JP2006055833A - Particulate water absorbing agent with water-absorbing resin as main component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water absorbing agent which maintains excellent water absorbing properties for a long time even when urine composition of human urine varies depending. <P>SOLUTION: This water absorbing agent comprises a water-absorbing resin obtained by crosslinking polymerization of an unsaturated monomer and exhibits Centrifuge retention capacity in a physiological saline solution of not lower than 32 g/g, mass median particle size (D50) of 200 to 400 μm, ratio of particles with diameter of smaller than 150 μm of 0 to 2 mass%, increased extractables by deterioration of 0 to 15 mass% and extractables in a deterioration test solution for one hour of 0.1 to 30 mass%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a particulate water-absorbing agent mainly composed of a water-absorbing resin. More specifically, the present invention relates to a particulate water-absorbing agent that exhibits an unprecedented excellent absorbability when actually used in absorbent articles such as diapers.

  At present, hydrophilic materials such as water absorbent resin and pulp for absorbing body fluid are widely used as sanitary materials such as paper diapers and sanitary napkins, so-called incontinence pads. Examples of the water-absorbing resin include a crosslinked polyacrylic acid partially neutralized product, a hydrolyzate of starch-acrylic acid graft polymer, a saponified vinyl acetate-acrylic ester copolymer, an acrylonitrile copolymer, or an acrylamide. A hydrolyzate of a copolymer or a cross-linked product thereof, and a cross-linked polymer of a cationic monomer are used as a main raw material.

  Conventionally, the above-mentioned water-absorbing resin has excellent liquid absorption amount and water absorption speed, gel strength, gel liquid permeability, suction force for sucking water from a base material containing aqueous liquid, etc. when in contact with aqueous liquid such as body fluid It is required to have excellent physical properties. Furthermore, in recent years, water-absorbing resin powders having a very narrow particle size distribution and water-absorbing resin powders having a high absorption capacity and a low water-soluble content have been demanded, and the absorption capacity under pressure and liquid permeability under pressure are high. It has come to be required. In addition, even in the state where the body fluid and urine are absorbed and swollen to form a gel, the gel has not been deteriorated for a long time, and a characteristic that the absorption performance is not lowered has been demanded.

  For example, many parameter patents and measurement methods defining various properties of these water-absorbing resins and water-absorbing agents mainly composed of water-absorbing resins have been filed (Patent Document 1, Patent Document 2, Patent Document 2, Patent Literature 3, Patent Literature 4, Patent Literature 5, Patent Literature 6, Patent Literature 7, Patent Literature 8, Patent Literature 9, Patent Literature 10, Patent Literature 11, Patent Literature 12, Patent Literature 13, Patent Literature 14, Patent Literature 15, Patent Literature 16, Patent Literature 17, Patent Literature 18, Patent Literature 19, Patent Literature 20, Patent Literature 21, Patent Literature 22, Patent Literature 23, Patent Literature 24, Patent Literature 25, Patent Literature 26, Patent Literature 27, (Patent Literature 28, Patent Literature 29, Patent Literature 30, Patent Literature 31, Patent Literature 32, Patent Literature 33).

  Patent Document 1 proposes a water absorbent resin excellent in gel strength, soluble content, and water absorption magnification. Patent Document 2 proposes a water absorbent resin excellent in non-pressurized liquid permeability, water absorption speed, and water absorption magnification. Patent Literature 3, Patent Literature 4, Patent Literature 5, Patent Literature 6 and the like have also been proposed as technologies that define a specific particle size distribution. In addition, many water-absorbing resins excellent in water absorption capacity under pressure under various loads and methods for measuring the same are proposed, and water-absorbing resins in combination with pressure absorption capacity alone or in combination with other physical properties are disclosed in Patent Document 7, Patent Document 8, Patent Literature 9, Patent Literature 10, Patent Literature 11, Patent Literature 12, Patent Literature 13, Patent Literature 14, Patent Literature 15, Patent Literature 16, and the like have been proposed.

  In addition, Patent Literature 17, Patent Literature 18 and the like have proposed water-absorbing resins excellent in impact resistance with reduced physical properties. A water-absorbing resin that defines the amount of dust is proposed in Patent Document 19 and the like, and a water-absorbing resin with less coloring is proposed in Patent Document 20 and the like. Regarding urinary resistance, water-absorbing resins excellent in gel durability and water-absorbing ability to L-ascorbic acid aqueous solutions are proposed in Patent Document 21 and Patent Document 22, and water-absorbing resins excellent in air permeability are proposed in Patent Document 23. Has been. A water-absorbing resin with little residual monomer is proposed in Patent Document 24.

Furthermore, it is described in Patent Document 25, US Patent 26, US Patent 27, US Patent 28, Patent Document that a water-absorbing resin having specific physical properties is suitable for water-absorbing articles such as diapers having specific physical properties, constitution or polymer concentration. 29, Patent Document 30, Patent Document 31, Patent Document 32, and the like. Further, Patent Document 33 proposes a method in which at least a part of resin particles is pulverized when performing surface crosslinking.
US Reissue Patent Re32649 Specification Specification of British Patent No. 2267094B US Pat. No. 5,051,259 US Pat. No. 5,419,956 US Pat. No. 6,087,002 European Patent No. 0629441 European Patent No. 0707603 EP 0712659 specification European Patent No. 1029886 US Pat. No. 5,462,972 US Pat. No. 5,453,323 US Pat. No. 5,797,893 US Pat. No. 6,127,454 US Pat. No. 6,184,433 US Pat. No. 6,297,335 US Reissue Patent Re37021 Specification US Pat. No. 5140076 Specification US Pat. No. 6,414,214 B1 US Pat. No. 5,994,440 US Pat. No. 6,444,744 US Pat. No. 6,194,531 European Patent No. 0940148 European Patent No. 1153656 European Patent No. 0605215 US Pat. No. 5,147,343 US Pat. No. 5,149,335 European Patent No. 053002 US Pat. No. 5,601,452 US Pat. No. 5,562,646 US Pat. No. 5,669,894 US Pat. No. 6,150,582 International Publication No. 02/053198 Pamphlet European Patent No. 093739

  Of the water-absorbing resins and water-absorbing agents that have been developed with a focus on many physical properties as described above, those that are targeted or specified for these properties have been manufactured and used, but these specific physical properties are controlled. Even so, there is still a problem that it is difficult to say that the actual use of disposable diapers and the like is sufficient.

  Therefore, the problems to be solved by the present invention have heretofore been a water-absorbing resin that has focused on physical properties such as a large number of water absorption rates, water absorption capacity without pressure, water absorption capacity under pressure, gel strength, durability, soluble content, and particle size. Despite the development and use of water-absorbing agents, it is possible to provide water-absorbing agents suitable for actual use in water-absorbing agents that have not been able to demonstrate sufficient performance in actual use even with control or design of these physical properties. is there.

  As a result of studying to solve the above problems, the present invention is a water-absorbing agent having a specific particle size distribution and a specific absorption ratio, because components contained in urine gradually destroy the cross-linked structure of the water-absorbing resin. It has been found that the degradation of water tends to occur and that the urine degradation increases the soluble content and changes the water absorption characteristics. Conventionally, various physical properties of a water-absorbing resin and a water-absorbing agent have been proposed by measuring physiological saline (0.9 mass% sodium chloride aqueous solution) or various artificial urine using urine as a model. The urine composition of urine is different in each patent, and the actual urine composition is not constant, and it varies greatly from moment to moment depending on the living environment, diet, age, season, and even time and physical condition of the same person. The conventional water-absorbing resin and water-absorbing agent have been evaluated for absorption characteristics using one kind of specific water-absorbing liquid such as a certain physiological saline or artificial urine as a urine model. It has been found that conventional water-absorbing agents cannot exhibit sufficient performance in actual use when the water-absorbing agent cannot be evaluated properly and the soluble content of the water-absorbing agent changes due to urine composition changes.

  Therefore, in the present invention, the deterioration of the water-absorbing agent caused by the urine composition change that changes depending on the season and physical condition is defined as `` urine deterioration '' even if the urine is discharged, even in the same person's urine. As an index of the degree, “increase in soluble content degradation” and “increase in soluble content degradation” were introduced. In the present invention, the soluble content deterioration increasing amount and the soluble content deterioration increasing magnification are defined by the following equations. However, in this specification, the deterioration test solution is a physiological saline containing 0.05% by mass L-ascorbic acid, and the physiological saline is a 0.9% by mass sodium chloride aqueous solution, and the use temperature is particularly high. Unless otherwise specified, it is room temperature (25 ° C. ± 2 ° C.). Moreover, the measuring method is based on the method shown in the Example mentioned later.

  When the soluble content in the deterioration test solution increases from before the deterioration, the soluble content is likely to be eluted from the absorber, and the diffusibility of the liquid to the absorber such as blood and urine is inhibited, so that the water absorption property is deteriorated. Moreover, the remarkable increase in the soluble content indicates that the cross-linking structure of the water-absorbing agent is broken, and it becomes difficult to hold body fluid such as urine taken into the water-absorbing agent, and the absorption performance is lowered. Such a decrease in water absorption performance appears as an increase in the return amount of the absorbent body or absorbent article. For this reason, it is preferable that the increase in the return amount is suppressed by limiting the “soluble content deterioration increase amount” and the “soluble content deterioration increase rate” to a specific range.

  On the other hand, as a result of examining urine deterioration in detail, the degree of urine deterioration tends to depend on the surface area of the absorbent, and the particle size distribution having a smaller mass average particle diameter, for example, an absorbent having a mass average particle diameter D50 of 400 μm or less, It was also found that the increase in soluble content due to urine degradation was significant. The mass average particle size is an important factor that affects the absorption behavior of the water-absorbent resin and water-absorbing agent and the finish of absorbent articles such as diapers. Simply increasing the mass average particle size to inhibit urine degradation It is not a problem that can be solved.

  Furthermore, urine deterioration has a correlation with the absorption capacity of the absorbent, and the higher the absorption capacity, the more the increase in soluble content due to urine deterioration. Therefore, in order to improve the absorption amount of absorbent articles such as diapers, simply increasing the absorption capacity of the water-absorbent resin cannot withstand long-term actual use.

  This is because today's thinning of the absorbent article is preferred, the mass average particle diameter D50 is as small as 400 μm or less, the absorption capacity is high, and the water-absorbing agent is limited to a certain range of soluble components regardless of changes in urine Shows a high absorption capacity under pressure, indicating that it can be an excellent water-absorbing agent compared to conventional ones. On the other hand, it is a water-absorbing agent with a small mass average particle diameter D50 of 400 μm or less and a high absorption capacity. The few indicated that actual preparation was difficult and did not exist before.

  From the above, in the present invention, the water-absorbing agent has a cross-linked structure, has a specific absorption capacity under no pressure, has a specific particle size distribution and average particle size, It was conceived that the above-mentioned problems can be solved with a water-absorbing agent having a specific mass-average particle diameter and excellent stability against urine, by setting the “soluble matter deterioration increasing ratio” within a specific range.

The first particulate water-absorbing agent of the present invention is
A particulate water-absorbing agent comprising as a main component a water-absorbing resin obtained by crosslinking and polymerizing an acid group and / or a salt-containing unsaturated monomer thereof, and satisfying the following (a) to (d).
(A) Absorption capacity (CRC) under no pressure to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm
(D) The soluble content deterioration increase amount shown by the said formula is 0-15 mass%, and the 1 hour soluble content in a degradation test liquid is 0.1-30 mass%.

The second particulate water-absorbing agent of the present invention is
A particulate water-absorbing agent mainly comprising a water-absorbing resin obtained by crosslinking polymerization of an acid group and / or a salt-containing unsaturated monomer, and satisfying the following (a) to (c) and (e) Agent.
(A) Absorption capacity (CRC) under no pressure to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm
(E) The soluble component deterioration increasing magnification represented by the above formula is 1 to 4 times, and the one hour soluble component in the deterioration test solution is 0.1 to 30% by mass.

The third particulate water-absorbing agent of the present invention is
A particulate water-absorbing agent comprising as a main component a water-absorbing resin obtained by crosslinking and polymerizing an acid group and / or a salt-containing unsaturated monomer thereof, wherein the following (a) to (c) and (f), (g) Filled particulate water-absorbing agent.
(A) Absorption capacity (CRC) under no pressure to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm
(F) 0.1 to 10% by mass of 16-hour soluble component in physiological saline
(G) Absorption capacity under high pressure (AAP 4.8 kPa) at 4.8 kPa into physiological saline is 21 g / g or more.

Moreover, the production method of the first particulate water-absorbing agent of the present invention,
A step of crosslinking polymerization of an unsaturated monomer aqueous solution containing unneutralized acrylic acid and / or a salt thereof as a main component in the presence of a crosslinking agent and a chain transfer agent;
Step of further surface cross-linking water-absorbent resin particles satisfying the following (a) to (c) obtained by polymerization (a) Absorption capacity under no pressure (CRC) to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm
It is characterized by including.

The method for producing the second particulate water-absorbing agent of the present invention,
Step of cross-linking polymerization of unsaturated monomer aqueous solution having concentration of unneutralized acrylic acid as main component of monomer in the presence of crosslinking agent Step of neutralizing after polymerization A step of further surface cross-linking the water-absorbent resin particles satisfying the following (a) to (c):
(A) Absorption capacity (CRC) under no pressure to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm
It is characterized by including.

The method for producing the third particulate water-absorbing agent of the present invention,
A step of crosslinking polymerization of an unsaturated monomer aqueous solution containing unneutralized acrylic acid and / or a salt thereof as a main component in the presence of a crosslinking agent;
Step of further surface cross-linking water-absorbent resin particles satisfying the following (a) to (c) obtained by polymerization (a) Absorption capacity under no pressure (CRC) to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm and selected from the group consisting of (i) during polymerization, (ii) before surface crosslinking after polymerization, (iii) during surface crosslinking, (iv) after surface crosslinking Adding a chelating agent at one or more times
It is characterized by including.

  According to the particulate water-absorbing agent of the present invention, since it has a specific absorption ratio and a specific particle size distribution, when actually used as an absorbent article such as a diaper, it has an unprecedented performance especially in a short-time absorption capacity. Demonstrate. In particular, the amount of return can be reduced, and the effect of improving the dryness of the diaper surface is remarkable.

  Moreover, since urine deterioration is suppressed, it is excellent in gel stability, absorption performance can be maintained over a long time, and the discomfort of the wearer can be reduced.

  In the present invention, urine deterioration can be suppressed, and at the same time, since it has a specific particle size distribution, there are few deflections, and piston flow properties are produced in the production of particulate water-absorbing agents and in powder conveyance during the production of absorbent articles such as diapers. And the pulsation in which the supply amount of the powder changes periodically is suppressed. Moreover, when manufacturing absorbent articles, such as a diaper, mixing with the particulate water-absorbing agent of this invention and hydrophilic fibers, such as a pulverized wood pulp, is easy, and it can be set as a uniform composition simply.

  Hereinafter, raw materials and reaction conditions used for the water-absorbent resin and water-absorbing agent of the present invention will be described. Moreover, in this specification, (a) Absorption capacity under non-pressure to physiological saline (CRC), (b) Mass average particle diameter (D50), (d) Increase in degradation of soluble component, (e) Soluble Minute degradation increase magnification, (f) 16 hours soluble component in physiological saline, (g) Absorption magnification under high pressure at 4.8 kPa into physiological saline (AAP 4.8 kPa), (i) To physiological saline Absorption capacity under pressure at 1.9 kPa (AAP 1.9 kPa), (j) Vortex water absorption rate into physiological saline, (k) Hygroscopic fluidity, (l) Logarithmic standard deviation of particle size distribution, and deterioration test solution The 1-hour soluble component is a numerical value measured by the method described in Examples described later.

