JP2005200630A - Water-absorbing resin material and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high water-absorbing resin material capable of exhibiting an excellent water-absorbing performance in a pressureless state, capable of exhibiting a high water-absorbing performance in a pressurized state as well, and capable of being most suitably used for a hygienic material, etc., and to provide a method for simply producing the high water-absorbing resin material, without requiring a surface crosslinking treatment process. <P>SOLUTION: This water-absorbing resin material has such a polymer molecular chain that 50 mol% or more of repeating units in the chain are carboxy group-containing units, a carboxy group neutralization rate in a central part of the resin material is not less than 60 mol%, and a carboxy group neutralization rate on an external surface of the resin material is not more than 50 mol%. The method for producing the water-absorbing resin material comprises polymerizing a monomer solution to form a polymer, drying the polymer, and heat-treating the polymer, wherein the monomer solution contains a mixture comprising an alkali metal salt of an unsaturated carboxylic acid and an ammonium salt thereof in an amount of more than 50 mol% based on the mixture, and further contains a condensation-type crosslinking agent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a water-absorbent resin body widely used in the field of sanitary materials such as disposable diapers and sanitary napkins, the field of agriculture and forestry, and the field of civil engineering, and a method for producing the same. In particular, the present invention relates to a water absorbent resin body for the field of sanitary materials such as disposable diapers and sanitary napkins that require a high water absorption capacity, and a method for producing the same, and more specifically, a water absorbent resin excellent in water absorption capacity under pressure and without pressure. The present invention relates to a body and a manufacturing method thereof.

  In recent years, a water-absorbing resin that gels by absorbing a large amount of water has been developed as a kind of synthetic polymer, and is widely used in the field of sanitary materials such as disposable diapers and sanitary napkins, agriculture and forestry, and civil engineering. Yes. Examples of such a water-absorbing resin include a crosslinked polyacrylic acid partially neutralized product (see, for example, Patent Document 1), a hydrolyzate of starch-acrylonitrile graft polymer (see, for example, Patent Document 2), and starch-acrylic acid graft weight. Neutralized product of polymer (for example, see Patent Document 3), saponified product of vinyl acetate-acrylic acid ester copolymer (for example, see Patent Document 4), hydrolyzate of acrylonitrile copolymer or acrylamide copolymer (for example, Patent Document) Many are known.

  The characteristics that the water-absorbent resin should have include conventionally, a high water absorption ratio when contacting with an aqueous liquid such as body fluid, an excellent absorption rate, liquid permeability, gel strength of swollen gel, and a group containing an aqueous liquid. A suction amount for sucking water from the material is required. However, the relationship between these characteristics does not necessarily show a positive correlation. For example, the higher the water absorption ratio, the lower the physical properties such as liquid permeability, gel strength, and absorption rate.

Thus, as a method for improving the water absorption properties of such a water absorbent resin in a well-balanced manner, a technique for crosslinking the vicinity of the surface of the water absorbent resin is known, and various methods have been proposed so far.
For example, a method using a polyhydric alcohol as a crosslinking agent (see, for example, Patent Documents 6 and 7), a method using a polyvalent glycidyl compound, a polyvalent aziridine compound, a polyvalent amine compound, and a polyvalent isocyanate compound (see, for example, Patent Document 8). ), A method using glyoxal (see, for example, Patent Document 9), a method using a polyvalent metal (see, for example, Patent Documents 10 and 11), a method using a silane coupling agent (see, for example, Patent Documents 12, 13, 14), and the like. Are known.
In addition, a method in which a crosslinking agent is uniformly distributed on the surface of the water-absorbent resin during the crosslinking reaction, and an inert inorganic powder is present when adding the crosslinking agent as an attempt to perform uniform surface crosslinking (see, for example, Patent Documents 15 and 16). Also known are a method in which a dihydric alcohol is present (see, for example, Patent Document 17), a method in which water and an ether compound are present (see, for example, Patent Document 18), and a method in which phosphoric acid is present (see, for example, Patent Document 19). Yes.

  In addition, as an application example of the above method, there is also known a method (for example, Patent Documents 20 and 21) in which a neutralized monomer having a specific composition is mixed with the above crosslinking agent for the purpose of reducing residual monomer and surface crosslinking is performed while heat treatment. Yes.

  However, although the balance of various physical properties of the water-absorbent resin is improved by these methods, it is still not sufficient, and further higher quality is required. In particular, when considering the necessary characteristics of the water-absorbent resin used in the absorbent article in a sanitary product that has been thinned using a large amount of water-absorbent resin, which is a recent trend, the above-mentioned conventional method still has a sufficient physical property level. It is the current situation that has not yet reached.

In recent years, the demand for disposable diapers for the elderly has been increasing with the increase in the average lifespan. Compared to infants, the disposable diaper for elderly people has a larger load on the disposable diaper and the amount of excretion per time is larger. There is a strong demand for a water-absorbing resin having an “excellent water absorption capacity under a high load”.
JP 55-84304 A Japanese Patent Publication No.49-43395 Japanese Patent Laid-Open No. 51-125468 JP-A-52-14689 Japanese Patent Publication No.53-15959 JP 58-180233 A JP-A 61-16903 JP 59-189103 A JP 52-117393 A JP 51-136588 A JP-A-61-257235 JP-A-61-211305 JP-A 61-252212 JP 61-264006 A JP-A-60-163958 JP 60-255814 A JP-A-1-292004 Japanese Patent Laid-Open No. 2-153903 Japanese National Patent Publication No. 8-508517 JP-A-6-122707 JP-A-6-122708

  The performance to be provided as a water-absorbing resin for hygiene materials includes high water absorption performance under no pressure and under pressure among various performances. However, these characteristics have a negative correlation, and it has been difficult in the past to make both the non-pressurized water absorption performance and the water absorption performance under pressure high.

  On the other hand, in recent years, absorbent articles such as disposable diapers have been thinned due to problems in use and functionality, and the amount of water-absorbing resin used in the absorbent layer tends to increase (for example, JP-A 2000-463). reference). However, on the other hand, in the hygiene material application, which is the main application of the water-absorbent resin, to reduce the amount of the water-absorbent resin in order to cope with further thinning and cost reduction of the water-absorbent composition. Therefore, improvement of the water absorption performance of the water absorbent resin is demanded as a means for solving the problem.

  An object of the present invention is a water-absorbent resin body having high water absorption performance under pressure and no pressure, which can be suitably used for sanitary materials such as disposable diapers, sanitary napkins, incontinence pads, etc. An object of the present invention is to provide a water-absorbent resin composition and to provide a production method capable of easily producing the water-absorbent resin body of the present invention by an inexpensive method.

  As a result of intensive studies to solve the above problems, the present inventors have found that a water-absorbent resin body characterized by having a specific structure in the distribution of the neutralization rate in the particles exhibits excellent water absorption performance. . Further, it contains a compound that becomes a condensation type crosslinking agent for the carboxyl group, and at least one kind of unsaturated carboxylic acid ammonium salt is more than 50 mol% and not more than 100 mol%, and the unsaturated carboxylic acid alkali metal salt is not less than 0 mol% and less than 50 mol%. By producing a water-absorbent resin body from the monomer component, it is possible to produce a water-absorbent resin body with good water absorption performance under pressure without sacrificing water absorption performance without pressure, The present invention has been completed.

