmol) of potassium persulfate as a water-soluble radical polymerization initiator and 0.0116 g (0.067 mmol) of ethylene glycol diglycidyl ether as an internal crosslinking agent were added to the beaker and dissolved to prepare the second aqueous solution.

[0085] While stirring at a stirrer speed of 1000 rpm, the first-stage polymerization slurry in the flask was cooled to 25°C, and the entire amount of the second-stage aqueous solution was added. After purging the flask with nitrogen for 30 minutes, the flask was again immersed in a 70°C water bath to raise the temperature of the reaction solution, and the second-stage polymerization reaction was carried out for 60 minutes to obtain a hydrogel polymer. The flask was then immersed in an oil bath set at 125°C, and 257.7 g of water was extracted from the system by azeotropic distillation of n-heptane and water. Next, 4.42 g (0.507 mmol) of a 2% by weight aqueous solution of ethylene glycol diglycidyl ether was added as a surface crosslinking agent to the flask, and the mixture was maintained at 83°C for 2 hours.

[0086] Thereafter, the temperature of the second-stage reaction mixture was raised in an oil bath at 125°C, and 245 g of water was extracted from the system by azeotropic distillation of n-heptane and water while refluxing n-heptane. Then, n-heptane was evaporated at 125°C to dry, thereby obtaining a dried product (polymerized product). This dried product was passed through a sieve with an opening of 850 μm, thereby obtaining 236.8 g of water-absorbent resin particles in the form of agglomerated spherical particles.

[0087] [Example 1] (Formation of coating layer) A mixed solution (80.0 g) of 4.0 g of polyether polyol (AGC, EXCENOL 750ED) and 76.0 g of distilled water (aqueous polyol solution) was prepared. A mixed solution (47.6 g) of 4.76 g of tolylene-2,4-diisocyanate and 42.84 g of acetone (isocyanate solution) was prepared.

[0088] Next, a round-bottomed cylindrical separable flask with an inner diameter of 11 cm and an internal volume of 2 L was prepared, equipped with a reflux condenser, a dropping funnel, a nitrogen gas inlet tube, and a stirrer (a stirring blade having two stages of four inclined paddle blades with a blade diameter of 5 cm). 40 g of the above-mentioned water-absorbent resin particles was added to this flask, and then 480 g of n-heptane was added as a hydrocarbon dispersion medium and stirred to obtain a dispersion. The above-mentioned polyol aqueous solution was added to this dispersion, and then stirred at room temperature for 30 minutes. Subsequently, the above-mentioned isocyanate solution was added, and then stirred at room temperature for 120 minutes to allow a sequential polymerization reaction to proceed on the surface of the water-absorbent resin particles, thereby obtaining a reaction product.

[0089] Thereafter, the reaction mixture was heated in an oil bath at 125°C, and 76 g of water was extracted from the system by azeotropic distillation of n-heptane and water while refluxing n-heptane. Then, a dried product (polymerized product) was obtained by evaporating n-heptane at 125°C. This dried product was passed through a sieve with an opening of 850 μm, thereby producing 38.2 g of coated resin particles in which water-absorbent resin particles were coated with polyurethane.

[0090] [Example 2] Coated resin particles were prepared in the same manner as in Example 1, except that the aqueous polyol solution was changed to 8.0 g of a mixture of 0.4 g of polyether polyol (AGC, EXCENOL 750ED) and 7.6 g of distilled water, and the isocyanate solution was changed to 4.76 g of a mixture of 0.48 g of tolylene-2,4-diisocyanate and 4.28 g of acetone.

[0091] [Comparative Example 1] The water-absorbent resin particles before forming the coating layer were used as they were.

[0092] The water-absorbent resin particles and the coated resin particles were evaluated as follows. The results are shown in Table 1.

[0093] (Proportion of coating material) The proportion of the coating material in the preparation of the coated resin particles was calculated by the following formula. Proportion of coating material (mass%) = {mass of coating material used to form the coating layer / (mass of water-absorbent resin particles used to form the coating layer + mass of coating material used to form the coating layer)} × 100 Specifically, in Example 1, the mass of the coating material used to form the coating layer was 8.76 g (mass of polyether polyol (4.0 g) + mass of tolylene-2,4-diisocyanate (4.76 g)), and the mass of the water-absorbent resin particles used to form the coating layer was 40 g, so the proportion of the coating material was calculated based on these values. The same calculation was made for Example 2.