(1) Water-absorbing resin The water-absorbing resin of the present invention is a water-swellable water-insoluble cross-linked polymer that can form a hydrogel. For example, water-swelling property is essential weight 5 in ion-exchanged water. It refers to a substance that absorbs a large amount of water, more than 50 times, preferably 50 times to 1000 times. Further, water-insoluble refers to a water-soluble component, that is, one hour soluble component of 50% by mass or less, and further to a range described later. In addition, these measuring methods are prescribed | regulated by an Example.

  In the present invention, as the water-absorbing resin, a water-absorbing resin obtained by crosslinking polymerization of an acid group and / or a salt-containing unsaturated monomer thereof is essential for achieving the present invention, preferably acrylic acid and / or A polyacrylic acid (partial) neutralized polymer obtained by polymerizing / crosslinking an unsaturated monomer containing the salt as a main component is used. A water-absorbing resin having a cross-linked structure may be used, and a water-absorbing resin obtained by polymerizing an acid group and / or a salt-containing unsaturated monomer thereof and then cross-linking with a cross-linking agent may be used.

(2) Water-absorbing agent and method for producing the same In the present invention, the water-absorbing agent is a solidifying agent for absorbing an aqueous liquid, the main component of which is a water-absorbing resin. Aqueous liquids are not limited to water but should absorb water containing water, such as urine, blood, feces, waste liquid, moisture and steam, ice, water and organic and inorganic solvents, rainwater, groundwater, etc. Preferably, it is urine, especially human urine. In the present invention, the water-absorbing resin can be used as it is as a water-absorbing agent, and may contain additives, water and the like as necessary. The content of the water-absorbing resin in the water-absorbing agent is 70 to 100% by mass, preferably 80 to 100% by mass, and more preferably 90 to 100% by mass, based on the water-absorbing agent. As other components, water is usually the main component or essential, and the additives described below are used.

  The water-absorbing agent of the present invention is not particularly limited as long as the water-absorbing agent satisfying the above characteristics can be produced. For example, the water-absorbing agent can be obtained by the following production methods 1 to 3.

  Production method 1: An unsaturated monomer aqueous solution containing unneutralized acrylic acid and / or its salt as a main component of the monomer is subjected to crosslinking polymerization in the presence of a crosslinking agent and a chain transfer agent, and then adjusted to a specific particle size distribution. And surface cross-linking the resulting water-absorbent resin particles having a specific absorption capacity.

  Production method 2: obtained by subjecting an unsaturated monomer aqueous solution having a specific concentration of unneutralized acrylic acid as a main component to cross-linking polymerization in the presence of a cross-linking agent, further neutralizing, and adjusting to a specific particle size distribution A method of further surface cross-linking the water-absorbent resin particles having a specific absorption rate.

  Production method 3: An unsaturated monomer aqueous solution containing unneutralized acrylic acid and / or a salt thereof as a main component of the monomer is subjected to crosslinking polymerization in the presence of a crosslinking agent, and then adjusted to a specific particle size distribution. Further, the water-absorbent resin particles having a specific absorption capacity are further surface-crosslinked, and selected from the group consisting of (i) during polymerization, (ii) before surface crosslinking after polymerization, (iii) during surface crosslinking, and (iv) after surface crosslinking. A method of adding a chelating agent at one or more times.

  Hereinafter, the production method of the water-absorbing agent of the present invention and further the water-absorbing agent of the present invention will be described in order.

(3) Unsaturated monomer As the unsaturated monomer constituting the water-absorbent resin (hereinafter simply abbreviated as a monomer), acrylic acid and / or a salt thereof is used as a main component. The body may be used in combination, or the water-absorbing resin may be obtained only from other monomers. Examples of such other monomers include methacrylic acid, (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, vinyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) Acryloxyalkanesulfonic acid and its alkali metal salt, ammonium salt, N-vinyl-2-pyrrolidone, N-vinylacetamide, (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, There are water-soluble or hydrophobic unsaturated monomers such as 2-hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, isobutylene, and lauryl (meth) acrylate. These may be used alone or in combination of two or more.

  In the present invention, when a monomer other than acrylic acid (salt) is used in combination, the proportion of the monomer other than acrylic acid (salt) used is the total amount of acrylic acid and its salt in order to achieve the present invention. The ratio is preferably 0 to 30 mol%, more preferably 0 to 10 mol%, and most preferably 0 to 5 mol%.

  In addition, when using an acid group-containing unsaturated monomer as the monomer, examples of the salt include alkali metal salts, alkaline earth metal salts, and ammonium salts. Sodium salts and potassium salts are preferred from the standpoints of availability and safety. The acid group-containing unsaturated monomer such as acrylic acid is preferably neutralized in terms of physical properties and pH, and the neutralization rate of the acid group is usually 20 to 100 mol%, more preferably 30 to 95 mol%, more preferably 40 to 80 mol%. The neutralization of the acid group may be performed with an aqueous solution containing a monomer, may be performed after obtaining a polymer as shown in Production Method 2, or may be used in combination.

(4) Internal cross-linking agent The water-absorbing resin used in the present invention is a cross-linked polymer, but the cross-linked structure may be formed by a self-cross-linking type that does not use a cross-linkable monomer. An internal cross-linking agent such as a body may be used. From the viewpoint of physical properties, it is preferable to copolymerize or react an internal crosslinking agent having two or more polymerizable unsaturated groups or two or more reactive groups in one molecule. In addition, since it is a crosslinked polymer, it becomes water-insoluble.

  Specific examples of these internal crosslinking agents include, for example, N, N′-methylenebis (meth) acrylamide, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, glycerin tri (meth) acrylate, glycerin acrylate methacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, tri Allylamine, poly (meth) allyloxyalkane, (poly) ethylene glycol diglycidyl ether, glycerol diglycidyl ether, ethylene glycol, polyethylene Glycol, propylene glycol, glycerol, pentaerythritol, ethylenediamine, ethylene carbonate, propylene carbonate, polyethylenimine, and glycidyl (meth) acrylate.

  These internal cross-linking agents may be used alone or in combination of two or more. These internal cross-linking agents may be added to the reaction system all at once or in divided portions. In the case of using at least one kind or two or more kinds of internal cross-linking agents, a compound having two or more polymerizable unsaturated groups in consideration of the absorption characteristics of the finally obtained water-absorbing resin or water-absorbing agent Is preferably used during the polymerization.

  The amount of these internal cross-linking agents used is preferably 0.001 to 2 mol%, more preferably 0.005 to 0.5 mol%, more preferably, relative to the unsaturated monomer (excluding the internal cross-linking agent). Preferably it is 0.01-0.2 mol%, Especially preferably, you may be in the range of 0.03-0.15 mol%. When the amount of the internal cross-linking agent used is less than 0.001 mol% and more than 2 mol%, sufficient absorption characteristics may not be obtained. If the amount of the internal cross-linking agent used is less than the above range, the cross-linked structure is not sufficiently formed, so that the soluble content in physiological saline and the degradation test solution described later increase, and the soluble content increases. This is not preferable because the amount of soluble matter deterioration increase ratio and the soluble matter for 16 hours increase. In addition, if the amount of the internal cross-linking agent used is more than the above range, the above-mentioned soluble content is reduced, but the absorption capacity of the absorbent article such as diapers is reduced due to a decrease in the absorption capacity of the water-absorbing resin or water-absorbing agent. Since it lowers, it is not preferable.

  When a crosslinked structure is introduced into the polymer using the internal cross-linking agent, the internal cross-linking agent is added to the reaction system before, during or after the polymerization of the monomer, or after the polymerization or neutralization. What should I do?

(5) Polymerization initiator As an initiator used when polymerizing the above-mentioned monomers to obtain the water-absorbent resin used in the present invention, potassium persulfate, ammonium persulfate, sodium persulfate, potassium peracetate, Radical polymerization initiators such as sodium peracetate, potassium percarbonate, sodium percarbonate, t-butyl hydroperoxide, hydrogen peroxide, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2-hydroxy- Photopolymerization initiators such as 2-methyl-1-phenyl-propan-1-one can be used. The amount of these polymerization initiators used is 0.001 to 2 mol%, preferably 0.01 to 0.1 mol% (based on the total monomers) in view of physical properties. When these polymerization initiators are less than 0.001 mol%, the amount of unreacted residual monomers increases. On the other hand, when the polymerization initiator exceeds 2 mol%, it is difficult to control the polymerization. Absent.

(6) Polymerization method In the present invention, bulk polymerization or precipitation polymerization can be performed, but it is preferable to perform aqueous solution polymerization or reverse phase suspension polymerization by using the monomer as an aqueous solution from the viewpoint of physical properties. When the monomer is an aqueous solution, the concentration of the monomer in the aqueous solution (hereinafter referred to as the monomer aqueous solution) is determined by the temperature of the aqueous solution and the monomer, and is not particularly limited. Is 10-70 mass%, More preferably, it is 20-60 mass%. Moreover, when performing the said aqueous solution polymerization, you may use together solvents other than water as needed, and the kind of solvent used together is not specifically limited. What is necessary is just to grind | pulverize after superposition | polymerization as needed.

  When starting the above polymerization, the above polymerization initiator is used. In addition to the aforementioned polymerization initiator, active energy rays such as ultraviolet rays, electron beams, and γ rays may be used alone or in combination with the polymerization initiator. The temperature at the start of polymerization depends on the type of polymerization initiator used, but is preferably in the range of 15 to 130 ° C, and more preferably in the range of 20 to 120 ° C.

  The reverse phase suspension polymerization is a polymerization method in which an aqueous monomer solution is suspended in a hydrophobic organic solvent. For example, U.S. Pat. Nos. 4,093,764, 4,367,323, 4,446,261, 4,683,274, and 5,244,735. Are described in US patents. Aqueous solution polymerization is a method of polymerizing an aqueous monomer solution without using a dispersion solvent. For example, US Pat. Nos. 4,462,001, 4,873,299, 4,286,082, 4,973,632, 4,985,518, 5,124,416, 5,250,640 are used. No. 5,264,495, US Pat. No. 5,145,906 and US Pat. No. 5,380,808, and European patents such as European Patents 081636, 09555086, and 0922717. Monomers and initiators exemplified in these polymerization methods can also be applied in the present invention.

  In the water-absorbing agent of the present invention, as described above, the neutralization rate of the acid group is usually 20 to 100 mol%, but in the polymerization step of the unsaturated monomer, the unsaturated monomer is not neutralized. It superposes | polymerizes as it is and may neutralize after superposition | polymerization and may superpose | polymerize using the unsaturated monomer neutralized previously. Therefore, the neutralization rate of the unsaturated monomer in the monomer aqueous solution can be performed in any range of 0 to 100 mol%. Among these, neutralization polymerization may be used in the above-described production method 1 and production method 3, and the neutralization rate is 20 to 100 mol%, more preferably 30 to 95 mol%, more preferably 40 to 80 mol%. Can be polymerized using an aqueous monomer solution. In addition, neutralization uses an unneutralized unsaturated monomer to initiate polymerization, and uses neutralization in the middle of polymerization, or an unsaturated monomer that has been previously neutralized to the above range. Including any aspect in which the neutralized unsaturated monomer is polymerized, such as an aspect and an aspect in which neutralization is further performed during the polymerization, the neutralization rate means a neutralization rate at the start of polymerization.

  On the other hand, a so-called acid polymerization & post-neutralization method may be used in which an unneutralized acid group-containing unsaturated monomer, in particular, unneutralized acrylic acid is polymerized as a main component, and acid groups are neutralized after polymerization. . This is manufacturing method 2 described above. That is, in the production method 2 of the present invention, an unsaturated monomer aqueous solution having a specific concentration mainly composed of unneutralized acrylic acid is subjected to cross-linking polymerization in the presence of a cross-linking agent, and then neutralized to adjust to a specific particle size. Then, the obtained water-absorbing resin particles having a specific water absorption ratio are further subjected to surface crosslinking. In production method 2, unneutralized acrylic acid is the main component, preferably 30 to 100 mol%, more preferably 90 to 100 mol%, and particularly 100 mol% is crosslinked using a monomer of unneutralized acrylic acid. After obtaining the polymer, it can be used as the water-absorbent resin of the present invention by partially adding an alkali metal salt and then neutralizing it to make an alkali metal base partially. When the water-absorbent resin obtained by the polymerization method is used as the water-absorbing agent of the present invention, it is possible to obtain an absorbent body having high absorbability and excellent stability to urine. When polymerizing unneutralized unsaturated monomers, the details are unclear, but there is a tendency to increase the amount of internal cross-linking agent used, and urine resistance can be improved by increasing the cross-linking density. it can.

  In the present invention, if necessary, other polymerizable monomers can be used together with acrylic acid. Specific types of other polymerizable monomer, internal cross-linking agent, polymerization initiator, addition amount, and the like are the same as those described in the above (3), (4), and (5). In Production Method 2, the concentration of the polymerizable monomer when a solvent is used is not particularly limited, but it is usually 5 to 30% by mass, preferably 10 to 30% by mass, and the polymerization initiation temperature is low. It is preferable to use an aqueous solution having a low temperature of 10 to 25 ° C.

  Alkali metal hydroxides (hydroxylated) are used as the alkali metal compounds used to neutralize the acid groups in the polymer obtained and neutralize the acid groups in the resulting polymer to partially form an alkali metal base. Sodium, potassium hydroxide, lithium hydroxide, etc.), alkali metal carbonates (sodium carbonate, sodium bicarbonate, etc.) and the like. Sodium salt and potassium salt are preferable from the viewpoint of the performance of the water-absorbing resin to be obtained, industrial availability, safety and the like. In the present invention, 50 to 90 mol%, preferably 60 to 80 mol% of the acid groups in the polymer are converted to an alkali metal salt by a neutralization reaction with an alkali metal compound.

In production method 2, the polymer after polymerization is essentially neutralized. The polymer as a method of neutralization with an alkali metal compound, adding an aqueous solution of an alkali metal compound when polymerized using a solvent, while cutting the obtained gel-like polymer to about 1 cm ³ or less pieces, There is a method of further kneading the gel with a kneader or meat chopper. Further, in obtaining the water-absorbing agent of the present invention, the neutralization temperature is 50 to 100 ° C., further 60 to 90 ° C., and the neutralization is carried out according to the first neutralization index (1) according to claim 1 of US Pat. It is preferable that the uniformity defined by the degree of neutralization of 200 particles is 10 or less.

(7) Chain transfer agent In this invention, you may use a chain transfer agent essential at the time of superposition | polymerization. When the water-absorbing resin obtained by polymerizing in the presence of a water-soluble chain transfer agent in addition to the aforementioned unsaturated monomer, internal cross-linking agent, and polymerization initiator is used as the water-absorbing agent of the present invention, absorption It is possible to obtain an absorber having high performance and excellent urine stability. When a chain transfer agent is used in combination, the amount of the internal crosslinking agent can be increased, and urine resistance degradation can be improved by increasing the crosslinking density.

  The water-soluble chain transfer agent used for polymerization in the present invention is not particularly limited as long as it is soluble in water or a water-soluble ethylenically unsaturated monomer, and thiols, thiolic acids, secondary alcohols, amines , Phosphites, hypophosphites and the like. Specifically, mercaptoethanol, mercaptopropanol, dodecyl mercaptan, thioglycols, thiomalic acid, 3-mercaptopropionic acid, isopropanol, sodium phosphite, potassium phosphite, sodium hypophosphite, formic acid, and salts thereof are used. One or two or more selected from these groups are used, and it is preferable to use a phosphorus compound, particularly a hypophosphite such as sodium hypophosphite because of its effect.