That is, this invention consists of the following.
[1] Among the repeating units in the polymer molecular chain, 50 mol% or more is a water-absorbent resin body composed of carboxyl group-containing units, and the carboxyl group neutralization rate at the center of the resin body is 60 mol% or more. A water-absorbent resin body having a surface carboxyl group neutralization rate of 50 mol% or less.
[2] The water-absorbent resin body according to the above [1], characterized by a skin structure in which a portion having a lower neutralization rate than the central portion of the resin body exists with a width of 13 μm or more from the outer surface of the resin body.
[3] The water-absorbent resin body according to [1] or [2], wherein the following (1) and (2) are satisfied.
(1) 50 mol% or more of the carboxyl group neutralized salt in the polymer molecular chain is an ammonium salt.
(2) The water absorption magnification under a pressure of 0.8 psi is 22 times or more.
[4] The water-absorbent resin body as described in [3] above, which is a powder particle water-absorbent resin having a particle size distribution of 40 μm to 1000 μm.
[5] It is characterized in that a monomer solution satisfying the following (3) to (5) is polymerized, pulverized, dried, pulverized, or polymerized, pulverized, pulverized, dried, and then heat-treated. A method for producing a water-absorbent resin body.
(3) At least one kind of unsaturated carboxylic acid ammonium salt (A), unsaturated carboxylic acid alkali metal salt (B), and a condensation type crosslinking agent (C) for a carboxyl group.
(4) The ratio of unsaturated carboxylic acid ammonium salt (A) is more than 50 mol% and 100 mol% or less with respect to all unsaturated carboxylic acid monomers, and the ratio of unsaturated carboxylic acid alkali metal salt (B) is all It is 0 mol% or more and less than 50 mol% with respect to the unsaturated carboxylic acid monomer.
(5) The content of the condensation type crosslinking agent (C) with respect to the carboxyl group is 0.01% by weight or more and 20% by weight or less based on the weight of all monomer components.
[6] The method for producing a water absorbent resin body according to [5], wherein the heat treatment is performed at 100 to 250 ° C.
[7] In addition to the condensation type crosslinking agent (C) for the carboxyl group as a crosslinking agent, the unsaturated monomer polymerizable crosslinking agent (D) is contained in an amount of 0.005 mol% to 1 mol% based on the total monomer components. The method for producing a water-absorbent resin body according to [5] or [6], wherein:
[8] The method for producing a water-absorbent resin body according to any one of [5] to [7], wherein the unsaturated carboxylates (A) and (B) are (meth) acrylates. .

The water-absorbing performance of the present invention shows good water-absorbing performance even under pressure while maintaining the non-pressurized water-absorbing performance at a high level, and is suitable for sanitary material applications such as disposable diapers.
Further, in the production method of the present invention, the water absorption performance under pressure is excellent without passing through the surface cross-linking treatment step that has been conventionally performed to produce a resin having a good balance between the non-pressurization and the water absorption capacity under pressure. This is very useful because the resin can be easily produced.

Hereinafter, the present invention will be described in more detail with reference to examples.
The water-absorbent resin body of the present invention is a water-absorbent resin body in which 50 mol% or more of the repeating units in the polymer molecular chain are composed of carboxyl group-containing units, and the neutralization rate of the carboxyl group at the center of the resin body is 60 mol% or more. Yes, the water-absorbent resin body has a carboxyl group neutralization rate of 50 mol% or less on the outer surface of the resin body.

  Of the repeating units in the polymer molecular chain, the carboxyl group-containing unit needs to be 50 mol% or more, and is preferably 80 mol% or more, more preferably 90 mol% or more from the viewpoint of water absorption performance.

  As the carboxyl group-containing monomer constituting the water-absorbent resin body of the present invention, acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, fumaric acid, sorbic acid, cinnamic acid, their anhydrides, And neutralized salts of unsaturated carboxylic acid monomers.

  The carboxyl group in the polymer molecular chain is preferably partially neutralized, and examples of the base include at least one of alkali metals such as sodium, potassium, and lithium, amines, and ammonia. As a kind of base, it is preferable to be partially neutralized with at least one kind including ammonia, and most preferably partially neutralized with ammonia alone. In the water absorbent resin body of the present invention, the neutralization rate has a distributed structure inside the resin body. That is, the carboxyl group neutralization rate at the center of the resin body is 60 mol% or more, preferably 65 mol% or more, most preferably 70 mol% or more, and the carboxyl group neutralization rate on the outer surface of the resin body is 50 mol% or less, preferably 45 mol% or less. Most preferably, it is 40 mol% or less. It is preferable that the neutralization rate of the central part of the resin body is the above-mentioned numerical value because it is difficult for the water absorption capacity to decrease without pressure. Moreover, when the neutralization rate of the outer surface of the resin body is the above numerical value, it is preferable that the water absorption capacity under pressure is difficult to decrease.

  The distribution structure of the neutralization rate inside the resin body, which is a requirement of the present invention, is determined by measuring the neutralization rate between the outer surface of the resin body and the center of the resin body by a microscopic ATR method which is one of infrared absorption analysis methods. Can be sought. The resin body outer surface means a portion exposed to the outside of the resin body, and the resin body central portion means the deepest part from the resin body outer surface of the resin body. The neutralization rate of the outer surface of the resin body is measured directly by the microscopic ATR method, and the resin body is measured by cleaving the resin body by using, for example, an ultramicrotome (ULTRACUT N manufactured by Reichert). After exposing the central portion, measurement is performed by the microscopic ATR method. As the measuring apparatus, for example, FTS-575 manufactured by Bio-Rad may be used.

As an indicator for defining the composition ratio of carboxylic acid and carboxylate, 1,695 cm ^-1 (carboxylate νC = 0 Baseline 1774~1616cm ^-1) and 1558cm ^{-1 -} peak of (carboxylate νCOO baseline 1616~1500cm ^-1) The area ratio (1695/1558 cm ⁻¹ ) is calculated. Separately, 10 mol%, 30 mol%, 50 mol%, 70 mol%, 90 mol%, and 100 mol% of the total carboxylic acid were measured using partially crosslinked polyacrylic acid neutralized with ammonia as a standard sample, and the composition ratio was determined from the prepared calibration curve. .

  According to one preferable aspect of the water-absorbent resin body in the present invention, the water-absorbent resin body has a structure in which a portion having a lower neutralization rate than the center portion of the resin body is present on the surface of the resin body with a width of 13 μm or more from the outer surface of the resin body. And Here, a structure in which a portion having a lower neutralization rate than the central portion of the resin body is present on the surface of the resin body is defined as a skin structure. The width of the skin structure in the resin body of the present invention is 13 μm or more, preferably 19 μm or more. When the width of the skin structure is 13 μm or more, the water absorption performance under pressure is improved, which is preferable.

The width of the skin structure existing in the resin body can be measured by IR imaging measurement. The resin body is cut into 2 μm-thick sections using an ultramicrotome (ULTRACUT N manufactured by Reichert), and measured in the manner of the IR transmission method. Measure all parts of the cut sample. The resin body is cut out so that the deepest part from the surface layer can be measured in the resin body. An apparatus used for IR imaging measurement is Spot-Light manufactured by Perkin Elmer. As an indicator for defining the composition ratio of carboxylic acid and carboxylate, 1,695 cm ^-1 (carboxylate νC = 0 Baseline 1774~1616cm ^-1) and 1558cm ^{-1 -} peak of (carboxylate νCOO baseline 1616~1500cm ^-1) The area ratio (1695/1558 cm ⁻¹ ) is calculated and the total absorbance image is converted to a Band Radio image. The width of the skin structure is from the surface layer to a point 40% lower than the Band Radio value of the surface layer.