[0094] (Water absorption) 2.0 g of water-absorbent resin particles were dispersed in 500 g of saline in a 500 mL beaker and stirred at 600 rpm for 1 hour to allow swelling. The mass (Wa) of a 75 μm JIS standard metal sieve was then measured, and the aqueous solution containing the swollen gel was filtered through the metal sieve. The metal sieve was left tilted at an angle of approximately 30 degrees to the horizontal for 30 minutes, and excess saline was removed. The mass (Wb) of the metal sieve containing the swollen gel was measured, and the water absorption was calculated using the following formula: Water absorption (g / g)=[Wb-Wa] / 2.0

[0095] (median particle size) The particle size distribution of 5 g of water-absorbent resin particles and 5 g of coated resin particles was measured using a continuous, fully automatic ultrasonic vibration sieving measuring instrument (Robot Sifter RPS-205, manufactured by Seishin Enterprise Co., Ltd.), JIS standard sieves with mesh sizes of 710 μm, 600 μm, 500 μm, 425 μm, 300 μm, 250 μm, and 150 μm, and a tray. The particle sizes remaining on the sieves were integrated in descending order of particle size, and the relationship between the mesh size of the sieves and the integrated value of the mass percentage of the particles remaining on the sieves was plotted on a logarithmic probability paper. The particle size corresponding to an integrated mass percentage of 50% by mass was determined as the median particle size by connecting the plots on the probability paper with a straight line.

[0096] (Unpressurized DW) The no-pressure DW of the water-absorbent resin particles and the coated resin particles was measured using a measuring device Z shown in FIG.

[0097] The measuring device Z includes a burette unit 71, a conduit 72, a flat measurement table 73, a nylon mesh 74, a stand 75, and a clamp 76. The burette unit 71 includes a burette 71a with a scale, a rubber stopper 71b that seals the upper opening of the burette 71a, a stopcock 71c connected to the lower tip of the burette 71a, and an air inlet tube 71d and a stopcock 71e connected to the lower part of the burette 71a. The burette unit 71 is fixed with a clamp 76. The measurement table 73 has a through-hole 73a with a diameter of 2 mm formed in its center and is supported by a height-adjustable stand 75. The through-hole 73a of the measurement table 73 and the stopcock 71c of the burette unit 71 are connected by a conduit 72. The inner diameter of the conduit 72 is 6 mm.

[0098] The measurements were performed in an environment with a temperature of 25°C and a humidity of 50±10%. First, the stopcocks 71c and 71e of the burette part 71 were closed, and saline solution 77 adjusted to 25°C was poured into the burette 71a through the opening at the top of the burette 71a. After sealing the opening of the burette 71a with a rubber stopper 71b, the stopcocks 71c and 71e were opened. The inside of the conduit 72 was filled with saline solution 77 while preventing air bubbles from entering. The height of the measurement table 73 was adjusted so that the height of the water surface of the saline solution 77 that had reached the through-hole 73a was the same as the height of the upper surface of the measurement table 73. After the adjustment, the height of the water surface of the saline solution 77 in the burette 71a was read using the scale on the burette 71a, and this position was designated as the zero point (the reading at 0 seconds).

[0099] A nylon mesh 74 (100 mm × 100 mm, 250 mesh, thickness: approximately 50 μm) was laid near the through-hole 73 a on the measurement table 73, and a cylinder with an inner diameter of 30 mm and a height of 20 mm was placed in the center of the nylon mesh 74. 1.00 g of water-absorbent resin particles or coated resin particles 78 was uniformly dispersed in the cylinder, and then the cylinder was carefully removed to obtain a sample in which the water-absorbent resin particles or coated resin particles 78 were dispersed in a circular pattern in the center of the nylon mesh 74. Next, the nylon mesh 74 on which the water-absorbent resin particles or coated resin particles 78 were placed was moved quickly so that its center was positioned at the position of the through-hole 73 a, without scattering the water-absorbent resin particles or coated resin particles 78, and measurement was started. The time when air bubbles were first introduced into the burette 71 a from the air inlet tube 71 d was defined as the start of water absorption (0 seconds).