  The amount of water-soluble chain transfer agent used is 0.001 to 1 mol% with respect to the total monomer, although it depends on the type and amount of water-soluble chain transfer agent and the concentration of the monomer aqueous solution, preferably 0.005 to 0.3 mol%. If the amount used is less than 0.001 mol%, the amount of the internal crosslinking agent used in the present invention is not preferable because the crosslinking density is high and the absorption capacity is too low. On the other hand, if the amount exceeds 1 mol%, the amount of water-soluble components increases and the stability is lowered, which is not preferable. The chain transfer agent may be polymerized after being dissolved in the monomer aqueous solution, or may be sequentially added during the polymerization. The water-soluble chain transfer agent is essential in the case of production method 1, but may be used in production method 2 and production method 3.

(8) Drying The cross-linked polymer obtained by the above polymerization method is a hydrogel cross-linked polymer, and the gel is pulverized and dried as necessary. Drying is usually performed in a temperature range of a heating medium temperature of 60 ° C to 250 ° C, preferably 100 ° C to 220 ° C, more preferably 120 ° C to 200 ° C. The drying time depends on the surface area of the polymer, the moisture content, and the type of dryer, and is selected to achieve the desired moisture content. In the present invention, the crosslinked polymer after drying is referred to as a water absorbent resin.

  The water content of the water-absorbent resin that can be used in the present invention is not particularly limited, but is a particle that exhibits fluidity even at room temperature, more preferably a water content of 0.2 to 30% by mass, and still more preferably 0.3 to The powder state is 15% by mass, particularly preferably 0.5 to 10% by mass. If the water content becomes high, not only does the fluidity deteriorate and the production is hindered, but the water-absorbent resin may not be pulverized or controlled to a specific particle size distribution. The water content of the water-absorbent resin is defined by the amount of water contained in the water-absorbent resin, and is measured by loss on drying at 180 ° C. for 3 hours.

  The drying method used includes heat drying, hot air drying, vacuum drying, infrared drying, microwave drying, dehydration by azeotropy with a hydrophobic organic solvent, and high moisture content using high-temperature steam. As described above, various methods can be employed, and the method is not particularly limited.

  If the water-absorbent resin of the present invention obtained by the above-mentioned production method can be handled as a powder, it is spherical, fibrous, rod-like, substantially spherical, flat, indeterminate, granulated particles, particles having a porous structure, etc. Although not particularly limited, an irregularly pulverized product obtained through a pulverization step can be preferably used.

(9) Grinding / classification, particle size control, and absorption ratio The water-absorbent resin used in the present invention is preferably adjusted to a specific particle size in order to obtain the particulate water-absorbing agent of the present invention.

  As the particle diameter of the water-absorbent resin used in the present invention, in order to obtain the water-absorbing agent of the present invention, the mass average particle diameter is usually 180 to 420 μm, preferably 200 to 400 μm, more preferably 225 to 380 μm, particularly preferably. The proportion of particles that are controlled narrowly to 250 to 350 μm and less than 150 μm is controlled to 0 to 3% by mass, preferably 0 to 2% by mass, and more preferably 0 to 1% by mass.

  Moreover, in order to obtain the water-absorbing agent of the present invention, the water-absorbent resin of the present invention has a bulk specific gravity (specified in JIS K-3362-1998) of preferably 0.40 to 0.90 g / ml, more preferably It is adjusted in the range of 0.50 to 0.80 g / ml. Moreover, the particle | grains between 600-150 micrometers are preferably 90-100 mass% of the whole, More preferably, it is 95-100 mass%, More preferably, it is set as 98-100 mass%. The logarithmic standard deviation (σζ) of the particle size distribution is preferably 0.20 to 0.50, more preferably 0.20 to 0.45, and particularly preferably 0.20 to 0.40.

  The particle size adjustment may be adjusted by dispersion polymerization and dispersion drying in the form of particles when the crosslinked polymer is produced by reverse phase suspension polymerization, but usually in the case of aqueous solution polymerization, While being classified, the mass average particle diameter D50 and the ratio of particles having a particle diameter of less than 150 μm are controlled to be adjusted to a specific particle size. For example, in the adjustment to a specific particle size in which the amount of fine particles of less than 150 μm is reduced while the mass average particle diameter D50 is reduced to 400 μm or less, if necessary, coarse particles and fine particles can be separated by a general classifier such as a sieve after the above-mentioned pulverization. It may be removed. The coarse particles removed at this time are preferably particles having a particle size of 5000 μm to 400 μm, more preferably particles having a particle size of 2000 μm to 400 μm, and still more preferably particles having a particle size of 1000 μm to 400 μm. . The fine particles removed by the particle size adjustment are preferably particles having a particle size of less than 200 μm, more preferably particles having a particle size of less than 150 μm. Although the removed coarse particles may be discarded as they are, they are generally pulverized again in the above pulverization step. Further, the removed fine particles can be reduced in loss by performing the step of enlarging the fine particles in the next item (10).

  In addition, although the water-absorbent resin obtained as described above in the present invention is adjusted to the above particle size, preferably, the absorption capacity under non-pressure (CRC) to physiological saline before surface crosslinking is 32 g / g or more. Preferably it is 35-70 g / g, More preferably, it is 40-65 g / g, Most preferably, it is 45-60 g / g. The absorption ratio can be controlled by adding a predetermined amount of an internal crosslinking agent to the unsaturated monomer aqueous solution, or by controlling the above-described polymerization conditions and drying conditions. The water-absorbing resin can be used as a water-absorbing agent as it is, and since the water-absorbing agent of the present invention has a non-pressure absorption capacity of 32 g / g or more, the water-absorbing resin has an absorption capacity under no pressure. It is necessary to be 32 g / g or more.

(10) Increasing the particle size of fine particles The fine particles removed by pulverization / classification and particle size control in (9) above can be regenerated into larger particles or particulate aggregates and used as the water absorbent resin of the present invention. it can. Although the methods described in US Pat. Nos. 6,228,930, 5,264,495, 4,950,692, 5,478,879 and European Patent 844270 can be used, the water absorbent resin thus regenerated is substantially porous. It has a structure.

  The ratio of the water absorbent resin regenerated by this step contained in the water absorbent resin of the present invention is preferably 0 to 50% by mass, more preferably 5 to 40% by mass, and most preferably 10 to 30% by mass. . When the water absorbent resin regenerated by this step is used as the water absorbent resin particles of the present invention, the surface area is larger than that of the non-regenerated one, so that a faster absorption rate is obtained, which is advantageous in terms of performance. . In general, the water-absorbent resin having a large particle diameter is mixed with the water-absorbent resin obtained in the above (8) drying step, and then pulverization / classification and particle size control are performed.

(11) Surface cross-linking treatment The water-absorbent resin used in the present invention is preferably adjusted to a specific particle size distribution as represented by the above-mentioned production methods 1 to 3, and the obtained water-absorbent resin having a specific absorption capacity is used. Further, it may be surface-crosslinked. The water absorption resin used in the present invention has its absorption capacity (CRC) lowered by, for example, such surface crosslinking, and is usually 95 to 50%, further 90 to 60% of the absorption capacity (CRC) before surface crosslinking. To fall. In addition, the reduction | decrease in absorptivity (CRC) can be suitably adjusted with the kind and quantity of a crosslinking agent, reaction temperature, time, etc.

  Although it does not specifically limit as a surface crosslinking agent which can be used by this invention, For example, the surface crosslinking agent illustrated by US Patent 6228930, 6071976, 6254990 etc. can be used. For example, mono, di, tri, tetra or polyethylene glycol, monopropylene glycol, 1,3-propanediol, dipropylene glycol, 2,3,4-trimethyl-1,3-pentanediol, polypropylene glycol, glycerin, polyglycerin , 2-butene-1,4-diol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, etc. Alcohol compounds; epoxy compounds such as ethylene glycol diglycidyl ether and glycidol; ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine, polyamide polyamine, etc. Haloepoxy compounds such as epichlorohydrin, epibromohydrin, α-methylepichlorohydrin; condensates of the above polyvalent amine compounds and the above haloepoxy compounds; oxazolidinone compounds such as 2-oxazolidinone; cyclic urea An alkylene carbonate compound such as ethylene carbonate may be used, and only one of these may be used, or two or more may be used in combination. In order to sufficiently exhibit the effects of the present invention, it is preferable to use a polyhydric alcohol as an essential component among these surface crosslinking agents. As a polyhydric alcohol, a C2-C10 thing is preferable and a C3-C8 thing is more preferable.

  The amount of the surface cross-linking agent used depends on the compounds to be used and combinations thereof, but is preferably in the range of 0.001 to 10% by mass, and in the range of 0.01 to 5% by mass with respect to the water absorbent resin. Is more preferable.

  When performing surface crosslinking in the present invention, it is preferable to use water as a solvent. At this time, although the amount of water used depends on the water content of the water-absorbing resin to be used, it is preferably in the range of 0.5 to 20% by mass, more preferably 0.5 to It is in the range of 10% by mass. In addition to water, a hydrophilic organic solvent may be used. When a hydrophilic organic solvent is used, the amount used is preferably in the range of 0 to 10% by mass, more preferably in the range of 0 to 5% by mass, and still more preferably 0 to 3% by mass with respect to the water absorbent resin. Is within the range.

  In the case of carrying out surface crosslinking in the present invention, it is preferable to preliminarily mix water and / or a hydrophilic organic solvent and a surface crosslinking agent and then spray or drop-mix the aqueous solution onto the water absorbent resin. The method is more preferred. The size of the droplets to be sprayed is preferably in the range of 0.1 to 300 μm, more preferably in the range of 0.1 to 200 μm, in terms of average particle diameter.

  As a mixing device used when mixing the water-absorbent resin, the surface cross-linking agent, water, and a hydrophilic organic solvent, it is preferable to have a large mixing force in order to uniformly and reliably mix the two. Examples of the mixing apparatus include a cylindrical mixer, a double wall conical mixer, a high-speed stirring mixer, a V-shaped mixer, a ribbon mixer, a screw mixer, a double-arm kneader, and a pulverizing kneader. Rotating mixers, airflow mixers, turbulators, batch-type Redige mixers, continuous-type Redige mixers, and the like are suitable.

  It is preferable that the water-absorbent resin after mixing the surface cross-linking agent is heat-treated. The heating temperature (heating medium temperature or material temperature) is preferably in the range of 100 to 250 ° C, more preferably in the range of 150 to 250 ° C, and the heating time is preferably in the range of 1 minute to 2 hours. Preferable examples of the combination of the heating temperature and the heating time are 0.1 to 1.5 hours at 180 ° C. and 0.1 to 1 hour at 200 ° C. A particulate water-absorbing resin is obtained by these steps.

(12) Granulation The water absorbent resin used in the present invention may be further granulated in addition to the above steps. As such a granulating step, a method of adding water to a surface-crosslinked water-absorbing resin and heating the water-absorbing resin while maintaining a water content of 1 to 10% by mass and, if necessary, pulverizing by the above method is suitable. Such granulation can be performed to adjust the water absorbent resin to a specific particle size.

  In the present invention, the granulation is preferably performed by spraying or dropping and mixing water or an aqueous solution in which other additive components are dissolved into the water-absorbent resin, and particularly preferably a spraying method. The size of the droplets to be sprayed is preferably in the range of 0.1 to 300 μm, more preferably in the range of 0.1 to 200 μm, in terms of average particle diameter. In the heat treatment, the water content of the water-absorbent resin (specified by loss on drying at 180 ° C. for 3 hours) is 1 to 10% by mass, more preferably 2 to 8% by mass, further 2 .5 to 6% by mass. A heating medium such as hot air can be used for heating, and the heating temperature (heating medium temperature or material temperature) is preferably within the range of 40 to 120 ° C, more preferably within the range of 50 to 100 ° C. The heating time is preferably in the range of 1 minute to 2 hours. The heating temperature is often indicated by the heat medium temperature. Preferable examples of the combination of heating temperature and heating time are 0.1 to 1.5 hours at 60 ° C. and 0.1 to 1 hour at 100 ° C. Heating and water addition may be performed in the same apparatus or in different apparatuses. The heating may be stirred or unstirred as long as the temperature and moisture content can be controlled, but it is preferably performed without stirring. More preferably, the water-absorbing resin to which water or the like is added is laminated to 1 to 100 cm, further 5 to 80 cm, particularly 10 to 70 cm, and heated. A water-absorbent resin cured by heating is obtained, and then pulverized, preferably further classified, to obtain a particulate water-absorbent resin.

  As a granulating apparatus that can be used, it is preferable to have a large mixing force, for example, a cylindrical mixer, a double-walled cone mixer, a high-speed stirring mixer, a V-shaped mixer, a ribbon mixer, A screw type mixer, a double arm type kneader, a pulverizing type kneader, a rotary type mixer, an airflow type mixer, a turbulizer, a batch type readyge mixer, a continuous type readyge mixer, and the like are suitable.

  The water added to the water absorbent resin may contain other additives such as a chelating agent, a plant component, an antibacterial agent, a water-soluble polymer, and an inorganic salt, which will be described later. In that case, the content of the additive is in the range of 0.001 to 50% by mass of the aqueous solution.

(13) Addition of chelating agent The particulate water-absorbing agent of the present invention can contain a chelating agent, particularly a polyvalent carboxylic acid and a salt thereof.

  In particular, the production method 3 of the present invention comprises a specific particle size distribution after crosslinking an unsaturated monomer aqueous solution containing unneutralized acrylic acid and / or a salt thereof as a main component in the presence of a crosslinking agent. The resulting water-absorbent resin particles having a specific absorption capacity are further surface-crosslinked, and a chelating agent is added at the time of polymerization, before or after or simultaneously with the surface crosslinking. Thus, the action of a component that degrades or destroys the crosslinked structure can be suppressed, and a water-absorbing agent excellent in urine resistance degradation can be produced.

  The chelating agent that can be used in the water-absorbing agent of the present invention is preferably a rate agent having a high ion sequestering ability and chelating ability for Fe and Cu, specifically a stability constant for Fe ions of 10 or more, preferably 20 The above chelating agents are preferred, aminopolycarboxylic acids and salts thereof are more preferred, and aminocarboxylic acids and salts thereof having 3 or more carboxyl groups are particularly preferred. In addition, among the above, the aminocarboxylate may be partially neutralized or all of the acid groups contained therein. Specific examples of these polycarboxylic acids include diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, cyclohexane-1,2-diaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, ethylene glycol diethyl etherdiaminetetraacetic acid, ethylenediaminetetraacetic acid. Examples include propionacetic acid, N-alkyl-N′-carboxymethylaspartic acid, N-alkenyl-N′-carboxymethylaspartic acid, and alkali metal salts, alkaline earth metal salts, ammonium salts, or amine salts thereof. One type or two or more types selected from these groups are used. Of these, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, N-hydroxyethylethylenediaminetriacetic acid and salts thereof are most preferable.

  In the present invention, the amount of the chelating agent, particularly amino polyvalent carboxylic acid, is a minor component, usually 0.00001 to 10 parts by weight, preferably 0.0001 to 1 part by weight, based on 100 parts by weight of the water-absorbent resin as the main component. Part. When the amount used exceeds 10 parts by mass, not only an effect commensurate with the use cannot be obtained, but it becomes uneconomical, and problems such as a decrease in the amount of absorption occur. On the other hand, when the amount is less than 0.00001 part by mass, a sufficient addition effect cannot be obtained.

  In the case of adding a chelating agent during the polymerization, the chelating agent may be added to the unsaturated monomer aqueous solution for polymerization, or the chelating agent may be added during the polymerization. Moreover, you may add a chelating agent to the obtained gel-like crosslinked polymer and water absorbing resin. In order to add a chelating agent at the time of surface cross-linking, surface cross-linking is performed using a solution containing a surface cross-linking agent to which a chelating agent is added. A chelating agent may be added to the resin. Furthermore, when performing the granulation process of said (12), as above-mentioned, you may spray the water which melt | dissolved the chelating agent, and it heats, keeping a moisture content 1-10 mass%. In the case of drying if necessary after the addition, the temperature may be in a range that does not detract from the effect of the chelating agent, and is usually in the range described in (12) granulation step. The chelating agent is indispensable in the case of production method 3, but may be used for the water-absorbent resin obtained in production method 1 and production method 2.