  In the water-absorbent resin body of the present invention, 50 mol% or more of the carboxyl group neutralized salt in the polymer molecular chain is preferably an ammonium salt in order to increase the water absorption capacity under pressure. More preferably, 70 mol% or more is an ammonium salt, and most preferably 100 mol% is an ammonium salt.

  The shape of the water-absorbent resin body of the present invention is not particularly limited as long as it does not change the gist of the present invention. Spherical particulate powders and amorphous particles widely used in water-absorbent resin compositions Powder, short fiber, long fiber, and sheet. From the viewpoint of ease of handling such as ease of mixing with pulp in the usage form in the sanitary material field, spherical particulate powder or irregular particulate powder is preferable, and the particle size distribution is preferably 40 μm to 1000 μm. More preferably, it is 50 micrometers-900 micrometers, Most preferably, it is 100-850 micrometers. When the particle size is remarkably small, it becomes a fine powder, which causes a problem in use such as being easily scattered. On the other hand, when it is large, there are problems such as a decrease in water absorption rate and unevenness of the water absorbent resin body in the absorbent article.

  Deodorant, antibacterial agent, fragrance, various inorganic powders, foaming agent, pigment, dye, hydrophilic short fiber, fertilizer, oxidizing agent, reducing agent, water, salt, etc. are further added to the water absorbent resin body of the present invention. Thus, various functions can be imparted to the water-absorbing agent to obtain a water-absorbing resin composition.

  Although the manufacturing method of the water absorbing resin body of this invention is not specifically limited, The method of heat-processing the resin body obtained by copolymerization of an unsaturated carboxylate monomer is raised. In the heat treatment, a neutralized resin body containing a carboxyl group by hydrolyzing a polymer containing an unsaturated carboxylic acid monomer or a polymer containing a nitrile group or an amide group May be manufactured and heat treatment described later may be performed. Other methods for treating a carboxylate-containing resin body into the structure of the water-absorbent resin body of the present invention include a method of ion exchange by acid treatment of a surface layer of a uniformly neutralized resin body, Examples of the method include polymerization using a different two kinds of monomers so as to form a layer structure, and a method in which a resin body obtained by copolymerization of the above-described unsaturated carboxylate monomer is heat-treated is preferable. That is, an aqueous monomer solution containing at least one unsaturated carboxylic acid ammonium salt (A), an unsaturated carboxylic acid alkali metal salt (B), and a compound (C) that is condensed with respect to a carboxyl group is polymerized and dried. After the pulverization, or after polymerization, pulverization and drying, heat treatment is performed.

  As the unsaturated carboxylic acid ammonium salt (A), acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, fumaric acid, sorbic acid, and cinnamic acid ammonium salts are preferred, and in particular, (meth) acrylic acid. The ammonium salt is preferred.

  The unsaturated carboxylic acid alkali metal salt (B) is preferably an alkali metal salt of acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, fumaric acid, sorbic acid, or cinnamic acid. An alkali metal salt of acrylic acid is preferred. Examples of the alkali metal in the unsaturated carboxylic acid alkali metal salt (B) include lithium, sodium and potassium.

  The composition of the unsaturated carboxylic acid ammonium salt (A) and the unsaturated carboxylic acid alkali metal salt (B) is such that (A) exceeds 50 mol% and 100 mol% or less, and (B) is 0 mol% or more and less than 50 mol%. Prepare to.

  In the resin body of the present invention, other monomers may be copolymerized as long as 50 mol% or more of all functional groups are within the range where carboxylic acid groups are formed. Unsaturated monomers that may be copolymerized include (meth) acrylic acid, itaconic acid, maleic acid, crotonic acid, sorbic acid, cinnamic acid, their anhydrides, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfone Acid, vinyltoluene sulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 2- (meth) acryloylethanesulfonic acid, 2- (meth) acryloylpropanesulfonic acid, 2-hydroxylethylacryloyl phosphate, Anionic unsaturated monomers and salts thereof such as 2-hydroxylethylmethacryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, vinyl phosphate, acrylamide, methacrylamide, N-ethyl (meth) acrylamide, Nn -Propyl (Meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol Nonionic hydrophilic group-containing unsaturated monomers such as mono (meth) acrylate, N-vinylpyrrolidone, N-acryloylpiperidine, N-acryloylpyrrolidine and the like can be mentioned.

  Further, in order to obtain the water-absorbent resin body of the present invention, hydrophilicity that forms a water-absorbent resin by hydrolysis of functional groups after polymerization, such as methyl (meth) acrylate, ethyl (meth) acrylate, vinyl acetate, etc. You may superpose | polymerize using a monomer. Examples of the hydrophobic monomer that can be used in combination include styrene, vinyl chloride, butadiene, isobutene, ethylene, propylene, stearyl (meth) acrylate, lauryl (meth) acrylate, and the like. More than one type can be added.

  Examples of the method for crosslinking the water-absorbent resin include a method in which a condensation type crosslinking agent is used to react with a functional group in the resin to crosslink, and a polymerizable crosslinking agent is used to copolymerize with an unsaturated monomer. The cross-linking method can be increased by irradiating the resin with an electron beam or radiation. The method preferably uses condensation-type cross-linking, most preferably the condensing type cross-linking agent that reacts with the functional group of the resin (C ) In the coexistence of the polymerizable crosslinking agent (D) and the unsaturated monomer.

  Glycidyl ether compounds such as ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, (poly) glycerin polyglycidyl ether, diglycerin polyglycidyl ether, propylene glycol diglycidyl ether, etc. Polyhydric alcohols such as (poly) glycerin, (poly) ethylene glycol, propylene glycol, 1,3-propanediol, polyoxyethylene glycol, triethylene glycol, tetraethylene glycol, diethanolamine, triethanolamine; ethylenediamine, di Polyvalent amines such as ethylenediamine, polyethyleneimine, hexamethylenediamine; zinc, calcium, magnesium, aluminum Include such polyvalent ions such as these crosslinking agents may be used two or more.

  The unsaturated monomer polymerizable crosslinking agent (D) is a compound having two or more unsaturated groups in one molecule that becomes a crosslinking agent at the time of polymerization. Specifically, diethylene glycol diacrylate, N, N '-Methylenebisacrylamide, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane diallyl ether, allyl glycidyl ether, pentaerythritol triallyl ether, pentaerythritol diacrylate monostearate, bisphenol diacrylate, isocyanuric acid diacrylate, tetra Examples include allyloxyethane and diallyloxyacetate, and two or more of these crosslinking agents may be used.

  The solvent of the monomer solution is not particularly limited as long as it has excellent solubility. Particularly preferred is water alone, but hydrophilic solvents such as ethanol, methanol, acetone and the like may be used alone or in combination. If necessary, a salt such as sodium chloride, a basic compound such as ammonia for pH control, or a suspending agent may be added during reverse phase suspension polymerization.

The polymerization method of the unsaturated monomer is not particularly limited, and generally used methods such as (water) solution polymerization, reverse layer suspension polymerization, spray polymerization, and belt polymerization can be applied.
The polymerization initiation method is not particularly limited, and polymerization with a radical polymerization initiator, polymerization by irradiation with radiation, electron beam, or ultraviolet polymerization with a photosensitizer can be performed. Examples of the initiator used for such radical polymerization include persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate; hydrogen peroxide; organics such as cumene hydroperoxide, t-butyl hydroperoxide and peracetic acid. Examples thereof include known initiators such as oxide oxides. When an oxidizing radical polymerization initiator is used, a reducing agent such as L-ascorbic acid or Rongalite may be used in combination. It is preferable to perform a deoxygenation operation in the monomer solution in advance before the start of polymerization. As a specific method, there is a method of removing dissolved oxygen by bubbling with an inert gas for a sufficient time. The atmosphere in the reactor is preferably replaced with an inert gas such as nitrogen or helium.