[0100] The amount of reduction in the saline solution 77 in the burette 71a (i.e., the amount of saline solution 77 absorbed by the water-absorbent resin particles or coated resin particles 78) was sequentially read in 0.1 mL increments, and the amount of reduction in the amount of saline solution 77 Wc [g] was read at 2 minutes, 5 minutes, 30 minutes, 120 minutes, and 240 minutes counting from the start of water absorption by the water-absorbent resin particles or coated resin particles 78. From Wc, the 2-minute, 5-minute, 30-minute, 120-minute, and 240-minute values ​​of the no-pressure DW were calculated using the following formula. The no-pressure DW is the amount of water absorbed per 1.00 g of the water-absorbent resin particles or coated resin particles 78. No-pressure DW value [mL / g] = Wc / 1.00

[0101] [Table 1]

[0102] By measuring the no-pressure DW, it was confirmed that the coated resin particles of Examples 1 and 2 started to absorb water later than the water-absorbent resin particles of Comparative Example 1. Furthermore, the water-absorbent resin particles of Comparative Example 1 reached a state where the no-pressure DW did not increase any more (a swollen state) 30 minutes after contact with physiological saline. On the other hand, the coated resin particles of Examples 1 and 2 continued to increase in no-pressure DW even after 30 minutes after contact with physiological saline, and it was confirmed that the time to reach a swollen state was delayed compared to Comparative Example 1.

[0103] (Confirmation of breakdown of coating layer) The swelling state of the water-absorbent resin particles and the coated resin particles after dropping physiological saline onto them was observed (magnification: 200 times) using a digital microscope (VHX-5000: KEYENCE Corporation). After absorbing water, the coating layer of the coated resin particles of Example 1 had collapsed as shown in Figure 7. On the other hand, after absorbing water, the water-absorbent resin particles of Comparative Example 1, which did not have a coating layer, maintained a spherical shape as shown in Figure 8.

[0104] [Example 3] As a coating liquid, a 23.3% aqueous dispersion emulsion of vinyl chloride copolymer (Viniblan 715, manufactured by Nissin Chemical Industry Co., Ltd.) was prepared.

[0105] 300 g of n-heptane and 25 g of water-absorbent resin particles were placed in the same flask as in Example 1, and the temperature was raised to 80 ° C while stirring at 1000 rpm to disperse the water-absorbent resin particles in n-heptane. Next, 32.2 g of an aqueous dispersion emulsion of a vinyl chloride copolymer was added to the flask and stirred for 10 minutes. The flask was then immersed in an oil bath set at 125 ° C, and 22 g of water was extracted from the system by azeotropic distillation of n-heptane and water while refluxing the n-heptane. By removing the n-heptane at 125 ° C, a precursor of coated resin particles was obtained. This precursor was passed through a sieve with an opening of 850 μm to obtain 28 g of coated resin particles.

[0106] [Example 4] As a coating material, sucrose fatty acid ester (Mitsubishi Chemical Foods Corporation, Surfhope SS-3) was prepared.

[0107] 250 g of n-heptane, 100 g of water-absorbent resin particles, and 10 g of sucrose fatty acid ester were placed in the same flask as in Example 1, and the mixture was stirred at 1000 rpm at 85°C for 10 minutes. Thereafter, the flask was immersed in an oil bath set at 125°C, and n-heptane was removed at 125°C to obtain a precursor of coated resin particles. This precursor was passed through a sieve with an opening of 850 μm, and 88 g of coated resin particles was obtained.

[0108] [Example 5] Polyvinyl chloride (FUJIFILM Wako Pure Chemical Industries, Ltd.) was prepared as a coating material. 20 g of polyvinyl chloride was mixed with 480 g of tetrahydrofuran to prepare a coating liquid.