(14) Other additives In the present invention, in addition to the chelating agent described above, the following (A) plant component, (B) polyvalent metal salt of organic acid, (C) inorganic fine particles ((D) complex hydrous oxide) Etc.) can be added as a trace component, thereby imparting various functions to the water-absorbing agent of the present invention. When the additive is a solution, the addition method is an embodiment in which the additive is added as an aqueous solution, an embodiment in which the additive is added in an aqueous dispersion, an embodiment in which the additive is added as it is, and when the additive is a powder, when it is insoluble in water, There are a mode of adding in an aqueous dispersion and a mode of adding as it is. When the powder is water-soluble, it can be added by the same method as in the case of the above solution.

  The amount of these other additives (A) to (D) and (E) used varies depending on the purpose and additional function, but is usually 0 as one type of additive with respect to 100 parts by mass of the water absorbent resin. -10 parts by mass, preferably 0.001-5 parts by mass, more preferably 0.002-3 parts by mass. Usually, when the amount is less than 0.001 part by mass, sufficient effects and additional functions cannot be obtained, and when the amount is 10 parts by mass or more, an effect commensurate with the addition amount may not be obtained or the absorption performance may be lowered.

(A) Plant component The water absorbing agent concerning this invention can mix | blend a plant component with the said quantity in order to exhibit deodorant property. The plant component that can be used in the present invention is preferably at least one compound selected from polyphenols, flavones and the like, and caffeine, and selected from tannin, tannic acid, pentaploid, gallic acid and gallic acid. More preferably, it is at least one kind.

  Examples of plants containing plant components that can be used in the present invention include camellia, cypress, mokoku and the like for camellia plants, and rice, sasa, bamboo, corn, wheat and the like for grasses. For example, in the plant of Rubiaceae, there are coffee.

  Examples of plant components that can be used in the present invention include extracts extracted from plants (essential oils), plants themselves (plant powders), plant meals and extracted meals that are by-produced in the manufacturing process in the plant processing industry and food processing industry. Although it is mentioned, it is not specifically limited.

(B) Multivalent metal salt The water-absorbing agent according to the present invention contains a polyvalent metal salt, particularly a polyvalent metal salt of an organic acid, in the above amount in order to improve powder fluidity and maintain fluidity after moisture absorption. I can do it.

  The polyvalent metal salt of organic acid used and the mixing method are exemplified in, for example, International Application No. PCT / 2004 / JP1355, and the organic acid polyvalent having 7 or more carbon atoms in the molecule can be used in the present invention. The valent metal salt is composed of a polyvalent metal salt such as fatty acid, petroleum acid, or polymer acid, that is, a polyvalent metal salt such as calcium, aluminum, magnesium, or zinc. One type or two or more types selected from these groups are used.

  Examples of the organic acid constituting the organic acid polyvalent metal salt include caproic acid, octylic acid, octic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, and other long-chain or branched fatty acids. Examples thereof include petroleum acids such as benzoic acid, myristic acid, naphthenic acid, naphthoic acid, and naphthoxyacetic acid, and polymer acids such as poly (meth) acrylic acid and polysulfonic acid, and are organic acids having a carboxyl group in the molecule. More preferred are caproic acid, octylic acid, octynic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, fatty acids such as bovine fatty acid and castor hardened fatty acid. More preferred are fatty acids having no unsaturated bond in the molecule, such as caproic acid, octylic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid. Most preferably, it is a long chain fatty acid having 12 or more carbon atoms in the molecule and having no unsaturated bond in the molecule, such as lauric acid, myristic acid, palmitic acid, and stearic acid.

(C) Inorganic fine particles The water-absorbing agent according to the present invention can contain inorganic fine particles, particularly water-insoluble inorganic fine particles, in order to maintain fluidity after moisture absorption. Specific examples of the inorganic powder used in the present invention include metal oxides such as silicon dioxide and titanium oxide, silicic acid (salts) such as natural zeolite and synthetic zeolite, kaolin, talc, clay, bentonite and the like. It is done. One type or two or more types selected from these groups are used. Among these, silicon dioxide and silicic acid (salt) are more preferable, and silicon dioxide and silicic acid (salt) having an average particle diameter measured by the Coulter counter method of 0.001 to 200 μm are more preferable.

(D) Composite Hydrous Oxide The water-absorbing agent according to the present invention exhibits excellent moisture-absorbing fluidity (powder fluidity after water-absorbing resin or water-absorbing agent absorbs moisture) and further exhibits excellent deodorizing performance. Therefore, a composite hydrous oxide containing zinc and silicon or zinc and aluminum can be blended.

(E) Others Other additives such as antibacterial agents, water-soluble polymers, water-insoluble polymers, water, and organic fine particles can be added as long as the water-absorbing agent of the present invention is obtained.

(15) Particulate water-absorbing agent of the present invention The particulate water-absorbing agent of the present invention using the above-mentioned production methods 1 to 3 as an example of the production method is a novel water-absorbing agent that exhibits a novel performance that has not existed before.

That is, the first particulate water-absorbing agent of the present invention is
A particulate water-absorbing agent comprising as a main component a water-absorbing resin obtained by crosslinking and polymerizing an acid group and / or a salt-containing unsaturated monomer thereof, and satisfying the following (a) to (d).
(A) Absorption capacity (CRC) under no pressure to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm
(D) The soluble content deterioration increase amount shown by the said formula is 0-15 mass%, and the 1 hour soluble content in a degradation test liquid is 0.1-30 mass%.

The second particulate water-absorbing agent of the present invention is
A particulate water-absorbing agent mainly comprising a water-absorbing resin obtained by crosslinking polymerization of an acid group and / or a salt-containing unsaturated monomer, and satisfying the following (a) to (c) and (e) Agent.
(A) Absorption capacity (CRC) under no pressure to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm
(E) The soluble component deterioration increasing magnification represented by the above formula is 1 to 4 times, and the one hour soluble component in the deterioration test solution is 0.1 to 30% by mass.

The third particulate water-absorbing agent of the present invention is
A particulate water-absorbing agent comprising as a main component a water-absorbing resin obtained by crosslinking and polymerizing an acid group and / or a salt-containing unsaturated monomer thereof, wherein the following (a) to (c) and (f), (g) Filled particulate water-absorbing agent.
(A) Absorption capacity (CRC) under no pressure to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm
(F) 0.1 to 10% by mass of 16-hour soluble component in physiological saline
(G) Absorption capacity under high pressure (AAP 4.8 kPa) at 4.8 kPa into physiological saline is 21 g / g or more.

  In the water-absorbing agent of the present invention, (b) the mass average particle diameter (D50) is usually controlled narrowly to 180 to 400 μm, preferably 200 to 400 μm, more preferably 225 to 380 μm, particularly preferably 250 to 350 μm, and (c ) The proportion of particles less than 150 μm is controlled to 0 to 3% by mass, preferably 0 to 2% by mass, more preferably 0 to 1% by mass. The particle size adjustment is preferably controlled before surface cross-linking, but may be pulverized, classified and granulated after surface cross-linking to adjust to a specific particle size. If the particle size distribution deviates from these, when used for diapers, it does not show suitable absorption characteristics and does not show high physical properties. In particular, (b) affects the absorption characteristics of absorbent articles such as diapers of water-absorbing agents. When the mass average particle diameter exceeds 400 μm, the surface area per unit mass decreases, so contact between the water-absorbing agent and urine, etc. The area is reduced and a long time is required to absorb the aqueous liquid. On the other hand, if it is less than 180 μm, the absorption time is shortened because the surface area per unit mass is large, but at the same time, the rate of penetration of the urine degradation component into the interior of the particle also increases, and the speed of urine degradation may increase. . Further, regeneration is required due to the increase in fine particles, which is not preferable in terms of cost. Furthermore, in continuous production, there is a possibility that fine particles exceeding the processing capacity of the particle classification device of less than 150 μm may be generated, and (c) it may be difficult to control the proportion of particles of less than 150 μm.

  Further, (c) when the amount of particles less than 150 μm exceeds 3% by mass, the absorption performance is reduced by gel blocking in the absorbent article, or the fine particle powder before swelling is transferred from the absorbent article to the surface topsheet. In some cases, the swollen gel that has absorbed body fluid during actual use may come into direct contact with the wearer's skin (gel-on-skin). In addition, there is a concern about loss due to scattering or the like during production of absorbent articles, or adverse effects on the work environment, which is not preferable from this viewpoint.

  The water-absorbing agent of the present invention has the above particle size distribution, and (a) the absorption capacity (CRC) of physiological saline under no pressure is 32 g / g or more, preferably 33 to 75 g / g, more preferably 35 to 70 g. / G, more preferably 40 to 65 g / g, particularly preferably 45 to 60 g / g. When the absorption capacity under no pressure is less than 32 g / g, a large amount of water-absorbing agent is required to secure a desired absorption capacity, which is not preferable in practice.

  The water-absorbing agent of the present invention satisfies the above characteristics, and (d) the amount of increase in degradation of soluble component is usually 0 to 15% by mass, more preferably 0 to 12, more preferably 0 to 10% by mass, particularly preferably. It is 0-8 mass%, Most preferably, it is 0-5 mass%. In the measurement of the “deterioration amount of soluble component degradation”, 0.05 mass% L-ascorbic acid-containing physiological saline was used as the degradation test solution because the deterioration of the water-absorbing agent due to urine was caused by L-ascorbine contained in urine. This is due to the acid and to adjust the osmotic pressure to the body fluid. As shown by the formula, the increase in soluble content deterioration is for comparing the absolute amount of soluble content increased due to urine deterioration, and the smaller the numerical value, the less the deterioration. In the present invention, if the amount of increase in soluble content deterioration is from 0 to 15% by mass, it indicates that the water-absorbing agent is stable against body fluids such as urine, and this numerical range is characteristic. When the amount of increase in soluble content deterioration exceeds 15% by mass, the stability of the water-absorbing agent to body fluids such as urine is insufficient, and sufficient absorption capacity cannot be exhibited when the absorbent is used for a long time in actual use.

  Similarly, (e) soluble component deterioration increasing ratio of the present invention is usually 1 to 4 times, preferably 1 to 3 times, more preferably 1 to 2 times, still more preferably 1 to 1.5 times, and particularly preferably. Is 1 to 1.3 times. The soluble component deterioration increasing rate indicates the soluble component generation rate due to deterioration, and the smaller the numerical value, the less the urine deterioration. If the soluble component deterioration increasing ratio is 1 to 4 times, this indicates that the water-absorbing agent is stable against body fluids such as urine. If the deterioration amount exceeds 4 times, the stability of the water-absorbing agent with respect to body fluids such as urine is insufficient, and sufficient absorption capacity cannot be exhibited when the absorber is used for a long time in actual use.

  The 1-hour soluble content in the deterioration test solution is preferably 0.1 to 30% by mass, more preferably 0.2 to 25% by mass, still more preferably 0.3 to 22% by mass, and particularly preferably 0. 4 to 20% by mass, most preferably 0.5 to 18% by mass. If the 1-hour soluble amount in the deterioration test solution exceeds the above upper limit range, the gel swollen during long-time use deteriorates with time, and the soluble amount increases. This soluble component is eluted from the absorber and may inhibit the diffusibility of the liquid to the absorber such as blood and urine. Moreover, although it does not restrict | limit achievement less than the said minimum, it sets in consideration of production conditions, such as cost.

  In addition, when the above (d) increase in degradation of soluble content and / or (e) increase in degradation of soluble content exceeds the above upper limit range, the crosslinked structure of the water-absorbing agent is remarkably broken, so that urine taken into the swollen gel, etc. It becomes difficult to retain the body fluid, and when used for a diaper or the like, it causes an increase in the amount of return. In addition, the swollen gel in which the cross-linked structure is broken is transformed into a water-soluble polymer, and the fluidized polymer may ooze out on the surface of an absorbent article such as a diaper. For this reason, it becomes a cause which increases the discomfort of the wearer of an absorbent article, and is not preferable.

  As described above, since the particle size distribution is correlated with the soluble content deterioration increase amount and the soluble content deterioration increase ratio, (b) while adjusting the mass average particle diameter D50 of 400 μm or less, Conventionally, there is no water-absorbing agent in which (d) an increase in soluble content deterioration and (e) an increase in soluble content deterioration are suppressed. However, in the present invention, (d) the amount of increase in soluble content deterioration and (e) the increase in soluble content deterioration is introduced, and these are controlled to 0 to 15% by mass and 1 to 4 times, respectively. It becomes a water-absorbing agent that has excellent usability and excellent water-absorbing characteristics over a long period of time. Such a water-absorbing agent can be produced, for example, by the above-described method, but can also be produced by methods other than those described above, as shown in the examples.

  Moreover, although the above-mentioned (d) soluble matter deterioration increase amount and (e) soluble content deterioration increase magnification should just satisfy | fill either one, it is more preferable to satisfy | fill simultaneously. In addition, although a measuring method is shown in the Example described later, a swollen gel obtained by adding 1 g of a water absorbing agent to a 25 ml deterioration test solution is used, but 25 times is assumed to swell in a diaper, It has been found that the above-mentioned increase in soluble content deterioration and the increase in soluble content deterioration correlate with the actual use of diapers. Furthermore, it has a specific particle size distribution, specific absorption capacity, and (d) an increase in soluble content deterioration and ( e) It has been found that a water-absorbing agent satisfying the increase in soluble matter deterioration gives a diaper with high physical properties regardless of changes in urine composition and use time even in actual use. Note that the evaluation and physical properties of soluble components described in JP-A-8-337726 and the like in which a water-absorbent resin is dispersed in a large excess of physiological saline at room temperature do not correlate with actual use and have no meaning. .

  The 1 hour soluble amount of the water-absorbing agent of the present invention in physiological saline is essentially 50% by mass or less, preferably 0.1 to 30% by mass, more preferably 0.2 to 25% by mass, and still more preferably. Is 0.3 to 20% by mass, still more preferably 0.4 to 15% by mass, particularly preferably 0.5 to 10% by mass, and preferably 0.5 to 8% by mass. When the 1-hour soluble amount exceeds the above upper limit range, the soluble component is eluted into the absorber at the time of water absorption, and the diffusibility of the liquid to the absorber such as blood or urine may be inhibited, which is not preferable. In general, it is difficult to achieve less than 0.1% by mass and it is not worth the cost.

In addition, in the case of the particulate water-absorbing agent, if (d) the soluble content deterioration increasing amount and (e) the soluble content deterioration increasing ratio are arbitrary, that is, in the case of the third particulate water absorbing agent, (f) The soluble matter in physiological saline for 16 hours is 0.1 to 10% by mass, further 0.6 to 8% by mass, particularly 0.7 to 5% by mass. If it exceeds 10% by mass, soluble components are eluted from the absorber during water absorption, and the diffusibility of the liquid into the absorber such as blood or urine may be inhibited. Moreover, when urine deterioration progresses, deterioration may advance to the extent that a crosslinked structure cannot be maintained, which is disadvantageous. Furthermore, (g) Absorption capacity under high pressure (AAP 4.8 kPa) at 4.8 kPa (about 50 g / cm ² , about 0.7 psi) into physiological saline is preferably 21 g / g or more, more preferably 22 g / g. g or more, more preferably 23 g / g or more, particularly preferably 24 g / g or more, and most preferably 25 g / g or more. If it is less than 21 g / g, the liquid contained in the water-absorbing agent may leak from the water-absorbing agent due to pressurization in actual use. When water absorption characteristics were examined in detail, even if (d) soluble matter deterioration increase amount and (e) soluble matter deterioration increase magnification were not satisfied, the above (a), (b), (c) When the above requirements (f) soluble for 16 hours and (g) absorption capacity under high pressure (AAP 4.8 kPa) are satisfied at the same time, even if the urine is absorbed for a long time in actual use, It was found that the performance was not degraded. The reason is that even if the crosslinked structure is slightly destroyed due to deterioration of urine, the performance of the absorbent body is maintained in actual use if the water-absorbing agent before destruction is kept low for 16 hours. It is.