  The inside of the polymerization reactor may be any of reduced pressure, normal pressure, and increased pressure. The polymerization start temperature is usually 0 to 50 ° C. The polymerization initiation temperature is preferably 10 to 40 ° C. The temperature in the reactor during the polymerization reaction may be determined depending on the situation, and the temperature may be controlled from the outside by cooling or heating. The concentration of the monomer solution is preferably 10 to 70%, and most preferably 30 to 50% from the viewpoint of economy and ease of reaction control.

  After the polymerization reaction, a hydrogel substance is generated. In order to make the resin into particles, this hydrogel material is crushed and dried, and after drying, it is pulverized to about several hundred μm and granulated. Alternatively, a method may be mentioned in which the hydrated gel is pulverized and simultaneously pulverized until the particle size after drying reaches an optimum size and then dried. The particle size distribution is preferably within 40 μm to 1000 μm, particularly preferably 50 μm to 900 μm, and more preferably 100 to 850 μm. The pulverization method is not particularly limited, and a conventionally known method can be appropriately used. In the case of reverse-phase suspension polymerization, it is sieved to an appropriate size after drying.

  The drying method is not particularly limited, and usually vacuum drying or hot air drying is used. The drying temperature is preferably in the range of 70 ° C to 180 ° C, particularly preferably 90 to 140 ° C. Multi-stage heating may be performed. If the drying temperature is too low, it takes too much time to dry, which is not economical. If the drying temperature is too high, the water-absorbing resin is decomposed, resulting in a decrease in water absorption performance.

The shape of the resin body is not particularly limited, but in any case, it is desirable that the shape is completed before the heat treatment.
A preferred method for the neutralization rate of the outer surface layer of the resin body to be lower than the internal neutralization rate is a heat treatment of the resin body obtained by the production method described above. The heat treatment may be performed continuously in the same apparatus after completion of drying, or may be a step independent of the drying step. The heating conditions are not particularly limited as long as the water absorption performance of the resin body is not deteriorated, and is appropriately set depending on the distribution structure of the neutralization rate and the width of the skin structure. The heating temperature is in the range of 100 to 250 ° C, preferably 120 to 200 ° C. Further, from the viewpoint of the distribution structure of the neutralization rate in the resin body and the water absorption performance, the heating temperature is preferably 10 to 150 ° C. higher than the drying temperature, and further 30 to 100 ° C. higher. preferable. The heating time is 10 minutes to 5 hours. The neutralization rate inside the resin body is 60 mol% or more, and the neutralization rate of the outer surface layer is appropriately selected from the above heating temperature and heating time so as to be in the range of 50 mol% or less.

Specific examples and comparative examples of the present invention are shown below, but the present invention is not limited to the following examples.
(1) Measuring method of neutralization ratio of resin body outer surface and inner part (i) Measuring device FTS-575 manufactured by Bio-Rad was used as a measuring device.
(Ii) Measurement conditions Microscopic ATR method (crystal plate Ge once reflection),
Back Ground: Air room temperature measurement,
Aperture: 50 × 50 μm,
Peak area of ^- (baseline 1616～1500Cm ^{-1-carboxylate} νCOO) 1695cm from the spectral data obtained by the 100 measurements ^-1 (carboxylic acid νC = 0 Baseline 1774～1616Cm ^-1) and 1558cm ^-1: accumulated number The ratio (1695/1558 cm ⁻¹ ) is determined.

(Iii) Preparation of calibration curve Partially crosslinked polyacrylic acid obtained by neutralizing 10 mol%, 30 mol%, 50 mol%, 70 mol%, 90 mol%, and 100 mol% of the total carboxylic acid with ammonia was used as a sample for preparing a calibration curve. The calibration curve sample is cleaved, and the central part is performed 5 times per sample by the microscopic ATR method. A calibration curve (5th order polynomial approximation curve) was created from the -COOH / -COO ^- peak area ratio. The cleaving was performed with an ultramicrotome (ULTRACUT N manufactured by Reichert).

(Iv) Sample measurement Measurement was performed in the same manner as the calibration curve sample. The particle diameter of the measurement sample was 300 to 700 μm. The outer surface of the resin body was directly measured by the ATR method, and the central portion of the resin body was cleaved by an ultramicrotome and then measured by the ATR method. The outer surface of the resin body was measured 3 times per sample, and the central part of the resin body was measured 5 times per sample, and the average value was taken as the measurement result.

(2) Measurement of the width of the skin structure; IR imaging measurement method (i) Pretreatment Cleaving a resin body having a particle size of 300 to 500 μm so that the central part of the resin body can be measured with an ultramicrotome (ULTRACUT N manufactured by Reichert) Then, a section was prepared to a thickness of about 2 μm. This section was fixed smoothly on a NaCl crystal plate and set in a microscopic IR imaging measurement apparatus.
(Ii) Measuring device IR imaging measurement was performed by a microscopic transmission method using Spot-Light manufactured by Perkin Elmer.

(Iii) Measurement conditions Measurement spot diameter: 6.25 × 6.25 μm,
Integration count: 4 times
Measurement atmosphere: Dry Air,
The measurement was performed within 30 minutes after the pretreatment.

Peak of ^- (baseline 1616～1500Cm ^{-1-carboxylate} νCOO) (iv) 1695cm from the spectral data obtained by IR spectrum analysis measurement ^-1 (carboxylic acid νC = 0 Baseline 1774～1616Cm ^-1) and 1558Cm ^-1 The area ratio (1695/1558 cm ⁻¹ ) was calculated, and the total absorbance image was converted into a Band Radio image, and it was confirmed that the neutralization rate of the outer surface of all the measurement samples was lower than that of the inner part. In addition, a line profile was taken from the Band Radio image in the cross-sectional direction, and the width up to a point 40% lower than the Band Radio value of the surface layer was measured to obtain the width of the skin structure.

(3) Water absorption performance measurement method; water absorption method under pressure Cylindrical instrument made of acrylic with a 250 mesh nylon net on the bottom (outer diameter 35.0 mm, inner diameter 24.5 mm, height 30 mm, weight D (g) ), Water-absorbing resin E (g) (about 0.16 g) is uniformly added, and the weight cannot be anything at 0.0 psi, but 99.3 g at 0.3 psi and 278. A 3 g weight (outer diameter 24.5 mm) is placed. 60 cc of physiological saline is placed in a SUS petri dish (inner diameter: 120 mm), and a cylindrical instrument is placed in it for 1 hour. After a predetermined period of time, drain water with a paper towel, and measure the weight F (g) of the entire instrument with a balance. The water absorption ratio is obtained by the following formula.
Water absorption ratio (g / g) = (F (g) −D (g) −weight of weight (g)) / E (g)

(4) Water-absorbing performance measuring method: Tea bag method Water-absorbing resin A (g) (about 0.5 g) is uniformly placed in a non-woven teabag bag (7 × 9 cm), and physiological saline at a liquid temperature of 25 ° C. Immerse in 500 cc for 1 hour. After a predetermined time, the tea bag bag is pulled up and drained naturally for 10 minutes, and then the weight B (g) of the tea bag bag is measured. The same operation as a blank is performed using only a tea bag bag without adding a water-absorbent resin, and the weight C (g) is measured. The water absorption ratio is obtained from the following formula.
Water absorption magnification (g / g) = (B (g) -C (g)) / A (g)

(Production Example 1)
(Preparation of ammonium acrylate by neutralization of acrylic acid)
Acrylic acid manufactured by Wako Pure Chemical Industries, Ltd. was used as a reagent special grade. 100 g of reagent acrylic acid was dissolved in 91.02 g of water. This aqueous solution was cooled in an ice bath, and while maintaining the liquid temperature at 30 ° C. or lower, 117.94 g of a 25 wt% aqueous ammonia solution was gradually added with stirring to obtain a 40 wt% aqueous ammonium acrylate solution.