[0109] 500 g of water-absorbent resin particles were placed in a container of a fluidized bed granulator (Powrex Corporation, FD-MP-01), and warm air at 40°C was blown from the bottom of the container. 500 g of a coating liquid was sprayed onto the water-absorbent resin particles being blown up by the air blown, while drying. After spraying the coating liquid, the particles were dried at 40°C for 30 minutes to obtain a precursor of coated resin particles. This precursor was passed through a sieve with an opening of 850 μm, and 470 g of coated resin particles was obtained.

[0110] [Example 6] Coating liquid a was prepared by mixing 1995 g of distilled water, 855 g of ethanol, and 150 g of polyvinyl alcohol (Kuraray Co., Ltd., Kuraray Poval 3-98).

[0111] 500 g of water-absorbent resin particles were placed in a container of a fluidized bed granulator, and hot air at 60°C was blown from the bottom of the container. Next, 3000 g of coating liquid a was sprayed onto the water-absorbent resin particles being blown up by the air blown, while drying. After spraying the coating liquid, the particles were dried at 60°C for 30 minutes to obtain a dried product. This dried product was passed through a sieve with an opening of 850 μm, and 575 g of a coated resin precursor (A) was obtained.

[0112] Coating liquid b was prepared by mixing 0.8 g of a 79 mass % isopropyl alcohol solution of titanium triethanolamine (Matsumoto Fine Chemical Co., Ltd., Orgatix TC-400) and 5.2 g of isopropyl alcohol.

[0113] An 11 cm round-bottomed cylindrical separable flask equipped with a 9 cm outer diameter anchor-shaped stirring blade made of fluororesin was prepared. 10 g of coated resin precursor (A) was added to the flask, and while stirring at 300 rpm, 6 g of coating liquid b was added and mixed at 25°C for 10 minutes to obtain a mixture. The mixture was heat-treated in a hot air dryer (ADVANTEC, FV-320) at 105°C for 2 hours to crosslink the polyvinyl alcohol and obtain coated resin precursor (B). The coated resin precursor (B) was passed through a sieve with 850 μm openings to obtain 11 g of coated resin particles.

[0114] [Example 7] Polyvinyl chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and polyethylene glycol (Tokyo Chemical Industry Co., Ltd., PEG6000) were prepared as coating materials. 522.5 g of tetrahydrofuran, 25 g of polyvinyl chloride, and 2.5 g of polyethylene glycol were mixed to prepare a coating solution.

[0115] 500 g of water-absorbent resin particles were placed in a container of a fluidized bed granulator (Powrex Corporation, FD-MP-01), and warm air at 40°C was blown from the bottom of the container. Next, 550 g of a coating liquid was sprayed onto the water-absorbent resin particles being blown up by the air blown, while drying. After spraying the coating liquid, the particles were dried at 40°C for 30 minutes to obtain a precursor of coated resin particles. This precursor was passed through a sieve with an opening of 850 μm, and 484 g of coated resin particles was obtained.

[0116] The water-absorbent resin particles and coated resin particles were evaluated as follows in addition to measuring the proportion of coating material and the median particle size. The results are shown in Table 2.

[0117] <Method for measuring the solubility of coating materials> When measuring the solubility of the coating material, 5 g of a solid coating material of an appropriate size for easy measurement was prepared and added to 100 g of distilled water to prepare a measurement solution.