  Further, it is known that the absorption ratio under high pressure (AAP 4.8 kPa) tends to be higher when the internal absorption agent is larger if the absorption ratio is the same. Although the details are not clear, it seems that the absorption capacity under high pressure (AAP 4.8 kPa) is indirectly related when the amount of internal cross-linking agent is increased and the degree of urine deterioration decreases. That is, it is necessary to set the performance of the water-absorbing agent before degradation within the above range in order to predict urine degradation and to exhibit the desired performance of the absorbent after degradation in the absorbent body. The upper limit of (g) is not particularly limited, but about 40 g / g may be sufficient due to cost increase due to difficulty in production.

  In addition, it is more preferable that the third particulate water-absorbing agent further satisfies (d) the increase in soluble component deterioration and (e) the increase in soluble component deterioration.

(16) Other characteristics of the particulate water-absorbing agent of the present invention (i) Absorption capacity under pressure at 1.9 kPa into physiological saline (AAP 1.9 kPa)
In the water-absorbing agent of the present invention, the absorption capacity under pressure under a pressure (under load) of 1.9 kPa is preferably 20 g / g or more, more preferably 25 g / g or more, and even more preferably 30 g / g. g or more, particularly preferably 35 g / g or more. If the absorption capacity under pressure is less than 20 g / g, the effect of the present invention may not be exhibited. The upper limit is not particularly limited, but about 60 g / g may be sufficient due to cost increase due to difficulty in production.

(H) Particles of 600 to 150 μm, (l) Logarithmic standard deviation The water-absorbing agent of the present invention preferably has a bulk specific gravity (defined by JIS K-3362) of preferably 0.40 to 0.90 g / ml, more preferably 0.50. It is adjusted to a range of ˜0.80 g / ml. Moreover, (h) The particle | grains between 600-150 micrometers are preferably 90-100 mass% of the whole, More preferably, it is 95-100 mass%, More preferably, it is set as 98-100 mass%. The (l) logarithmic standard deviation (σζ) of the particle size distribution is preferably 0.20 to 0.40, more preferably 0.20 to 0.38, and particularly preferably 0.20 to 0.36. Within this range, high physical properties can be obtained when used for diapers.

(K) Hygroscopic fluidity The water-absorbing agent of the present invention has excellent powder handling properties because of its low hygroscopic fluidity described in the examples described later. The hygroscopic fluidity is preferably 0 to 30% by mass or less, more preferably 0 to 20% by mass, further preferably 0 to 10% by mass, and particularly preferably 0 to 5% by mass. When the hygroscopic fluidity is larger than 30% by mass, for example, when producing a diaper or the like, there is an adverse effect such as difficulty in producing a diaper because the fluidity of the powder is deteriorated. These hygroscopic fluidity is achieved by the use of the aforementioned additives.

(J) Vortex absorption rate The absorption rate of the water-absorbing agent of the present invention is 60 seconds or less, preferably 1 to 55 seconds, more preferably 2 to 50 seconds. When the absorption rate exceeds 60 seconds, sufficient absorption capacity may not be exhibited when a water-absorbent resin is used for an absorbent body such as a diaper.

(17) Absorbent article The application of the particulate water-absorbing agent of the present invention is not particularly limited, but is preferably used for an absorbent body and an absorbent article.

  The absorber of the present invention is obtained using the particulate water-absorbing agent. In the present invention, the absorbent body is an absorbent material molded mainly with a particulate water-absorbing agent and hydrophilic fibers. In the absorbent body of the present invention, the content (core concentration) of the water absorbing agent with respect to the total mass of the water absorbing agent and the hydrophilic fiber is preferably 20 to 100% by mass, more preferably 30 to 100% by mass, and particularly preferably. It is 40-100 mass%.

  Furthermore, the absorbent article of the present invention is an absorbent article comprising the above-described absorbent body of the present invention, a top sheet having liquid permeability, and a back sheet having liquid impermeability.

The manufacturing method of the absorbent article of the present invention is, for example, that an absorbent body (absorbing core) is prepared by blending or sandwiching a fiber base material and the water-absorbing agent of the present invention, and the absorbent core is a liquid-permeable base material ( Sandwiched with a surface sheet) and a liquid-impermeable substrate (back sheet), and if necessary, equipped with an elastic member, a diffusion layer, an adhesive tape, etc., absorbent articles, especially children's diapers, Adult diapers and sanitary napkins can be used. Such an absorbent core is compression molded to a density of 0.06 to 0.50 g / cc and a basis weight of 0.01 to 0.20 g / cm ² . Examples of the fiber base used include hydrophilic fibers such as pulverized wood pulp, cotton linters and cross-linked cellulose fibers, rayon, cotton, wool, acetate, and vinylon. Preferably, they are airlaid.

  The water-absorbing agent of the present invention exhibits excellent absorption characteristics. Specific examples of absorbent articles using this include adult paper diapers, which have been growing rapidly in recent years, and sanitary materials such as diapers for children, sanitary napkins, so-called incontinence pads, and the like. It is not something. What is common is that the water-absorbing agent of the present invention present in the absorbent article has a low return amount and is improved to an absorbent article with a remarkable dry feeling, which is a burden on the wearer and the caregiver. Can be greatly reduced.

  EXAMPLES Examples and comparative examples of the present invention will be specifically described below, but the present invention is not limited to the following examples.

  Various performances of the water absorbing agent were measured by the following methods. Further, these characteristics were evaluated using a water-absorbing resin instead of the water-absorbing agent. All electric devices used in the examples were used under conditions of 100 V and 60 Hz. Furthermore, unless otherwise specified, the water-absorbing resin, water-absorbing agent, and absorbent article were used under the conditions of 25 ° C. ± 2 ° C. and relative humidity of 50% RH. Moreover, 0.90 mass% sodium chloride aqueous solution was used as physiological saline.

  In addition, as a comparison, when a comparative test is performed with a commercially available water-absorbent resin, a diaper, or a water-absorbent resin taken out from the diaper, if moisture is absorbed in the distribution process, it is appropriately dried under reduced pressure (eg, 60 to 80 ° C. for about 16 hours). ) And the moisture content of the water-absorbent resin is dried to equilibrium (around 5% by mass, 2 to 8% by mass) and then compared.

(A) Absorption capacity under no pressure with respect to physiological saline (CRC / Cenrifuge Retention Capacity)
0.20 g of the water-absorbing agent was evenly placed in a non-woven bag (60 mm × 85 mm) and immersed in physiological saline adjusted to 25 ± 2 ° C. After 30 minutes, the bag was pulled up, drained at 250 G (250 × 9.81 m / s ² ) for 3 minutes using a centrifuge (manufactured by Kokusan Co., Ltd., model H-122 small centrifuge), Mass W2 (g) was measured. Moreover, the same operation was performed without using a water absorbing agent, and the mass W1 (g) at that time was measured. And from these masses W1 and W2, the absorption capacity (g / g) was calculated according to the following formula.

(B) Absorption capacity at a high pressure of 4.8 kPa in saline (Absorbency Against Pressure at 4.8 kPa; AAP 4.8 kPa)
0.900 g of a water-absorbing agent is uniformly sprayed on a metal mesh at the bottom of a plastic support cylinder having an inner diameter of 60 mm in which a 400-mesh stainless steel mesh (mesh size 38 μm) is welded to one side (bottom) of a cylindrical cross section, A piston (cover plate) whose outer diameter is slightly smaller than 60 mm and no gap is formed on the wall surface with the support cylinder and the vertical movement is not hindered is placed thereon, and the support cylinder, water-absorbing agent, and piston mass W3 ( g) was measured. On this piston, a load adjusted so that a load of 4.8 kPa (about 50 g / cm ² , about 0.7 psi) including the piston can be uniformly applied to the water-absorbing agent is measured. Completed the device. A glass filter having a diameter of 90 mm and a thickness of 5 mm was placed inside a petri dish having a diameter of 150 mm, and physiological saline adjusted to 25 ± 2 ° C. was added so as to be at the same level as the upper surface of the glass filter. On top of that, a sheet of 9 cm diameter filter paper (Toyo Filter Paper Co., Ltd., No. 2) was placed so that the entire surface was wetted, and excess liquid was removed.

  The set of measuring devices was placed on the wet filter paper, and the liquid was absorbed under load. When the liquid level dropped from the top of the glass filter, the liquid was added to keep the liquid level constant. After 1 hour, the set of measuring devices was lifted, and the mass W4 (g) (the mass of the supporting cylinder, the swollen water absorbing agent and the piston) after removing the load was measured again. And from these masses W3 and W4, the absorption capacity under high pressure (AAP 4.8 kPa) (g / g) was calculated according to the following formula.

(C) Absorption capacity under pressure at 1.9 kPa in physiological saline (Absorbency Against Pressure at 1.9 kPa: AAP 1.9 kPa)
In the above (b), the same operation is performed except that the load uniformly applied to the water absorbing agent including the piston is changed to 1.9 kPa (about 20 g / cm ² , about 0.3 psi). By using, the absorption capacity under pressure (AAP 1.9 kPa) was calculated.

(D) Mass (weight) average particle diameter (D50), logarithmic standard deviation (σζ) and mass percentage of particle diameter less than 150 μm Water absorbing agent is 850 μm, 710 μm, 600 μm, 500 μm, 425 μm, 300 μm, 212 μm, 150 μm, 106 μm, Classification was performed using a 45 μm JIS standard sieve, and the mass percentage with a particle size of less than 150 μm was measured. The residual percentage R of each particle size was plotted on a logarithmic probability paper. Thereby, the particle size corresponding to R = 50% by mass was read as the mass average particle size (D50). In addition, the logarithmic standard deviation (σζ) is expressed by the following equation, and the smaller the value of σζ, the narrower the particle size distribution.

  In addition, the classification sieve is prepared by charging 10.00 g of the water-absorbing agent into the above-mentioned JIS standard sieve (The IIDA TESTING SIEVE: inner diameter 80 mm) and using a low-tap type sieve shaker (manufactured by Iida Seisakusho, ES-65 type sieve). Classification for 5 minutes using a shaker.

  The mass average particle diameter (D50) is a particle diameter of a standard sieve corresponding to 50% by mass of the whole particle with a standard sieve having a constant mesh as described in US Pat. No. 5,051,259.

(E) Soluble component (soluble component in physiological saline for 1 hour and 16 hours)
First, preparations before measurement of 1-hour and 16-hour soluble components in physiological saline (hereinafter referred to as 1-hour soluble components and 16-hour soluble components, respectively) will be described. Calibrate the pH electrode with a pH 4.0, pH 7.0, pH 10.0 buffer. Next, 50 ml of a physiological saline solution prepared in advance as a blank was weighed into a 100 ml glass beaker, and 0.1 mol / L sodium hydroxide aqueous solution was dropped until pH 10 while stirring with a 30 mm long stirrer chip. The blank sodium hydroxide aqueous solution dropping amount V _ab (ml) was determined. While stirring continuously, 0.1 mol / L hydrochloric acid aqueous solution was dropped until pH 2.7 was obtained, and a blank hydrochloric acid dropping amount V _bb (ml) was determined.

  200 ml of physiological saline prepared in advance was added to a 250 ml polypropylene cup with a lid, and 1.0 g (= m (g)) of the water-absorbing agent obtained in Examples or Comparative Examples described later was added thereto. Then, a soluble matter was extracted by stirring at 500 ± 50 rpm for 1 hour or 16 hours using a stirring bar having a length of 30 mm and a thickness of 8 mm. After stirring for 1 hour or 16 hours, the mixture was filtered using filter paper (manufactured by Toyo Filter Paper Co., Ltd., No. 2, retention particle diameter defined by JIS P 3801) to obtain a filtrate.

  20 ml of the obtained filtrate (recorded as F (ml)) was weighed into a 100 ml glass beaker and made up to 50 ml with physiological saline to obtain a titration filtrate. In addition, when not much filtrate was obtained and less than 20 ml, after recording the whole amount as F (ml), it was made up to 50 ml with 0.90 mass% sodium chloride aqueous solution to obtain a filtrate for titration. .

Then, while stirring the measurement filtrate with a cylindrical stirrer having a length of 30 mm and a thickness of 8 mm, a 0.1 mol / L sodium hydroxide aqueous solution was dropped until pH 10 was reached, and a sodium hydroxide aqueous solution dropping amount V _a ( ml). While continuing stirring, a 0.1 mol / L aqueous hydrochloric acid solution was added dropwise until the pH reached 2.7, and a hydrochloric acid aqueous solution dropping amount V _b (ml) was determined. Moreover, the calculation formula which calculates | requires soluble content (%) is as follows.

Here, W _a (g) is the relative mass of the unit having an acid group among the soluble components of the water-absorbing agent, and W _b is neutralized by an alkali metal among the soluble components contained in the water-absorbing agent. It is the relative mass of the unit having a carbochelate group, and can be determined by the following calculation formulas.

  Here, 72 is the mass per mole of the repeating unit of the acrylic acid polymer, and when the monomer having an acid group other than acrylic acid is copolymerized, the average mass of the repeating unit including the monomer is changed. It is done. Moreover, 94 is the mass per 1 mol of repeating units of the sodium acrylate polymer. When a monomer having an acid group other than acrylic acid is copolymerized, potassium, lithium or the like is used as the alkali metal salt in addition to sodium. In the case, it is changed appropriately.

N _a (mol) is the number of moles of an acid group in the soluble component contained in the filtrate, and N _b (mol) is a carbochelate group neutralized by an alkali metal in the soluble component contained in the filtrate. The number of moles is determined by the following formula.

Here, N ₁ (mol) is the total number of moles of soluble components contained in the measurement filtrate, and is determined by the following calculation formula.

  The amount of soluble content determined by the above formula is obtained by stirring for 1 hour in physiological saline and stirring for 16 hours in physiological saline when using a filtrate obtained by stirring for 1 hour in physiological saline. When the filtrate was used, it was distinguished as soluble content (%) for 16 hours.

(F) Evaluation of urine resistance (1 hour soluble content in degradation test solution, soluble content degradation increase amount, soluble content degradation increase ratio)
L-ascorbic acid was added to physiological saline prepared in advance so as to be 0.05% by mass to prepare a deterioration test solution. Specifically, a degradation test solution was prepared by dissolving 0.50 g of L-ascorbic acid in 999.5 g of physiological saline.

  25 ml of the deterioration test solution was added to a 250 ml polypropylene cup with a lid, and 1.0 g of a water absorbing agent was added thereto to form a swollen gel. The container was covered and sealed, and the swollen gel was allowed to stand in an atmosphere of 37 ° C. for 16 hours.

  After 16 hours, 175 ml of physiological saline and a cylindrical stirrer having a length of 30 mm and a thickness of 8 mm were added, and the soluble matter after deterioration was extracted from the hydrogel by stirring for 1 hour as in (d). did.

  After extraction with stirring for 1 hour, filtration was performed by the same method as in the previous method (d) measurement of soluble content, pH titration was performed, and 1 hour soluble content (%) in the deterioration test solution was obtained by the same calculation formula. . In addition, when comparing the absolute amount of the soluble component which deteriorated and increased in evaluating urinary resistance, the soluble component degradation increase amount (% by mass) was calculated using the following formula.

  In addition, when comparing the amount of soluble content after degradation and the amount of soluble content after degradation compared to the undegraded state in evaluating urine resistance, the following formula is used. It was used to calculate the soluble component deterioration increase ratio (times).