(Production Example 2)
(Preparation of ammonium acrylate by hydrolysis of acrylonitrile)
(1) Preparation of biocatalyst Acinetobacter sp. AK226 (FERM BP-2451) having nitrilase activity is 0.1% sodium chloride, 0.1% potassium dihydrogen phosphate, 0.05% magnesium sulfate heptahydrate, sulfuric acid In a medium prepared by adjusting an aqueous solution containing iron heptahydrate 0.005%, manganese sulfate pentahydrate 0.005%, ammonium sulfate 0.1%, potassium nitrate 0.1% (both wt%) to pH = 7. Then, 0.5% by weight of acetonitrile was added as a nutrient source and cultured aerobically at 30 ° C. This was washed with a 30 mM phosphate buffer (pH = 7.0) to obtain a cell suspension (dry cell 15% by weight). Subsequently, 2.5% in a mixed solution of acrylamide, N, N′-methylenebisacrylamide, 5% N, N, N ′, N′-tetramethylethylenediamine aqueous solution, cell suspension, and 30 mM phosphate buffer. A potassium persulfate aqueous solution was mixed to obtain a heavy product. The final composition is 3% dry cell concentration, 52% 30 mM phosphate buffer (pH = 7), 18% acrylamide, 1% methylenebisacrylamide, 5% N, N, N ′, N′-tetramethylethylenediamine. An aqueous solution of 12% and a 2.5% potassium persulfate aqueous solution of 14% (both by weight) were used. The polymer was cut into about 1 × 3 × 3 mm square particles to obtain immobilized cells. The immobilized cells were washed with 30 mM phosphate buffer (pH = 7) to prepare an immobilized cell catalyst (hereinafter referred to as biocatalyst).

(2) Hydrolysis with a biocatalyst 400 g of distilled water is put into an Erlenmeyer flask with an internal volume of 500 ml, and 1 g of the above biocatalyst (corresponding to 0.03 g of dry cells) is put in a wire mesh basket in the liquid. After sealing with a rubber stopper, the inner temperature was kept at 20 ° C. by immersion in a constant temperature water bath, and the mixture was stirred with a stirrer.
Acrylonitrile was intermittently fed in an amount of 2% by weight (acrylonitrile concentration was controlled at 0.5% by weight or more), and an accumulation reaction of ammonium acrylate was carried out, and 30% by weight could be accumulated.
The obtained aqueous solution of ammonium acrylate was colorless and transparent. In addition, when 5 L of the reaction solution was prepared under the same conditions and purified using a UF membrane (Asahi Kasei Pencil type module SIP-0013), no clogging or other phenomena were observed, and the entire solution could be processed. A highly pure 30% by weight ammonium acrylate aqueous solution was obtained. To this aqueous solution, 200 ppm of methoxyquinone was added, and concentrated to 40% by weight under light-shielding reduced pressure, and used for polymerization.

(Production Example 3)
(Preparation of sodium acrylate by neutralization of acrylic acid)
Acrylic acid manufactured by Wako Pure Chemical Industries, Ltd. was used as a reagent special grade. 100 g of reagent acrylic acid was dissolved in 81.6 g of water. This aqueous solution was cooled in an ice bath, and while maintaining the liquid temperature at 30 ° C. or lower, 137.1 g of 40.5 wt% NaOH aqueous solution was gradually added with stirring to obtain 40 wt% sodium acrylate aqueous solution.

Example 1
To a 300 ml separable flask, 90 g of 40 wt% ammonium acrylate aqueous solution of Production Example 1 and 0.0187 g of N, N′-methylenebisacrylamide are added. The flask is bathed in a water bath so that the liquid temperature is maintained at 30 ° C. The aqueous solution was deaerated by bubbling with nitrogen gas, and the reaction system was purged with nitrogen. Next, 0.86 g of 42 wt% glycerin aqueous solution was added with a syringe, and after stirring well, 0.0917 g of 30 wt% aqueous hydrogen peroxide solution and 0.0415 g of Rongalite dissolved in 1 g of water were added to initiate polymerization. The internal temperature starts from 30 ° C and rises to 100 ° C in 10 minutes from the start of the reaction. Then, it heats in a water bath for 3 hours so that internal temperature may be maintained at 70 degreeC. Then, after taking out a gel from a Separa flask and carrying out rough crushing, it is made to dry at 100 degreeC using a vacuum dryer. After drying, the mixture is pulverized with a homogenizer, and 100 to 850 μm is collected by sieving. This is heated in an inert oven at 180 ° C. for 15 minutes in a nitrogen atmosphere. The water absorbent resin body obtained as described above is referred to as a water absorbent resin body (1).
Table 1 shows the results of measuring the neutralization rate of the outer surface of the resin body of the water absorbent resin body (1) and the neutralization ratio of the resin body center and the results of water absorption measurement.

Example 2
To a 300 ml separable flask, 90 g of 40 wt% ammonium acrylate aqueous solution of Production Example 1 and 0.0187 g of N, N′-methylenebisacrylamide are added. The flask is bathed in a water bath so that the liquid temperature is maintained at 30 ° C. The aqueous solution was deaerated by bubbling with nitrogen gas, and the reaction system was purged with nitrogen. Next, 0.86 g of 42 wt% glycerin aqueous solution was added with a syringe, and after stirring well, 0.0917 g of 30 wt% aqueous hydrogen peroxide solution and 0.0415 g of Rongalite dissolved in 1 g of water were added to initiate polymerization. The internal temperature starts from 30 ° C and rises to 70 ° C in 10 minutes from the start of the reaction. Then, it heats in a water bath for 3 hours so that internal temperature may be maintained at 70 degreeC. Then, after taking out a gel from a Separa flask and carrying out rough crushing, it is made to dry at 100 degreeC using a vacuum dryer. After drying, the mixture is pulverized with a homogenizer, and 100 to 850 μm is collected by sieving. This is heated at 170 ° C. in an inert oven for 30 minutes under a nitrogen atmosphere. The water absorbent resin body thus obtained is referred to as a water absorbent resin body (2).
Table 1 shows the results of measuring the neutralization rate of the outer surface of the resin body of the water absorbent resin body (2) and the neutralization ratio of the resin body center, the skin structure width obtained by IR imaging, and the results of water absorption measurement. Show. Moreover, the micrograph of the sample which performed IR imaging is shown in FIG. 1, and the result of the line profile which digitized 1695 / 1558cm ^-1 peak area ratio performed along the broken line of FIG. 1 in IR imaging measurement is shown in FIG. .