[0118] (Measurement solutions in Examples 1 and 2) 9.2 g of polyether polyol and 27.6 g of acetone were mixed to prepare 36.8 g of a polyol solution, and 10.8 g of tolylene-2,4-diisocyanate and 32.4 g of acetone were mixed to prepare 43.2 g of an isocyanate solution. A polyurethane solution was prepared by adding 36.8 g of polyol solution and 43.2 g of isocyanate solution to a Teflon beaker with an inner diameter of 6.2 cm and stirring with a magnetic stirrer until homogeneous. The magnetic stirrer was removed, the mixture was allowed to stand at 25°C for 15 hours, and then covered with aluminum foil. The aluminum foil was perforated and heated in a hot air dryer (ADVANTEC, FV-320) at 40°C for 1 hour, followed by 80°C for 1 hour, to obtain a polymer film. The polymer film was then pulverized in a centrifugal grinder (Retsch, ZM200, screen diameter: 1 mm, 6000 rpm) to obtain powdered polyurethane. The polyurethane was then added to the same Teflon beaker and covered with aluminum foil. The aluminum foil was perforated and heated in a hot air dryer (FV-320) at 105°C for 2 hours to completely dry, yielding a coating material. 100 g of distilled water at 25°C was placed in a 200 mL beaker and stirred at 600 rpm using a rotor (8 mm x 30 mm, without ring). The coating material was classified, and 5 g of the coating material that passed through an 850 μm sieve and remained on a 75 μm sieve was placed in the beaker and stirred for 1 hour to obtain a mixed solution. The mixed solution was suction filtered using a 34 μm stainless steel mesh. The filtrate was collected and used as the measurement solution.

[0119] (Measurement solution of Example 3) 100 g of a 23.3% aqueous dispersion emulsion of vinyl chloride copolymer was placed in a Teflon-coated tray (bottom dimensions 250 x 185 mm) and covered with aluminum foil. Holes were punched into the aluminum foil and heated in a hot air dryer (FV-320) at 105°C for 2 hours to obtain a polymer film of vinyl chloride copolymer. The polymer film was cut into small pieces with scissors, placed in the Teflon-coated tray, and covered with aluminum foil. Holes were punched into the aluminum foil and heated in a hot air dryer (FV-320) at 105°C for 2 hours to completely dry, obtaining a coating material. The coating material was classified, and 5 g of the coating material that passed through a sieve with 850 μm openings and remained on a sieve with 75 μm openings was used to prepare a measurement liquid in the same manner as in the preparation of the measurement liquids in Examples 1 and 2.

[0120] (Measurement solutions in Examples 4 and 5) The coating material was classified, and 5 g of the coating material that passed through a sieve with 850 μm openings and remained on a sieve with 75 μm openings was used to prepare a measurement liquid in the same manner as in the preparation of the measurement liquids in Examples 1 and 2.

[0121] (Measurement solution of Example 6) 100g of polyvinyl alcohol solution was prepared by mixing 10g of polyvinyl alcohol and 90g of distilled water. 20g of titanium triethanolamine solution was prepared by mixing 2.5g of a 79% titanium triethanolamine solution in isopropyl alcohol and 17.5g of isopropyl alcohol. 70g of the polyvinyl alcohol solution and 14g of the titanium triethanolamine solution were added to a 300mL beaker and stirred magnetically at 25°C for 30 minutes to produce a polymer solution. The polymer solution was added to a Teflon-coated tray and covered with aluminum foil. Holes were punched into the aluminum foil and heated in a hot air dryer (FV-320) at 105°C for 2 hours to obtain a crosslinked polyvinyl alcohol film. The crosslinked film was cut into small pieces with scissors, placed in a Teflon-coated tray, and covered with aluminum foil. The aluminum foil was punched and heated in a hot air dryer (FV-320) at 105°C for 2 hours to completely dry, obtaining a coating material. The coating material was classified, and 5 g of the coating material that passed through a sieve with 850 μm openings and remained on a sieve with 75 μm openings was used to prepare a measurement liquid in the same manner as in the preparation of the measurement liquids in Examples 1 and 2.

[0122] (Measurement solution of Example 7) Polyvinyl chloride and polyethylene glycol were each classified, and 4.55 g of polyvinyl chloride that passed through a sieve with 850 μm openings and remained on a sieve with 75 μm openings and 0.45 g of polyethylene glycol were mixed to obtain 5 g of powder coating material. Using the coating material, a test solution was obtained in the same manner as in Examples 1 and 2.