(G) Absorption rate evaluation (Vortex method)
To 1000 parts by mass of a 0.90% by mass aqueous sodium chloride solution (saline) prepared in advance, 0.02 part by mass of food blue No. 1 as a food additive was added, and the liquid temperature was adjusted to 30 ° C. 50 ml of the physiological saline was weighed into a 100 ml beaker, and while stirring at 600 rpm with a cylindrical stirrer having a length of 40 mm and a thickness of 8 mm, 2.0 g of a water-absorbing agent was added, and the absorption rate (seconds) was measured. In accordance with the standard described in JIS K 7224-1996 “Explanation of water absorption rate test method for highly water-absorbent resin”, the end point is from when the water-absorbing agent absorbs physiological saline and covers the stirrer chip with the test solution. Time was measured as absorption rate (seconds).

(H) Hygroscopic fluidity (% by mass)
2g of water absorbing agent is evenly sprayed on the bottom of an aluminum cup with a bottom diameter of 52mm and a height of 22mm, and is quickly applied to a constant temperature and humidity chamber (PLATIOUS LUCIFER PL-2G manufactured by Tabayie Spec) adjusted to 25 ° C and 90% relative humidity in advance. And left for 60 minutes. Thereafter, the water-absorbing water-absorbing agent is transferred to a JIS standard sieve having a diameter of 7.5 cm and an opening of 2000 μm. At this time, if the water-absorbing water-absorbing agent adheres firmly to the aluminum cup and cannot be transferred to the sieve, the moisture-absorbing and blocked water-absorbing agent is peeled off with care so as not to collapse as much as possible and transferred to the sieve. Immediately, this was sieved for 8 seconds with a vibration classifier (IIDA SIEVE SHAKER, TYPE: ES-65 type, SER. No. 0501), the mass W5 (g) of the water-absorbing agent remaining on the sieve and the water absorption that passed through the sieve. The mass W6 (g) of the agent was measured. The hygroscopic fluidity (mass%) was calculated by the following formula. The lower the moisture-absorbing fluidity, the better the fluidity when absorbing moisture, and the handleability of the powder is improved.

(I) Deodorization test (evaluation of water-absorbing agent)
50 ml of human urine collected from 20 adults was added to a 120 ml polypropylene cup with a lid, and 2.0 g of a water absorbing agent was added thereto to form a swollen gel. Human urine was used within 2 hours after excretion. The container was capped and the swollen gel was kept at 37 ° C. The lid was opened 6 hours after liquid absorption, and the deodorizing effect was determined by 20 adult panelists smelling from about 3 cm from the top of the cup. For the determination, the score was described in 6 stages for each person using the following criteria, and the average value was obtained. In addition, the deodorizing effect was evaluated with a standard product obtained by performing the same operation using only human urine without adding a water-absorbing agent and setting the odor to 5.

0: Odorless 1: Smell that can be finally detected 2: Smell that can be detected but acceptable 3: Smell that can be easily detected 4: Strong odor 5: Intense odor (j) Absorber performance evaluation (10-minute return and deterioration return)
In order to evaluate the performance of the water-absorbing agent as an absorber, an absorber for evaluation was prepared and the return amount was evaluated.

  First, a method for producing an absorber for evaluation was shown below.

1 part by mass of a water absorbing agent to be described later and 2 parts by mass of pulverized wood pulp were dry-mixed using a mixer. Next, the obtained mixture was spread on a wire screen formed to 400 mesh (mesh size: 38 μm) and formed into a web having a diameter of 90 mmφ. Further, this web was pressed at a pressure of 196.14 kPa (2 kgf / cm ² ) for 1 minute to obtain an absorbent for evaluation having a basis weight of about 0.05 g / cm ² .

  Subsequently, a method for evaluating the return amount for 10 minutes is shown below.

  The absorber for evaluation was laid on the bottom of a SUS petri dish having an inner diameter of 90 mmφ, and the nonwoven fabric having a diameter of 90 mmφ was laid thereon. Subsequently, 30 ml of the deterioration test solution used in the above (f) urine resistance evaluation was poured from above the nonwoven fabric and allowed to absorb liquid for 10 minutes under no load. Thereafter, 30 sheets of filter paper (No. 2 manufactured by Toyo Filter Paper Co., Ltd.) having an outer diameter of 90 mmφ, whose total mass (W7 (g)) was measured in advance, were placed on the nonwoven fabric. Subsequently, a piston and a weight having an outer diameter of 90 mmφ (a total sum of the piston and the weight was 20 kg) were placed on the filter paper so that the load was uniformly applied to the absorbent body, the nonwoven fabric, and the filter paper. A load was applied for 5 minutes, and the returned liquid was absorbed into the filter paper. Then, the mass (W8 (g)) of 30 filter papers was measured, and the return amount for 10 minutes was measured from the following calculation formula.

  In addition, the method for evaluating the degradation return amount is shown below.

  The evaluation absorbent prepared in the same manner as described above was operated in the same manner as described above, and 30 ml of a deterioration test solution prepared in advance was poured from above the non-woven fabric to absorb liquid under no load for 16 hours at 37 ° C. Was left in the atmosphere. In addition, the petri dish was sealed in a polyethylene bag having a size of 140 mm × 200 mm so that moisture would not evaporate as much as possible during standing.

  After a predetermined time, 30 sheets of filter paper (No. 2 manufactured by Toyo Filter Paper Co., Ltd.) having an outer diameter of 90 mmφ whose total mass (W9 (g)) was measured in advance were placed on the nonwoven fabric. Subsequently, a piston and a weight having an outer diameter of 90 mmφ (a total sum of the piston and the weight was 20 kg) were placed on the filter paper so that the load was uniformly applied to the absorbent body, the nonwoven fabric, and the filter paper. A load was applied for 5 minutes, and the returned liquid was absorbed into the filter paper. Then, the mass (W10 (g)) of 30 filter papers was measured, and the degradation return amount was measured from the following calculation formula.

[Reference Example 1]
In 1500 g of an aqueous solution of sodium acrylate having a neutralization rate of 75 mol% (monomer concentration: 24% by mass), 4.3 g of polyethylene glycol diacrylate (average added mole number of ethylene oxide 9) was dissolved to obtain a reaction solution. The obtained reaction solution was poured into a stainless bat having a size of 320 mm long × 220 mm wide × 50 mm high. At this time, the thickness of the reaction solution was 17 mm. The stainless steel bat was sealed with a polyethylene film provided with a nitrogen inlet, an exhaust port, and a polymerization initiator inlet, and then immersed in a 30 ° C. water bath, while adjusting the temperature of the reaction solution to 30 ° C. Then, nitrogen gas was introduced into the reaction solution to remove dissolved oxygen in the solution. Thereafter, nitrogen gas was introduced into the upper space of the reaction vessel and continued to be exhausted from the opposite side. As a polymerization initiator, 5.1 g of a 10 mass% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride, 2.5 g of a 10 mass% aqueous solution of sodium persulfate, and 1 mass of L-ascorbic acid 0.4 g of a 0.1% aqueous solution and 2.2 g of a 0.35 mass% aqueous solution of hydrogen peroxide were injected and mixed well with a magnetic stirrer. Since the polymerization started 1 minute after the polymerization initiator was charged, the operation of immersing the stainless steel vat in a water bath having a liquid temperature of 12 ° C. to a height of 10 mm from the bottom of the vat was repeated repeatedly to control the polymerization temperature. Since a polymerization peak of 80 ° C. was exhibited 55 minutes after the start of the polymerization, it was immersed in a water bath at a liquid temperature of 70 ° C. to a height of 10 mm from the bottom of the vat and held for 60 minutes in order to age the gel. The obtained hydrogel polymer was pulverized with a meat chopper (No. 32 type meat chopper, Hiraga Manufacturing Co., Ltd.) with a die having a diameter of 9.5 mm, on a wire mesh of 50 mesh (mesh size 300 μm). And dried with hot air at 160 ° C. for 60 minutes. Next, the dried product was pulverized with a roll mill, classified and prepared with a wire mesh having openings of 710 μm and 150 μm to obtain an irregularly crushed water-absorbent resin powder (a). Table 1 shows the absorption capacity without load (CRC), the mass average particle diameter (D50), and the ratio (%) of particles less than 150 μm of the obtained water-absorbent resin (a). In addition, it evaluated similarly about the water absorbing resin (b)-(l) obtained by the following reference examples, and it shows in Table 1.

  A surface cross-linking agent 3.9 consisting of 0.55 parts by mass of propylene glycol, 0.35 parts by mass of 1,4-butanediol, and 3 parts by mass of water is added to 100 parts by mass of the obtained water absorbent resin powder (a). Mass parts were mixed. The mixture was heat-treated at a heat medium temperature of 210 ° C. for 40 minutes to obtain a water absorbent resin (1).

[Reference Example 2]
4.0 g of polyethylene glycol diacrylate (average added mole number of ethylene oxide 9) was dissolved in 5500 g of an aqueous solution of sodium acrylate having a neutralization rate of 75 mol% (monomer concentration 40% by mass) to prepare a reaction solution. Next, the reaction solution was supplied to a reactor formed by attaching a lid to a stainless steel double-armed kneader with an internal volume of 10 L having two sigma-shaped blades, and the system was nitrogenated while maintaining the reaction solution at 30 ° C. The gas was replaced. Subsequently, 29.8 g of a 10% by weight aqueous solution of sodium persulfate and 1.5 g of a 1% by weight aqueous solution of L-ascorbic acid were added while stirring the reaction solution, and polymerization started 1 minute later. A polymerization peak temperature of 93 ° C. was exhibited 15 minutes after the start of polymerization, and a hydrogel polymer was taken out 60 minutes after the start of polymerization. The obtained hydrogel polymer was subdivided into particles of 1 to 4 mm. This finely divided hydrogel polymer was spread on a 50 mesh (mesh size 300 μm) wire net and dried with hot air at 160 ° C. for 60 minutes. Subsequently, the dried product was pulverized using a roll mill, and further classified and prepared with a wire mesh having openings of 710 μm and 150 μm to obtain an amorphous crushed water-absorbent resin powder (b).

  To 100 parts by mass of the obtained water absorbent resin powder (b), 0.5 part by mass of propylene glycol, 0.03 part by mass of ethylene glycol diglycidyl ether, 0.3 part by mass of 1,4-butanediol, and water 3.53 parts by mass of a surface cross-linking agent consisting of 2.7 parts by mass was mixed. The mixture was heat-treated at a heat medium temperature of 210 ° C. for 45 minutes to obtain a water absorbent resin (2).

[Reference Example 3]
2.5 g of polyethylene glycol diacrylate (average added mole number of ethylene oxide 9) was dissolved in 5500 g of an aqueous solution of sodium acrylate having a neutralization rate of 75 mol% (monomer concentration 38 mass%) to prepare a reaction solution. Next, after degassing this reaction solution in the same manner as in Reference Example 2, the above reaction solution was supplied to the reactor of Reference Example 2, and the system was purged with nitrogen gas while keeping the reaction solution at 30 ° C. Subsequently, while stirring the reaction solution, 29.8 g of a 10% by weight aqueous solution of sodium persulfate and 1.5 g of a 1% by weight aqueous solution of L-ascorbic acid were added, and polymerization started about 1 minute later. A polymerization peak temperature of 86 ° C. was exhibited 17 minutes after the start of the polymerization, and a hydrogel polymer was taken out 60 minutes after the start of the polymerization. The obtained hydrogel polymer was fragmented into particles of about 1 to 4 mm. This hydrogel polymer was dried and pulverized in the same manner as in Reference Example 2, and further classified and prepared with a wire mesh having openings of 710 μm and 150 μm to obtain amorphous crushed water absorbent resin powder (c).

  Next, 3.53 parts by mass of a surface cross-linking agent having the same composition as in Reference Example 2 was mixed with 100 parts by mass of the obtained water absorbent resin powder (c). The mixture was heat treated at a heat medium temperature of 195 ° C. for 40 minutes to obtain a water absorbent resin (3).

[Reference Example 4]
To 5500 g of an aqueous solution of sodium acrylate having a neutralization rate of 75 mol% (monomer concentration 33% by mass), 19.6 g of polyethylene glycol diacrylate (average number of moles of added ethylene oxide 9), disodium phosphite · 5 36.3 g of hydrate was dissolved to prepare a reaction solution. Next, after degassing this reaction solution in the same manner as in Reference Example 2, the above reaction solution was supplied to the reactor of Reference Example 2, and the system was purged with nitrogen gas while keeping the reaction solution at 30 ° C. Subsequently, while stirring the reaction solution, 20.5 g of a 10% by weight aqueous solution of sodium persulfate and 1.0 g of a 1% by weight aqueous solution of L-ascorbic acid were added, and polymerization started about 1 minute later. A polymerization peak temperature of 85 ° C. was exhibited 17 minutes after the start of polymerization, and a hydrogel polymer was taken out 60 minutes after the start of polymerization. The obtained hydrogel polymer was fragmented into particles of about 1 to 4 mm. This hydrogel polymer was dried and pulverized in the same manner as in Reference Example 2, and further classified and prepared with a wire mesh having openings of 600 μm and 150 μm to obtain an irregularly crushed water absorbent resin powder (d).

  Next, 3.53 parts by mass of a surface cross-linking agent having the same composition as in Reference Example 2 was mixed with 100 parts by mass of the obtained water absorbent resin powder (d). The above mixture was heat-treated at a heat medium temperature of 210 ° C. for 35 minutes to obtain a water absorbent resin (4).

[Reference Example 5]
To 5500 g of an aqueous solution of sodium acrylate having a neutralization rate of 70 mol% (monomer concentration of 30% by mass), 20.0 g of polyethylene glycol diacrylate (average added mole number of ethylene oxide 9) and 3.3 g of sodium phosphinate were added. Dissolved to give a reaction solution. Next, after degassing this reaction solution in the same manner as in Reference Example 2, the above reaction solution was supplied to the reactor of Reference Example 2, and the system was purged with nitrogen gas while keeping the reaction solution at 30 ° C. Subsequently, while stirring the reaction solution, 22.6 g of a 10% by weight aqueous solution of sodium persulfate and 1.1 g of a 1% by weight aqueous solution of L-ascorbic acid were added, and polymerization started about 1 minute later. A polymerization peak temperature of 82 ° C. was exhibited 18 minutes after the start of the polymerization, and a hydrogel polymer was taken out 40 minutes after the start of the polymerization. The obtained hydrogel polymer was fragmented into particles of about 1 to 4 mm. This hydrogel polymer was dried and pulverized in the same manner as in Reference Example 2, and further classified and prepared with a wire mesh having openings of 600 μm and 150 μm to obtain amorphous crushed water-absorbent resin powder (e).

  Next, the surface cross-linking agent 3 comprising 100 parts by mass of the obtained water-absorbent resin powder (e), 0.5 parts by mass of propylene glycol, 0.3 parts by mass of 1,3-propanediol, and 3 parts by mass of water. 8 parts by weight were mixed. The mixture was heat treated at a heat medium temperature of 195 ° C. for 40 minutes to obtain a water absorbent resin (5).