Example 3
In a 300 ml flask, 97.66 g of reagent acrylic acid (manufactured by Wako Pure Chemical, special grade reagent), 126.55 g of water, and 81.35 g of 25 wt% aqueous ammonia are slowly cooled so that the liquid temperature does not exceed 30 ° C. Added. Further, 7.8 g of activated carbon was added, stirred for 1 hour under light shielding, and the activated carbon was removed by filtration to obtain a 90% neutralized ammonium acrylate aqueous solution.
To a 300 ml separable flask, 90 g of 90% neutralized ammonium acrylate aqueous solution and 0.0198 g of N, N′-methylenebisacrylamide are added. The flask is bathed in a water bath so that the liquid temperature is maintained at 30 ° C. The aqueous solution was deaerated by bubbling with nitrogen gas, and the reaction system was purged with nitrogen. Next, 0.86 g of 42 wt% glycerin aqueous solution was added with a syringe, and after stirring well, 0.0953 g of 30 wt% aqueous hydrogen peroxide solution dissolved in 1 g of water and 0.0419 g of Rongalite were added to initiate polymerization. The internal temperature started from 30 ° C. and increased to 102 ° C. 5 minutes after the start of the reaction. Then, it heats in a water bath for 3 hours so that internal temperature may be maintained at 70 degreeC. Thereafter, the gel is taken out from the Separa flask and roughly crushed and then dried at 100 ° C. for 4 hours using an inert oven in a nitrogen atmosphere. After drying, the mixture is pulverized with a homogenizer, and 100 to 850 μm is collected by sieving. This is heated at 170 ° C. in an inert oven for 30 minutes under a nitrogen atmosphere. The water absorbent resin body thus obtained is designated as a water absorbent resin body (3).
Table 1 shows the results of measuring the neutralization rate of the outer surface of the resin body of the water absorbent resin body (3) and the neutralization ratio of the central portion of the resin body and the results of water absorption measurement.

Example 4
In a 300 ml flask, 88.64 g of reagent acrylic acid (manufactured by Wako Pure Chemicals, special grade reagent), 107.05 g of water, and 57.43 g of 25 wt% ammonia water are slowly cooled so that the liquid temperature does not exceed 30 ° C. Added. Further, 7.1 g of activated carbon was added, stirred for 1 hour under light shielding, and the activated carbon was removed by filtration to obtain a 70% neutralized ammonium acrylate aqueous solution.
To a 300 ml separable flask, 90 g of 70% neutralized ammonium acrylate aqueous solution and 0.0198 g of N, N′-methylenebisacrylamide are added. The flask is bathed in a water bath so that the liquid temperature is maintained at 30 ° C. The aqueous solution was deaerated by bubbling with nitrogen gas, and the reaction system was purged with nitrogen. Next, 0.86 g of 42 wt% glycerin aqueous solution was added with a syringe, and after stirring well, 0.0953 g of 30 wt% aqueous hydrogen peroxide solution dissolved in 1 g of water and 0.0419 g of Rongalite were added to initiate polymerization. The internal temperature started from 30 ° C and increased to 105 ° C 5 minutes after the start of the reaction. Then, it heats in a water bath for 3 hours so that internal temperature may be maintained at 70 degreeC. Thereafter, the gel is taken out from the Separa flask and roughly crushed and then dried at 100 ° C. for 4 hours using an inert oven in a nitrogen atmosphere. After drying, the mixture is pulverized with a homogenizer, and 100 to 850 μm is collected by sieving. This is heated in an inert oven at 170 ° C. for 20 minutes in a nitrogen atmosphere. The water absorbent resin body thus obtained is referred to as a water absorbent resin body (4).
Table 1 shows the results of measuring the neutralization rate of the outer surface of the resin body of the water absorbent resin body (4) and the neutralization ratio of the resin body center portion, and the results of water absorption measurement.

Example 5
Add 19.6 g of acrylic acid, 15.2 g of water, and 8.7 g of 28 wt% aqueous ammonia solution to a 300 ml separable flask. The flask is bathed in a water bath so that the liquid temperature is maintained at 30 ° C. The aqueous solution was deoxygenated by bubbling with nitrogen gas, and the reaction system was purged with nitrogen. Next, after adding a 64 wt% glycerin aqueous solution with a 3.1 g syringe and stirring well, 0.0413 g of ammonium persulfate dissolved in 1 g of water and 0.0005 g of L-ascorbic acid are added to initiate polymerization. The internal temperature starts from 30 ° C and increases to 75 ° C in 5 minutes from the start of the reaction. Heat in a water bath for 3 hours so that the internal temperature is maintained at 75 ° C. 5 minutes after recording the maximum temperature. After a predetermined time has elapsed, the gel is taken out from the separable flask and roughly crushed, and then dried at 100 ° C. using a vacuum dryer. After drying, the mixture is pulverized with a homogenizer, and 100 to 850 μm is collected by sieving. This is heated at 150 ° C. in an inert oven for 5 hours under a nitrogen atmosphere. The water absorbent resin body obtained as described above is referred to as a water absorbent resin body (5). Table 2 shows the results of water absorption measurement of the water absorbent resin body (5).

Example 6
To a 300 ml separable flask, 90 g of 40% by weight ammonium acrylate aqueous solution of Preparation Example 1 and 0.0250 g of ethylene glycol dimethacrylate are added. The flask is bathed in a water bath so that the liquid temperature is maintained at 30 ° C. The aqueous solution was deoxygenated by bubbling with nitrogen gas, and the reaction system was purged with nitrogen. Next, after adding 50 wt% glycerin aqueous solution with a 2.1 g syringe and stirring well, 0.0917 g of 30 wt% hydrogen peroxide aqueous solution and 0.0415 g of Rongalite each dissolved in 1 g of water are added to initiate polymerization. . The internal temperature starts from 30 ° C and increases to 100 ° C in 10 minutes from the start of the reaction. Heat in a water bath for 3 hours so that the internal temperature is maintained at 75 ° C. 5 minutes after recording the maximum temperature. After a predetermined time has elapsed, the gel is taken out from the separable flask and roughly crushed, and then dried at 100 ° C. using a vacuum dryer. After drying, the mixture is pulverized with a homogenizer, and 100 to 850 μm is collected by sieving. This is heated in an inert oven at 150 ° C. for 60 minutes in a nitrogen atmosphere. The water absorbent resin body obtained as described above is referred to as a water absorbent resin body (6). Table 2 shows the results of water absorption measurement of the water absorbent resin body (6).

Example 7
To a 300 ml separable flask, 90 g of 40 wt% ammonium acrylate aqueous solution of Production Example 1 and 0.0248 g of ethylene glycol dimethacrylate are added. The flask is bathed in a water bath so that the liquid temperature is maintained at 30 ° C. The aqueous solution was deoxygenated by bubbling with nitrogen gas, and the reaction system was purged with nitrogen. Next, after adding a 50 wt% ethylene glycol aqueous solution with a 0.72 g syringe and stirring well, 0.0615 g of ammonium persulfate and 0.0007 g of L-ascorbic acid dissolved in 1 g of water are added to initiate polymerization. The internal temperature starts from 30 ° C and increases to 70 ° C in 10 minutes from the start of the reaction. Heat in a water bath for 3 hours so that the internal temperature is maintained at 75 ° C. 5 minutes after recording the maximum temperature. After a predetermined time has elapsed, the gel is taken out from the separable flask and roughly crushed, and then dried at 100 ° C. using a vacuum dryer. After drying, the mixture is pulverized with a homogenizer, and 100 to 850 μm is collected by sieving. This is heated at 170 ° C. in an inert oven for 30 minutes under a nitrogen atmosphere. The water absorbent resin body thus obtained is referred to as a water absorbent resin body (7). Table 2 shows the results of water absorption measurement of the water absorbent resin body (7).