[0123] (Calculation of solubility) 60 g of the test solution was placed in a weighed 100 mL beaker and dried for 15 hours in a hot air dryer (FV-320) at 140°C, and the mass of the solid content (Ws) contained in the test solution was measured. The solubility of the coating material in 100 g of water was calculated using the following formula. Solubility (g)=(Ws / 60)×100

[0124] (Water retention capacity) 2.0 g of water-absorbent resin particles or coated resin particles were dispersed in 500 g of saline in a 500 mL beaker and stirred at 600 rpm for 30 minutes to swell. The swollen gel was poured into a cotton bag (membrane broadcloth No. 60, 100 mm wide x 200 mm long), the top of the cotton bag was tied with a rubber band, and the bag was dehydrated for 1 minute using a spin dryer (Kokusan Co., Ltd., product number H-122) set to a centrifugal force of 167 G. The mass of the cotton bag containing the swollen gel after dehydration, Wd (g), was measured. The same procedure was repeated without the addition of water-absorbent resin particles or coated resin particles. The empty mass of the cotton bag when wet, We (g), was measured, and the water retention capacity of the saline solution was calculated using the following formula: Water retention capacity (g / g) = [Wd-We] / 2.0

[0125] (Water absorption rate) 0.200 g of water-absorbent resin particles or coated resin particles were precisely weighed and spread on the bottom of an acrylic cylinder with an inner diameter of 2.0 cm and a depth of 8.0 cm, and the height H0 of the layer of water-absorbent resin particles or coated resin particles was measured at 25°C. Next, 20 g of physiological saline was poured into the acrylic cylinder from the top. The height Hn of the layer of water-absorbent resin particles or coated resin particles was measured n minutes (1 minute and 5 minutes) after the entire amount of physiological saline was poured. The water absorption rates after 1 minute and 5 minutes were calculated using the following formula. Water absorption rate (cm)=Hn-H0

[0126] [Table 2] [Explanation of symbols]

[0127] 1, 2, 3, 4, 78...coated resin particles, 10, 10a...water-absorbent resin particles, 12, 14, 16...coating layer A, 18...coating layer B, 71...burette part, 71a...burette, 71b...rubber stopper, 71c, 71e...cock, 71d...air introduction tube, 72...conduit, 73...measuring table, 74...nylon mesh, 73a...through hole, 75...stand, 76...clamp, 77...physiological saline solution, Z...measuring device.

Claims

1. a coating layer covering at least a part of the surface of the water-absorbent resin particles; The water absorption capacity of the water-absorbent resin particles is 10 to 100 g / g at 25°C, the coating layer contains polyurethane as a water-insoluble component, The coated resin particles, wherein the coating layer is disintegrable due to expansion caused by the absorption of water by the water-absorbing resin particles.

2. A method for producing coated resin particles, comprising a step of mixing water-absorbent resin particles with a coating material, and then polymerizing the coating material to form a coating layer on at least a part of the surface of the water-absorbent resin particles, the coated resin particles have the water-absorbent resin particles and a coating layer that covers at least a part of the surface of the water-absorbent resin particles, The water absorption capacity of the water-absorbent resin particles is 10 to 100 g / g at 25°C, the coating layer contains a water-insoluble component, the water-insoluble component comprises at least one selected from the group consisting of polyurethane, polyolefin, polyester, polyamide, polystyrene, polycarbonate, polyacrylate, polyacetal, polyvinyl chloride, sucrose fatty acid ester, and acid-modified products thereof; The method for producing the coated resin particles, wherein the coating layer is disintegrable due to swelling caused by the absorption of water by the water-absorbing resin particles.

3. A method for producing coated resin particles, comprising a step of mixing water-absorbent resin particles with a coating material, and then crosslinking the coating material with a crosslinking agent to form a coating layer on at least a part of the surface of the water-absorbent resin particles, the coated resin particles have the water-absorbent resin particles and a coating layer that covers at least a part of the surface of the water-absorbent resin particles, The water absorption capacity of the water-absorbent resin particles is 10 to 100 g / g at 25°C, the coating layer contains a water-insoluble component, the water-insoluble component comprises at least one selected from the group consisting of polyurethane, polyolefin, polyester, polyamide, polystyrene, polycarbonate, polyacrylate, polyacetal, polyvinyl chloride, sucrose fatty acid ester, and acid-modified products thereof; The method for producing the coated resin particles, wherein the coating layer is disintegrable due to swelling caused by the absorption of water by the water-absorbing resin particles.

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