[Reference Example 6]
In 1500 g of acrylic acid aqueous solution (monomer concentration 20% by mass), 1.9 g of tetraallyloxyethane was dissolved as a reaction solution, and the obtained reaction solution was poured into the stainless steel bat of Reference Example 1. At this time, the thickness of the reaction solution was 17 mm. The stainless steel bat was sealed in the same manner as in Reference Example 1, and then immersed in a 20 ° C. water bath, while adjusting the temperature of the reaction solution to 20 ° C., nitrogen gas was introduced into the reaction solution and dissolved in the solution. Oxygen was removed. Thereafter, nitrogen gas was introduced into the upper space of the reaction vessel and continued to be exhausted from the opposite side. Subsequently, while stirring the reaction solution with a magnetic stirrer, 8.3 g of a 10% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride as a polymerization initiator and 5% by mass of L-ascorbic acid were used. When 0.6 g of an aqueous solution and 2.1 g of a 3.5% by mass aqueous solution of hydrogen peroxide were added, polymerization started about 1 minute later. During the polymerization reaction, cooling and heating were repeated from the lower surface of the bat, and a peak temperature of 75 ° C. was exhibited 35 minutes after the start of polymerization. After the obtained hydrogel polymer was cut with scissors about 5 cm square, the obtained hydrogel polymer of about 5 cm square was supplied to the same meat chopper as in Reference Example 1 at a constant rate while being 22% by mass. 702 g of aqueous sodium carbonate solution was supplied at a constant rate, and at the same time, post-neutralization was performed while pulverizing the gel. The crushed gel discharged from the meat chopper was kept in an atmosphere at about 70 ° C. until it did not turn red even when the phenolphthalein solution was applied to the gel, and then dried and crushed in the same manner as in Reference Example 1, By classifying and blending with an opening 600 μm and 150 μm wire mesh, an irregularly crushed water-absorbent resin powder (f) was obtained.

  Next, 100 parts by mass of the obtained water absorbent resin powder (f), 0.5 parts by mass of propylene glycol, 0.03 parts by mass of ethylene glycol diglycidyl ether, 0.3 parts by mass of 1,3-propanediol, Then, 3.83 parts by mass of a surface cross-linking agent consisting of 3 parts by mass of water was mixed. The mixture was heat-treated at a heat medium temperature of 195 ° C. for 40 minutes to obtain a water absorbent resin (6).

[Reference Example 7]
The dried hydrogel polymer obtained in Reference Example 2 was pulverized using the same roll mill as in Reference Example 2 under the pulverization conditions that were finer than those in Reference Example 2, and further a wire mesh with openings of 425 μm and 150 μm. By classifying and blending, an irregularly shaped water-absorbent resin powder (g) was obtained.

  Subsequently, from 100 parts by mass of the obtained water absorbent resin powder (g), from 1 part by mass of propylene glycol, 0.03 part by mass of ethylene glycol diglycidyl ether, 3 parts by mass of water, and 0.9 part by mass of methanol 4.93 parts by mass of the resulting surface cross-linking agent was mixed. The mixture was heat-treated at a heat medium temperature of 210 ° C. for 45 minutes to obtain a water absorbent resin (7).

[Reference Example 8]
The dried product of the hydrogel polymer obtained in Reference Example 3 was pulverized using the same roll mill as in Reference Example 3 under the pulverization conditions that were finer than those in Reference Example 3, and further a wire mesh having openings of 500 μm and 150 μm. By classifying and blending, an irregularly shaped water-absorbent resin powder (h) was obtained.

  Next, 3.53 parts by mass of a surface cross-linking agent having the same composition as in Reference Example 3 was mixed with 100 parts by mass of the obtained water absorbent resin powder (h). The mixture was heat-treated at a heat medium temperature of 210 ° C. for 45 minutes to obtain a water absorbent resin (8).

[Reference Example 9]
The dried product of the hydrogel polymer obtained in Reference Example 2 was pulverized using the same roll mill as in Reference Example 2 under the pulverization conditions that were coarser than those in Reference Example 2, and further a wire mesh with openings of 850 μm and 106 μm. By classifying and blending, an irregularly crushed water-absorbent resin powder (i) was obtained.

  Next, 3.53 parts by mass of the same surface crosslinking agent as in Reference Example 2 was mixed with 100 parts by mass of the obtained water absorbent resin powder (i). The mixture was heat-treated at a heat medium temperature of 210 ° C. for 55 minutes to obtain a water absorbent resin (9).

[Reference Example 10]
The dried hydrogel polymer obtained in Reference Example 3 was pulverized by using the same roll mill as in Reference Example 9 under the pulverization conditions that were more coarse than those in Reference Example 9, and further having openings of 850 μm and 150 μm. By classifying and blending with a wire mesh, an irregularly crushed water-absorbent resin powder (j) was obtained.

  Next, 3.53 parts by mass of the same surface cross-linking agent as in Reference Example 2 was mixed with 100 parts by mass of the obtained water absorbent resin powder (j). The mixture was heat treated at a heat medium temperature of 195 ° C. for 45 minutes to obtain a water absorbent resin (10).

[Reference Example 11]
In Reference Example 4, a water-absorbent resin (11) was obtained in the same manner as in Reference Example 4 except that disodium phosphite pentahydrate was not added.

[Example 1]
The water absorbent resin (1) obtained in Reference Example 1 was used as it is as the water absorbent (1). Absorption capacity under no pressure of water-absorbing agent (1), absorption capacity under high pressure at 4.8 kPa, soluble for 16 hours in physiological saline, absorption capacity under pressure at 1.9 kPa, urine resistance evaluation results, The absorption rate evaluation and the particle size distribution are shown in Tables 2 to 4.

[Example 2]
To 100 parts by mass of the water-absorbent resin (2) obtained in Reference Example 2, 2 parts by mass of diethylenetriaminepentaacetic acid aqueous solution was spray-mixed so that diethylenetriaminepentaacetic acid sodium salt was 50 ppm with respect to the water-absorbent resin (2). The obtained mixture was cured at 60 ° C. for 1 hour to obtain a water absorbing agent (2). The water absorbing agent (2) was evaluated in the same manner as in Example 1, and the results are shown in Tables 2 to 4. In addition, the water-absorbing agent (2) obtained was granulated through the spray mixing of the aqueous liquid and the curing step.

[Example 3]
To 100 parts by mass of the water-absorbent resin (3) obtained in Reference Example 3, 2 parts by mass of diethylenetriaminepentaacetic acid aqueous solution was spray-mixed so that diethylenetriaminepentaacetic acid sodium salt was 100 ppm with respect to the water-absorbent resin (3). The obtained mixture was cured at 60 ° C. for 1 hour to obtain a water absorbing agent (3). The water absorbing agent (3) was evaluated in the same manner as in Example 1, and the results are shown in Tables 2 to 4. In addition, the water-absorbing agent (3) obtained was granulated through the spray mixing and curing process of the aqueous liquid.

[Example 4]
2 parts by mass of water was spray mixed with 100 parts by mass of the water absorbent resin (4) obtained in Reference Example 4. The obtained mixture was cured at 60 ° C. for 1 hour to obtain a water absorbing agent (4). The water absorbing agent (4) was evaluated in the same manner as in Example 1, and the results are shown in Tables 2 to 4. In addition, the obtained water absorbing agent (4) was granulated by passing through the water spray mixing and hardening process.

[Example 5]
In Example 4, the same operation was carried out except that the water absorbent resin (4) obtained in Reference Example 4 was changed to the water absorbent resin (5) obtained in Reference Example 5 to obtain a water absorbent (5). It was. The water absorbing agent (5) was evaluated in the same manner as in Example 1, and the results are shown in Tables 2 to 4. In addition, the water-absorbing agent (5) obtained was granulated through the water spray mixing and curing step.

[Example 6]
In Example 4, the same operation was carried out except that the water absorbent resin (4) obtained in Reference Example 4 was changed to the water absorbent resin (6) obtained in Reference Example 6 to obtain a water absorbent (6). It was. The water absorbing agent (6) was evaluated in the same manner as in Example 1, and the results are shown in Tables 2 to 4. In addition, the water-absorbing agent (6) obtained was granulated through the water spray mixing and curing steps.

[Example 7]
In Example 2, the same operation was performed except that the water absorbent resin (2) obtained in Reference Example 2 was changed to the water absorbent resin (7) obtained in Reference Example 7, to obtain a water absorbent (7). It was. The water absorbing agent (7) was evaluated in the same manner as in Example 1, and the results are shown in Tables 2 to 4. In addition, the obtained water-absorbing agent (7) was granulated by passing through the water spray mixing and hardening process.

[Example 8]
In Example 3, the same operation was carried out except that the water absorbent resin (3) obtained in Reference Example 3 was replaced with the water absorbent resin (8) obtained in Reference Example 8, to obtain a water absorbent (8). It was. The water absorbing agent (8) was evaluated in the same manner as in Example 1, and the results are shown in Tables 2 to 4. In addition, the water-absorbing agent (8) obtained was granulated through the spray mixing and curing process of water.

[Comparative Example 1]
In Example 2, the same operation was performed except that the water absorbent resin (2) obtained in Reference Example 2 was changed to the water absorbent resin (9) obtained in Reference Example 9, and a comparative water absorbent (1) Got. The comparative water-absorbing agent (1) was evaluated in the same manner as in Example 1, and the results are shown in Tables 2 to 4. The comparative water-absorbing agent (1) thus obtained was granulated by passing through the water spray mixing and curing steps.

[Comparative Example 2]
In Example 3, the same operation was performed except that the water absorbent resin (3) obtained in Reference Example 3 was replaced with the water absorbent resin (10) obtained in Reference Example 10, and a comparative water absorbent (2) Got. The comparative water-absorbing agent (2) was evaluated in the same manner as in Example 1, and the results are shown in Tables 2-4. In addition, the comparative water-absorbing agent (2) obtained was granulated by passing through the water spray mixing and curing step.

[Comparative Example 3]
In Example 2, the same operation was carried out except that the aqueous diethylenetriaminepentaacetate solution was changed to water to obtain a comparative water-absorbing agent (3). The comparative water-absorbing agent (3) was evaluated in the same manner as in Example 1, and the results are shown in Tables 2 to 4. Further, the hygroscopic fluidity was evaluated, and the results are shown in Table 5. In addition, the comparative water-absorbing agent (3) obtained was granulated through the spray mixing and curing process of water.

[Comparative Example 4]
In Example 3, the same operation was carried out except that the aqueous diethylenetriaminepentaacetate solution was changed to water to obtain a comparative water-absorbing agent (4). The comparative water-absorbing agent (4) was evaluated in the same manner as in Example 1, and the results are shown in Tables 2 to 4. Further, the hygroscopic fluidity was evaluated, and the results are shown in Table 5. In addition, the comparative water-absorbing agent (4) obtained was granulated by passing through the water spray mixing and curing step.

[Comparative Example 5]
In Example 4, the same operation was performed except that the water absorbent resin (4) obtained in Reference Example 4 was changed to the water absorbent resin (11) obtained in Reference Example 11, and a comparative water absorbent (5) Got. The comparative water-absorbing agent (5) was evaluated in the same manner as in Example 1, and the results are shown in Tables 2 to 4. Note that the comparative water-absorbing agent (5) obtained was granulated through the water spray mixing and curing step.

[Example 9]
To 100 parts by mass of the water-absorbing agent (1) obtained in Example 1, 0.3 parts by mass of particulate aluminum stearate (manufactured by Kanto Chemical Co., Ltd.) was added and mixed (dry blended) to obtain the water-absorbing agent (9). Got. When the particle size distribution of the obtained water-absorbing agent (9) was measured, there was almost no change. The mass-average particle diameter (D50), logarithmic standard deviation (σζ), and mass percentage less than 150 μm were the water-absorbing agent before mixing. The same value as (1) was shown. Further, the urine resistance evaluation and the 16-hour soluble component in physiological saline showed the same value as the water-absorbing agent (1) before mixing. Absorption capacity under no pressure of water-absorbing agent (9), absorption capacity under pressure at 1.9 kPa, soluble content for 16 hours in physiological saline, urine resistance evaluation, absorption rate evaluation, under high pressure at 4.8 kPa Absorption capacity and moisture absorption fluidity were measured and are shown in Table 5.

[Example 10]
To 100 parts by mass of the water-absorbing agent (2) obtained in Example 2, 0.3 parts by mass of particulate silicon dioxide (trade name: Aerosil 200 (average particle diameter of primary particles: 12 nm); manufactured by Nippon Aerosil Co., Ltd.) Addition and mixing (dry blending) gave the water-absorbing agent (10). When the particle size distribution of the obtained water-absorbing agent (10) was measured, there was almost no change, and the mass average particle diameter (D50), logarithmic standard deviation (σζ), and mass percentage less than 150 μm were the water-absorbing agent before mixing. The same value as (2) was shown. The urine resistance evaluation and the 16-hour soluble component in physiological saline also showed the same value as the water-absorbing agent (2) before mixing. The water absorbing agent (10) was evaluated in the same manner as in Example 9, and the results are shown in Table 5.

[Example 11]
A water absorbing agent (11) was obtained in the same manner as in Example 10 except that the particulate silicon dioxide was changed to the particulate aluminum stearate. When the particle size distribution of the obtained water-absorbing agent (11) was measured, there was almost no change, and the mass average particle diameter (D50), logarithmic standard deviation (σζ), and mass percentage less than 150 μm were the water-absorbing agent before mixing. The same value as (2) was shown. The urine resistance evaluation and the 16-hour soluble component in physiological saline also showed the same value as the water-absorbing agent (2) before mixing. The water absorbing agent (11) was evaluated in the same manner as in Example 9, and the results are shown in Table 5.

[Example 12]
The same operation as in Example 10 was carried out except that the water absorbing agent (2) obtained in Example 2 was changed to the water absorbing agent (3) obtained in Example 3, to obtain a water absorbing agent (12). When the particle size distribution of the obtained water-absorbing agent (12) was measured, there was almost no change, and the mass-average particle diameter (D50), logarithmic standard deviation (σζ), and mass percentage less than 150 μm were the water-absorbing agent before mixing. The same value as (3) was shown. The urine resistance evaluation and the 16-hour soluble content in physiological saline also showed the same value as the water-absorbing agent (3) before mixing. The water absorbing agent (12) was evaluated in the same manner as in Example 9, and the results are shown in Table 5.

[Example 13]
In Example 10, the water absorbing agent (2) obtained in Example 2 was changed to the water absorbing agent (3) obtained in Example 3, except that the particulate silicon dioxide was changed to particulate aluminum stearate. The water absorbing agent (13) was obtained. When the particle size distribution of the obtained water-absorbing agent (13) was measured, there was almost no change. The mass-average particle diameter (D50), logarithmic standard deviation (σζ), and mass percentage less than 150 μm were the water-absorbing agent before mixing. The same value as (3) was shown. The urine resistance evaluation and the 16-hour soluble content in physiological saline also showed the same value as the water-absorbing agent (3) before mixing. The water absorbing agent (13) was evaluated in the same manner as in Example 9, and the results are shown in Table 5.

[Example 14]
To 100 parts by mass of the water-absorbing agent (4) obtained in Example 4, 0.3 parts by mass of fine particle silicon dioxide (trade name / Aerosil 200) was added and mixed (dry blended) to obtain the water-absorbing agent (14). Obtained. When the particle size distribution of the obtained water-absorbing agent (14) was measured, there was almost no change, and the mass-average particle size (D50), logarithmic standard deviation (σζ), and mass percentage less than 150 μm were the water-absorbing agent before mixing. The same value as (4) was shown. The urine resistance evaluation and the 16-hour soluble content in physiological saline also showed the same value as the water-absorbing agent (4) before mixing. The water absorbing agent (14) was evaluated in the same manner as in Example 9, and the results are shown in Table 5.

[Example 15]
To 100 parts by mass of the water-absorbing agent (5) obtained in Example 5, 0.3 parts by mass of particulate magnesium stearate (manufactured by Kanto Chemical Co., Ltd.) was added and mixed (dry blended) to obtain the water-absorbing agent (15). Got. When the particle size distribution of the obtained water-absorbing agent (15) was measured, there was almost no change, and the mass-average particle diameter (D50), logarithmic standard deviation (σζ), and mass percentage less than 150 μm were the water-absorbing agent before mixing. The same value as (5) was shown. The urine resistance evaluation and the 16-hour soluble component in physiological saline also showed the same value as the water-absorbing agent (5) before mixing. The water absorbing agent (15) was evaluated in the same manner as in Example 9, and the results are shown in Table 5.