Example 8
0.0187 g of N, N′-methylenebisacrylamide was added as a crosslinking agent to 90 g of a 40 wt% ammonium acrylate aqueous solution obtained by the biocatalyst of Production Example 2 and dissolved. This solution was transferred to a 300 ml separable flask and purged with nitrogen at 30 ° C. for 30 minutes while stirring. 0.414 g of diethylene glycol was added thereto, 0.0414 g of Rongalite was further added, and 0.092 g of a 30 wt% aqueous hydrogen peroxide solution was subsequently added to initiate polymerization. The temperature increased from 5 minutes after the start, and the maximum temperature reached 100 ° C. After polymerization for 1 hour, the hydrogel was crushed to about 5 mm square and dried at 100 ° C. for 2 hours in an inert oven with a nitrogen atmosphere. The dried polymer was pulverized with a homogenizer, and further dried at 100 ° C. in an inert oven for 2 hours. The polymer after drying was classified to 106 to 850 μm. Thereafter, heating was performed at 170 ° C. for 30 minutes. The water absorbent resin body obtained as described above is referred to as a water absorbent resin body (8). Table 2 shows the results of water absorption measurement of the water absorbent resin body (8).

Example 9
0.0187 g of N, N′-methylenebisacrylamide was added as a crosslinking agent to 90 g of a 40 wt% ammonium acrylate aqueous solution obtained by the biocatalyst of Production Example 2 and dissolved. This solution was transferred to a 300 ml separable flask and purged with nitrogen at 30 ° C. for 30 minutes while stirring. To this, 0.587 g of triethylene glycol was added, 0.0414 g of Rongalite was further added, and 0.092 g of a 30 wt% aqueous hydrogen peroxide solution was subsequently added to initiate polymerization. The temperature increased from 3 minutes after the start, and the maximum temperature reached 105 ° C. After polymerization for 1 hour, the hydrogel was crushed to about 5 mm square and dried at 100 ° C. for 2 hours in an inert oven with a nitrogen atmosphere. The dried polymer was pulverized with a homogenizer, and further dried at 100 ° C. in an inert oven for 2 hours. The polymer after drying was classified to 106 to 850 μm. Thereafter, heating was performed at 170 ° C. for 30 minutes. The water absorbent resin body obtained as described above is referred to as a water absorbent resin body (9). Table 2 shows the results of water absorption measurement of the water absorbent resin body (9).

Example 10
0.0187 g of N, N′-methylenebisacrylamide was added as a crosslinking agent to 90 g of a 40 wt% ammonium acrylate aqueous solution obtained by the biocatalyst of Production Example 2 and dissolved. This solution was transferred to a 300 ml separable flask and purged with nitrogen at 30 ° C. for 30 minutes while stirring. 0.263 g of erythritol was added thereto, 0.0414 g of Rongalite was further added, and 0.092 g of a 30% by weight aqueous hydrogen peroxide solution was subsequently added to initiate polymerization. The temperature rose from 1 minute after the start, and the maximum temperature reached 102 ° C. After polymerization for 1 hour, the hydrogel was crushed to about 5 mm square and dried at 100 ° C. for 2 hours in an inert oven with a nitrogen atmosphere. The dried polymer was pulverized with a homogenizer, and further dried at 100 ° C. in an inert oven for 2 hours. The polymer after drying was classified to 106 to 850 μm. Thereafter, heating was performed at 170 ° C. for 30 minutes. The water absorbent resin body obtained as described above is designated as a water absorbent resin body (10). Table 2 shows the results of water absorption measurement of the water absorbent resin body (10).

Example 11
In a 300 ml flask, 118.18 g of reagent acrylic acid (manufactured by Wako Pure Chemicals, reagent special grade), 168.51 g of water, 16.03 g of 30% by weight NaOH aqueous solution and 109.38 g of 25% by weight ammonia water were cooled with ice. Slow addition was performed so that the liquid temperature did not exceed 30 ° C.
90 g of the monomer aqueous solution and 0.0378 g of N, N′-methylenebisacrylamide are added to a 300 ml separable flask. The flask is bathed in a water bath so that the liquid temperature is maintained at 30 ° C. The aqueous solution was deaerated by bubbling with nitrogen gas, and the reaction system was purged with nitrogen. Next, 0.86 g of 42 wt% glycerin aqueous solution was added with a syringe, and after stirring well, 0.0953 g of 30 wt% aqueous hydrogen peroxide solution dissolved in 1 g of water and 0.0419 g of Rongalite were added to initiate polymerization. The internal temperature started from 30 ° C and increased to 105 ° C 5 minutes after the start of the reaction. Then, it heats in a water bath for 3 hours so that internal temperature may be maintained at 70 degreeC. Thereafter, the gel is taken out from the Separa flask and roughly crushed and then dried at 100 ° C. for 4 hours using an inert oven in a nitrogen atmosphere. After drying, the mixture is pulverized with a homogenizer, and 100 to 850 μm is collected by sieving. This is heated at 170 ° C. in an inert oven for 30 minutes under a nitrogen atmosphere. The water absorbent resin body thus obtained is designated as a water absorbent resin body (11).
Table 2 shows the results of water absorption measurement of the water absorbent resin body (11).

Comparative Example 1
To a 300 ml separable flask, 171.13 g of 40 wt% ammonium acrylate aqueous solution, 18.53 g of acrylic acid and 35.34 g of water were added to obtain 38 wt% ammonium acrylate / acrylic acid = 75/25 aqueous solution. 7.8 g of activated carbon was added and stirred for 1 hour under light shielding. After the activated carbon was filtered off, 0.0968 g of trimethylolpropane triacrylate was added as a crosslinking agent and dissolved. 90 g of this solution was transferred to a 300 ml separable flask and purged with nitrogen at 30 ° C. for 30 minutes while stirring. To this was added 0.018 g of sodium bisulfite, followed by 0.0276 g of ammonium persulfate. After polymerization for 1 hour, the polymer was pulverized to about 5 mm and dried at 150 ° C. for 1 hour in an inert oven in a nitrogen atmosphere. The dried polymer was pulverized with a homogenizer and classified to 106 μm to 850 μm. After mixing 100 parts of the classified polymer with 2 parts of propylene glycol, 3 parts of water and 30 parts of isopropyl alcohol, the mixture was heat-treated at 150 ° C. for 60 minutes. The resin body obtained as described above is referred to as a comparative water absorbent resin body (1).
Table 1 shows the results of measuring the neutralization rate of the outer surface of the resin body of the comparative water-absorbent resin body (1) and the neutralization ratio of the central portion of the resin body, the measurement results of the skin structure width obtained by IR imaging, and the results of water absorption measurement. Shown in

Comparative Example 2
Reagent acrylic acid (manufactured by Wako Pure Chemical Industries, special grade reagent) 28.32 g was dissolved in water 52.96 g. This aqueous solution was cooled in an ice bath, and while maintaining the liquid temperature at 30 ° C. or lower, 18.35 g of a 25 wt% aqueous ammonia solution was gradually added with stirring, and 40 wt% ammonium acrylate / acrylic acid = 70/30. An aqueous solution was obtained. After 90 g of this ammonium acrylate / acrylic acid = 70/30 aqueous solution was brought to 10 ° C. and purged with nitrogen for 30 minutes, 0.72 g of ammonium carbonate and 0.147 g of triallylamine were added. As initiators, 0.1387 g of ammonium persulfate, 0.0322 g of 30% by weight hydrogen peroxide, and 0.0016 g of L-ascorbic acid were added. After polymerization for 1 hour, it was crushed and dried in an inert oven in a nitrogen atmosphere at 120 ° C. for 2 hours. After drying, 0.25 part of ethylene glycol diglycidyl ether, 2 parts of water, and 2 parts of ethanol were mixed with 100 parts of the polymer, followed by heat treatment at 120 ° C. for 60 minutes. The resin body obtained as described above is referred to as a comparative water absorbent resin body (2).
Table 1 shows the results of measuring the neutralization rate of the outer surface of the resin body of the comparative water-absorbent resin body (2) and the neutralization ratio of the center of the resin body, the skin structure width obtained by IR imaging, and the results of water absorption measurement. Shown in