[Examples 16 to 18]
In Example 10, the water-absorbing agents (16) to (18) were obtained by changing the water-absorbing agents (2) obtained in Example 2 to the water-absorbing agents (6) to (8) obtained in Examples 6 to 8. ) Respectively. When the particle size distribution of the obtained water-absorbing agents (16) to (18) was measured, none of them changed, and the mass average particle diameter (D50), logarithmic standard deviation (σζ), and mass percentage with a particle diameter of less than 150 μm. Showed the same values as the water-absorbing agents (6) to (8) before mixing. Moreover, the urine resistance evaluation and the 16-hour soluble component in physiological saline also showed the same values as the water-absorbing agents (6) to (8) before mixing. The water absorbing agents (16) to (18) were evaluated in the same manner as in Example 9, and the results are shown in Table 5.

[Comparative Examples 6-7]
In Example 10, the water-absorbing agent (2) obtained in Example 2 was changed to the water-absorbing agent for comparison (1) and (2) obtained in Comparative Examples 1 and 2, so that the water-absorbing agent for comparison (6 ) And (7) were obtained. When the particle size distributions of the comparative water-absorbing agents (6) and (7) obtained were measured, neither of them was changed, and the mass average particle diameter (D50), logarithmic standard deviation (σζ), and particle diameter of less than 150 μm. The mass percentage showed the same value as the comparative water-absorbing agent (1) and (2) before mixing. Further, the urine resistance evaluation and the 16-hour soluble component in physiological saline also showed the same values as the comparative water-absorbing agents (1) and (2) before mixing. The comparative water-absorbing agents (6) and (7) were evaluated in the same manner as in Example 9, and the results are shown in Table 5.

  In addition, the hygroscopic fluidity of the comparative water-absorbing agents (3) and (4) was also evaluated, and the results are shown in Table 5.

[Example 19]
To 100 parts by mass of the water-absorbent resin (2) obtained in Reference Example 2, 15% by mass aqueous solution of diethylenetriaminepentaacetic acid sodium acetate solution and leaf extract of camellia plant (product name: FS-80MO, seller: Shiraimatsu Shinyaku) 2 parts by weight of aqueous solution (diethylenetriaminepentaacetic acid sodium salt is 50 ppm with respect to the water-absorbent resin (2), 15 parts by weight of the camellia plant leaf extract) % Aqueous solution was adjusted to 0.1% with respect to the water absorbent resin (2)). The obtained mixture was cured at 60 ° C. for 1 hour to obtain a water absorbing agent (19). The particle size distribution of the water-absorbing agent (19) obtained was the same as that in Example 10 in which the 15% by mass aqueous solution of the leaf extract of camelliaceae was not added. Further, the absorption capacity of the water-absorbing agent (19) under no pressure, the absorption capacity under pressure at 1.9 kPa, the deodorization test, the soluble matter for 16 hours in physiological saline, the urine resistance evaluation, and the high at 4.8 kPa. The absorption capacity under pressure was measured and shown in Table 6.

[Example 20]
In Example 10, a particulate silicon dioxide was mixed with a composite hydrous oxide of zinc and silicon (trade name: CERATIOX SZ-100, manufactured by Titanium Industry Co., Ltd., mass ratio of zinc and silicon: 82/18, average particle diameter: A water absorbing agent (20) was obtained by performing the same operation except that the thickness was changed to 0.36 μm. The particle size distribution of the water-absorbing agent (20) obtained was the same as that of the water-absorbing agent (10). Further, the water absorbing agent (20) was evaluated in the same manner as the water absorbing agent (19), and the results are shown in Table 6.

[Example 21]
In Example 19, the same operation was performed except that the water absorbent resin (2) obtained in Reference Example 2 was changed to the water absorbent resin (3) obtained in Reference Example 3, and the water absorbent (21) was obtained. Obtained. The particle size distribution of the water-absorbing agent (21) obtained was the same as that of the water-absorbing agent (12). The water absorbing agent (21) was evaluated in the same manner as the water absorbing agent (19), and the results are shown in Table 6.

[Example 22]
In Example 12, a particulate silicon dioxide was mixed with a composite hydrous oxide of zinc and silicon (trade name: CERATIOX SZ-100, manufactured by Titanium Industry Co., Ltd., mass ratio of zinc and silicon: 82/18, average particle size: A water absorbing agent (22) was obtained by performing the same operation except that the thickness was changed to 0.36 μm. The particle size distribution of the water-absorbing agent (22) obtained was the same as that of the water-absorbing agent (12). The water absorbing agent (22) was evaluated in the same manner as the water absorbing agent (19), and the results are shown in Table 6.

  In addition, Table 6 also shows the results of deodorizing tests of the comparative water-absorbing agents (3) and (4).

[Example 23]
In order to evaluate the performance of the water-absorbing agent (2) obtained in Example 2 as an absorber, the absorber for evaluation (1) was prepared according to the method for evaluating the performance of the absorber (j) above, and the return amount and deterioration return for 10 minutes. The amount was measured. The results are shown in Table 7.

[Examples 24-27]
By changing the water-absorbing agent (2) used in Example 23 to the water-absorbing agents (13) and (16) to (18) obtained in Examples 13 and 16 to 18, the absorber for evaluation (2) To (5) were obtained.

  Table 7 shows the return amount evaluation results of the obtained absorbent articles (2) to (5).

[Comparative Examples 8-12]
By changing the water-absorbing agent (2) used in Example 23 to the comparative water-absorbing agents (3) to (7) obtained in Comparative Examples 3 to 7, the comparative evaluation absorbers (1) to (5) )

  Table 7 shows the evaluation results of the return amounts of the obtained comparative evaluation absorbent bodies (1) to (5).

[Example 28]
In 1500 g of acrylic acid aqueous solution (monomer concentration 20%), 3.1 g of N, N′-methylenebisacrylamide was dissolved as a reaction solution, and the obtained reaction solution was poured into the stainless steel vat of Reference Example 1. At this time, the thickness of the reaction solution was 17 mm. The stainless steel vat is sealed in the same manner as in Reference Example 1, and then immersed in a 20 ° C. water bath, while adjusting the temperature of the reaction solution to 20 ° C., nitrogen gas is introduced into the reaction solution and dissolved in the solution. Oxygen was removed. Thereafter, nitrogen gas was introduced into the upper space of the reaction vessel and continued to be exhausted from the opposite side. Subsequently, while stirring the reaction solution with a magnetic stirrer, 20.0 g of a 10% by mass aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride as a polymerization initiator and 1% by mass of L-ascorbic acid. When 18.0 g of an aqueous solution and 20.0 g of a 3.5% by mass aqueous solution of hydrogen peroxide were added, polymerization started about 1 minute later. During the polymerization reaction, cooling and heating were repeated from the lower surface of the bat, and a peak temperature of 60 ° C. was exhibited 12 minutes after the start of polymerization. A hydrogel polymer was taken out 100 minutes after the start of polymerization. The obtained hydrogel polymer was cut with about 5 cm square scissors, and then the obtained hydrogel polymer of about 5 cm square was fed to the same meat chopper as in Reference Example 1 at a constant rate while being 40% by mass. 749 g of an aqueous sodium hydroxide solution was supplied at a constant rate, and at the same time, post-neutralization was performed while gel pulverization. The crushed gel discharged from the meat chopper was kept in an atmosphere at about 70 ° C. until it did not turn red even when the phenolphthalein solution was applied to the gel, and then dried and crushed in the same manner as in Reference Example 1, By classifying and blending with an opening 710 μm and a 150 μm wire mesh, an irregularly crushed water-absorbent resin powder (l) was obtained. Table 1 shows the absorption capacity without load (CRC), mass-average particle diameter (D50), and ratio (%) of particles less than 150 μm of the obtained water-absorbent resin (l).

  Next, 100 parts by mass of the obtained water absorbent resin powder (l), 0.5 parts by mass of propylene glycol, 0.03 parts by mass of ethylene glycol diglycidyl ether, and 0.3 parts by mass of 1,4-butanediol, Then, 3.53 parts by mass of a surface cross-linking agent consisting of 2.7 parts by mass of water was mixed. The mixture was heat treated at a heat medium temperature of 195 ° C. for 60 minutes to obtain a water absorbent resin (12).

  The obtained water-absorbing resin (12) was used as it was as the water-absorbing agent (23), and was evaluated in the same manner as in Example 1. The results are shown in Tables 2 to 4.

[Example 29]
To 100 parts by mass of the water-absorbing agent (23) obtained in Example 28, 0.1 part by mass of particulate calcium stearate (Nippon Yushi Co., Ltd.) was added and mixed (dry blended) to obtain the water-absorbing agent (24). It was. When the particle size distribution of the water-absorbing agent (24) obtained was measured, the particle size distribution did not change much, and the mass average particle size (D50), logarithmic standard deviation (σζ), and mass percentage less than 150 μm were the water absorption before mixing. The value was the same as that of the agent (23). Furthermore, the urine resistance evaluation and the 16-hour soluble component in physiological saline also showed the same value as the water-absorbing agent (23) before mixing. The water absorbing agent (24) was evaluated in the same manner as in Example 9, and the results are shown in Table 5.

[Example 30]
In order to evaluate the performance of the water-absorbing agent (23) obtained in Example 28 as an absorber, the absorber for evaluation (6) was prepared according to the method for evaluating the performance of the absorber (j) above, and the return amount and deterioration return for 10 minutes. The amount was measured. The results are shown in Table 7.

  As shown in Tables 2 to 4, the particulate water-absorbing agent of the present invention has a controlled particle size, a high absorption capacity, a controlled particle size, and can be used in physiological saline and physiological saline containing L-ascorbic acid. The difference in solute content is very small. Therefore, stable performance is exhibited regardless of changes in urine components (individual differences, seasonal differences, etc.) and usage time.

  As shown in Table 5, the particulate water-absorbing agent of the present invention is also excellent in absorption rate and moisture absorption fluidity. If necessary, a deodorizing agent can be added as shown in Table 6 by adding a deodorant. Also shows performance.

  As shown in Table 7, the particulate water-absorbing agent of the present invention gives an absorbent article (absorber in Table 7) with a small return amount to any liquid, and further absorbs as in Comparative Example 11. Since the gel fine particles do not protrude from the body, a stable high-performance absorbent article (diaper) is provided regardless of changes in urine components (individual differences, seasonal differences, etc.) and usage time.

  The water-absorbent resin obtained by the present invention is controlled to a specific particle size distribution and has excellent stability against urine. When used in an absorbent body such as a diaper, it is very superior to conventional absorbent bodies. There exists an effect that the absorber with the outstanding absorption performance can be provided.

Claims (19)

A particulate water-absorbing agent comprising as a main component a water-absorbing resin obtained by crosslinking and polymerizing an acid group and / or a salt-containing unsaturated monomer thereof, and satisfying the following (a) to (d).
(A) Absorption capacity (CRC) under no pressure to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm
(D) The soluble matter deterioration increase amount shown by the following formula is 0 to 15% by mass, and the one-hour soluble component in the deterioration test solution is 0.1 to 30% by mass, provided that the deterioration test solution is 0 0.05% by mass L-ascorbic acid-containing physiological saline.

A particulate water-absorbing agent mainly comprising a water-absorbing resin obtained by crosslinking polymerization of an acid group and / or a salt-containing unsaturated monomer, and satisfying the following (a) to (c) and (e) Agent.
(A) Absorption capacity (CRC) under no pressure to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm
(E) The soluble component deterioration increasing ratio represented by the following formula is 1 to 4 times, and the one hour soluble component in the deterioration test solution is 0.1 to 30% by mass. It is a physiological saline containing 05 mass% L-ascorbic acid.

A particulate water-absorbing agent comprising as a main component a water-absorbing resin obtained by crosslinking and polymerizing an acid group and / or a salt-containing unsaturated monomer thereof, wherein the following (a) to (c) and (f), (g) Filled particulate water-absorbing agent.
(A) Absorption capacity (CRC) under no pressure to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm
(F) 0.1 to 10% by mass of 16-hour soluble component in physiological saline
(G) Absorption capacity under high pressure (AAP 4.8 kPa) at 4.8 kPa into physiological saline is 21 g / g or more.   The particulate water-absorbing agent according to any one of claims 1 to 3, wherein the water-absorbent resin is further surface-crosslinked.   Furthermore, (h) 90-100 mass% of a particulate water-absorbing agent exists in the range of 600-150 micrometers, The particulate water-absorbing agent in any one of Claims 1-4.   Furthermore, the particulate water absorbing agent in any one of Claims 1-5 whose (i) absorption capacity | capacitance (AAP1.9 kPa) under pressure in 1.9 kPa to a physiological saline is 20 g / g or more.   Furthermore, the particulate water absorbing agent in any one of Claims 1-6 whose (j) vortex water absorption speed | rate to physiological saline is 60 second or less.   Furthermore, the particulate water-absorbing agent according to any one of claims 1 to 7, wherein (k) the moisture absorption blocking rate is 0 to 20% by mass.   The particulate water-absorbing agent according to any one of claims 1 to 8, wherein (l) logarithmic standard deviation of the particle size distribution is 0.20 to 0.40.   The particulate water-absorbing agent according to any one of claims 1 to 9, further comprising one or more trace components selected from a chelating agent, a deodorant, a polyvalent metal salt, and inorganic fine particles in addition to the water-absorbing resin as a main component.   The particulate water-absorbing agent according to claim 10, wherein the chelating agent is selected from aminocarboxylic acids and salts thereof.   The particulate water-absorbing agent according to claim 10, wherein the deodorant is a plant component.   The particulate water-absorbing agent according to claim 10, wherein the polyvalent metal salt is a polyvalent metal salt of an organic acid.   The particulate water-absorbing agent according to claim 10, wherein the inorganic fine particles are a composite hydrous oxide.   The particulate water-absorbing agent according to any one of claims 1 to 14, wherein the particle shape of the water-absorbent resin is irregularly crushed.   An absorptive article of feces, urine or blood, wherein the absorptive article is formed by including the particulate water-absorbing agent according to any one of claims 1 to 18 and hydrophilic fibers. A method for producing the particulate water-absorbing agent according to any one of claims 1 to 15,
A step of crosslinking polymerization of an unsaturated monomer aqueous solution containing unneutralized acrylic acid and / or a salt thereof as a main component in the presence of a crosslinking agent and a chain transfer agent;
Step of further surface cross-linking water-absorbent resin particles satisfying the following (a) to (c) obtained by polymerization (a) Absorption capacity under no pressure (CRC) to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm
A method for producing a granular water-absorbing agent. A method for producing the particulate water-absorbing agent according to any one of claims 1 to 15,
A step of crosslinking and polymerizing an unsaturated monomer aqueous solution having a concentration of 10 to 30% by weight of unneutralized acrylic acid as a main component in the presence of a crosslinking agent;
A step of neutralizing after polymerization,
A step of further surface-crosslinking the water-absorbent resin particles satisfying the following (a) to (c) obtained by neutralization,
(A) Absorption capacity (CRC) under no pressure to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm
A method for producing a particulate water-absorbing agent. A method for producing the particulate water-absorbing agent according to any one of claims 1 to 15,
A step of crosslinking polymerization of an unsaturated monomer aqueous solution containing unneutralized acrylic acid and / or a salt thereof as a main component in the presence of a crosslinking agent;
Step of further surface cross-linking water-absorbent resin particles satisfying the following (a) to (c) obtained by polymerization (a) Absorption capacity under no pressure (CRC) to physiological saline is 32 g / g or more (b) Mass average particle diameter (D50) is 200 to 400 μm
(C) 0-2% by mass of particles less than 150 μm and selected from the group consisting of (i) during polymerization, (ii) before surface crosslinking after polymerization, (iii) during surface crosslinking, (iv) after surface crosslinking Adding a chelating agent at one or more times;
A method for producing a particulate water-absorbing agent.