Comparative Example 3
Reagent acrylic acid (Wako Pure Chemical Industries, reagent special grade) 28.32 g was dissolved in water 52.96 g. This aqueous solution was cooled in an ice bath, and while maintaining the liquid temperature at 30 ° C. or lower, 18.35 g of a 25 wt% aqueous ammonia solution was gradually added with stirring, and 40 wt% ammonium acrylate / acrylic acid = 70/30. An aqueous solution was obtained. After 90 g of this ammonium acrylate / acrylic acid = 70/30 aqueous solution was brought to 10 ° C. and purged with nitrogen for 30 minutes, 0.72 g of ammonium carbonate and 0.147 g of triallylamine were added. As initiators, 0.1387 g of ammonium persulfate, 0.0322 g of 30% by weight hydrogen peroxide, and 0.0016 g of L-ascorbic acid were added. After polymerization for 1 hour, the mixture was crushed and dried in an inert oven in a nitrogen atmosphere at 150 ° C. for 1 hour. After drying, it was heated at 170 ° C. for 30 minutes in an inert oven in a nitrogen atmosphere. The resin obtained as described above is referred to as a comparative water absorbent resin body (3). Table 2 shows the results of water absorption measurement of the comparative water absorbent resin body (3).

Comparative Example 4
67.75 g of the sodium acrylate aqueous solution obtained in Production Example 3 was dissolved in 13.35 g of water. To this sodium acrylate aqueous solution, 8.9 g of acrylic acid was added to obtain 90 g of 40 wt% sodium acrylate / acrylic acid = 70/30 aqueous solution. As a cross-linking agent, 0.0992 g of N, N′-methylenebisacrylamide was added and dissolved. This solution was transferred to a 300 ml separable flask and purged with nitrogen at 30 ° C. for 30 minutes while stirring. Polymerization is started by adding 0.0007 g of L-ascorbic acid dissolved in 1 g of water and 0.046 g of ammonium persulfate. After polymerization for 3 hours, the hydrogel was crushed to about 5 mm square and dried at 150 ° C. for 1 hour in an inert oven with a nitrogen atmosphere. The dried polymer was pulverized with a homogenizer and then classified to 106 to 850 μm. After mixing 100 parts of the classified polymer with 2 parts of propylene glycol, 3 parts of water and 30 parts of isopropyl alcohol, the mixture was heat-treated at 170 ° C. for 30 minutes. The resin obtained as described above is referred to as a comparative water absorbent resin body (4). Table 2 shows the results of water absorption measurement of the comparative water absorbent resin body (4).

Comparative Example 5
17.54 g of acrylic acid and 43.1 g of water were added to 54.73 g of the aqueous ammonium acrylate solution obtained in Production Example 1 to obtain 90 g of 40 wt% ammonium acrylate / acrylic acid = 50/50 aqueous solution. 1 g of activated carbon was added and stirred for 1 hour in the dark. After filtering off the activated carbon, 0.0992 g of N, N′-methylenebisacrylamide as a cross-linking agent was added to 90 g of this solution and dissolved. This solution was transferred to a 300 ml separable flask and purged with nitrogen at 30 ° C. for 30 minutes while stirring. Polymerization is started by adding 0.0004 g of L-ascorbic acid and 0.046 g of ammonium persulfate dissolved in 1 g of water. After polymerization for 3 hours, the hydrogel was crushed to about 5 mm square and dried at 150 ° C. for 1 hour in an inert oven with a nitrogen atmosphere. The dried polymer was pulverized with a homogenizer and then classified to 106 to 850 μm. After mixing 100 parts of the classified polymer with 2 parts of propylene glycol, 3 parts of water and 30 parts of isopropyl alcohol, the mixture was heat-treated at 170 ° C. for 30 minutes. The resin obtained as described above is referred to as a comparative water absorbent resin body (5). Table 2 shows the results of water absorption measurement of the comparative water absorbent resin body (5).

  The water-absorbent resin body and the method for producing the same according to the present invention can be suitably used in the field of application of a highly water-absorbent resin that is required for water absorption performance under high pressure and used for sanitary materials and the like.

A micrograph of a sample section subjected to IR imaging. A broken line shows the line which measured. The line profile which digitized 1695 / 1558cm < ^-1 > peak area ratio measured along the broken line of FIG. 1 in IR imaging measurement. The vertical axis represents the peak area ratio, and the horizontal axis represents the measurement position on the sample line.

Claims (8)

  Of the repeating units in the polymer molecular chain, 50 mol% or more is a water-absorbent resin body composed of carboxyl group-containing units, the carboxyl group neutralization rate at the center of the resin body is 60 mol% or more, and the carboxyl on the outer surface of the resin body A water-absorbent resin body having a group neutralization rate of 50 mol% or less.   The water-absorbent resin body according to claim 1, wherein a portion having a lower neutralization rate than the central portion of the resin body is present in a width of 13 μm or more from the outer surface of the resin body. The water-absorbent resin body according to claim 1 or 2, wherein the following (1) and (2) are satisfied.
(1) 50 mol% or more of the carboxyl group neutralized salt in the polymer molecular chain is an ammonium salt.
(2) The water absorption magnification under a pressure of 0.8 psi is 22 times or more.   4. The water absorbent resin body according to claim 3, wherein the water absorbent resin body is a powder particulate water absorbent resin having a particle size distribution of 40 [mu] m to 1000 [mu] m. A water-absorbing characteristic, wherein the monomer solution satisfying the following (3) to (5) is polymerized, crushed, dried, pulverized, or polymerized, crushed, pulverized, dried, and then heated. A method for producing a resin body.
(3) At least one kind of unsaturated carboxylic acid ammonium salt (A), unsaturated carboxylic acid alkali metal salt (B), and a condensation type crosslinking agent (C) for a carboxyl group.
(4) The ratio of unsaturated carboxylic acid ammonium salt (A) is more than 50 mol% and 100 mol% or less with respect to all unsaturated carboxylic acid monomers, and the ratio of unsaturated carboxylic acid alkali metal salt (B) is all It is 0 mol% or more and less than 50 mol% with respect to the unsaturated carboxylic acid monomer.
(5) The content of the condensation type crosslinking agent (C) with respect to the carboxyl group is 0.01% by weight or more and 20% by weight or less based on the weight of all monomer components.   The method for producing a water absorbent resin body according to claim 5, wherein the heat treatment is performed at 100 to 250 ° C.   In addition to the condensation type crosslinking agent (C) for the carboxyl group as a crosslinking agent, the unsaturated monomer polymerizable crosslinking agent (D) is contained in an amount of 0.005 mol% to 1 mol% with respect to all monomer components. The method for producing a water-absorbent resin body according to claim 5, wherein the water-absorbent resin body is produced.   The method for producing a water-absorbent resin body according to any one of claims 5 to 7, wherein the unsaturated carboxylates (A) and (B) are (meth) acrylates.

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