JP2006168324A - Water absorbent composite, its manufacturing method and material using water absorbent composite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water absorbent composite having a high water absorbing speed, characterized in that a water absorbent polymer is uniformly fixed to fibers before and after the absorption of water and having proper flexibility. <P>SOLUTION: The water absorbent composite is constituted of a multilayered structure having a water absorbent polymer layer between first and second base materials and characterized in that the water absorbent polymer layer is fixed to both of the first and second base materials. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a water-absorbent composite and a method for producing the same. The absorbent article of the present invention can be suitably used for sanitary materials such as disposable diapers and sanitary products, industrial materials necessary for absorbing and retaining waste water, and agricultural materials such as freshness-retaining agents such as vegetables and water retention agents. .

  Most commercially available water-absorbing polymers are in the form of powder. For example, for use as sanitary materials such as sanitary napkins and paper diapers, it is necessary to uniformly disperse them on substrates such as tissues, nonwoven fabrics, and cotton. There is. However, the water-absorbing polymer powder dispersed by such a method is difficult to fix on the substrate with good stability, and is often partially assembled after dispersion. In addition, when the water-absorbing gel after water absorption is not stably fixed on the base material and easily moves from the base material, a region where the water-absorbing gel does not exist is formed and body fluid or the like has permeated again. There was a problem of leakage.

  As a method for solving these problems, a method of fixing a water-absorbing polymer powder on a substrate with a binder is known. However, since the binder adheres to the surface of the water-absorbing polymer, the water-absorbing swelling is inhibited and sufficient. There was a problem that the absorption ability could not be demonstrated. Moreover, the absorber which made the fiber adhere to the water-absorbing polymer surface is also proposed (patent documents 1-3). Before water absorption, the fiber is firmly bonded to the fiber, so that the stability is also fixed. However, these absorbent materials have a problem that the fiber easily deviates from the water-absorbing gel by absorbing the liquid.

In order to solve these problems, an absorbent material in which fibers are embedded in a water-absorbing polymer has been proposed (Patent Publications 4 to 7). These absorbent materials are obtained by swelling a water-absorbing polymer with water or the like, mixing or kneading fibers, embedding in the water-absorbing polymer, drying, and crushing. The obtained absorbent material has a sharp surface and is partially angular.
JP 51-35685 A JP 56-65630 A JP 58-163438 A Japanese Patent Laid-Open No. 61-62463 JP 63-63723 A JP-A-1-135350 Japanese Patent Publication No. 8-19609

  However, when these absorbents are pressed to increase the density in order to reduce the thickness of sanitary materials and the like, the water-absorbing polymers collide with each other to form corners, and sometimes the water-absorbing polymers themselves are distorted and cracked. Sometimes. As a result, there arises a problem that the water-absorbing polymer which has become free from the fibers leaks from the absorbent article. For this reason, it has been difficult to increase the density of the absorbent material in which the water-absorbing polymer is stably fixed. Further, when the water-absorbing gel and the fiber are kneaded and mixed, a part of the short fiber is completely embedded in the water-absorbing polymer, and the completely embedded fiber does not exhibit the original effect but only inhibits the swelling. Further, since the fiber and the water-absorbing polymer are not firmly bound by polymerization, a gap is formed between the fiber and the water-absorbing gel at the time of swelling, and the water-absorbing gel easily moves on the fiber. Further, by kneading the water-absorbing gel under mechanical pressure, the polymer chain is broken and the original water-absorbing performance cannot be obtained.

  A first object of the present invention is to provide a water-absorbing composite having a moderate wateriness, having a high water absorption rate, and a water-absorbing polymer being uniformly fixed to fibers through before and after water absorption. The second object of the present invention is to provide a method for efficiently producing a water-absorbing composite having such characteristics.

A first object of the present invention is a multilayer structure having a water-absorbing polymer layer between a first base material and a second base material, and the water-absorbing polymer layer includes both the first base material and the second base material. Achievable with a water-absorbing composite characterized by sticking.
In the water-absorbent composite of the present invention, the water-absorbing polymer constituting the water-absorbing polymer layer is (1) a bounded particulate structure that is bound to each other while maintaining the particle shape, and / or (2) a webbed structure. It is preferable to have. In the water-absorbent composite of the present invention, it is preferable that the average particle diameter of the water-absorbing polymer particles constituting the binder-particulate water-absorbing polymer is 50 to 1000 μm. The web-like water-absorbing polymer is a web-like dispersed layer having a thickness of 50 to 1000 μm and an average diameter of 200 to 50000 μm, or having a thickness of 50 to 1000 μm and an average pore diameter of 100 to 50000 μm A web-like continuous layer having a rate of 10 to 80% is preferred. In the water-absorbent composite of the present invention, it is preferable that at least one of the first base material and the second base material is a fibrous base material.

  The second object of the present invention is to form in the gas phase droplets comprising a reaction mixture in which polymerization is initiated by mixing an aqueous solution of a polymerizable monomer that gives a water-absorbing polymer and a redox polymerization initiator, Dropping the droplet of the polymerizable monomer onto the first substrate, and laying the second substrate in a state where the average polymerization rate of the polymerizable monomer on the first substrate is 10 to 80%. It was achieved by a method for producing a water-absorbing composite, characterized in that it is carried out. When laying the second base material, it is preferable to pressurize at 0.0001 to 1 MPa.

  The water-absorbing composite of the present invention has a high water absorption rate, and the water-absorbing polymer is uniformly fixed to the fiber through before and after water absorption, and has moderate flexibility. Further, since the water-absorbing polymer having adhesiveness, adhesiveness, and hygroscopicity is coated with the base material, it is possible to avoid contact with sliding parts such as a take-up roller, and the line operability is excellent. For this reason, the water-absorbent composite of the present invention is suitably used for sanitary materials such as disposable diapers and sanitary goods, industrial materials necessary for absorption and retention of wastewater, agricultural materials such as freshness-retaining agents such as vegetables and water-retaining agents. can do. Moreover, according to the method for producing a water-absorbent composite of the present invention, a water-absorbent composite having such characteristics can be produced efficiently.

BEST MODE FOR CARRYING OUT THE INVENTION

  Hereinafter, the water-absorbent composite of the present invention and the production method thereof will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

I. Water-absorbent composite (structure features)
The water-absorbing composite of the present invention has a multilayer structure having a water-absorbing polymer layer between a first base material and a second base material, and the water-absorbing polymer layer includes both the first base material and the second base material. It is characterized by being fixed. The water-absorbing polymer constituting the water-absorbing polymer layer preferably has (1) a bounded particulate structure that is bound to each other while maintaining the particle shape, and / or (2) a webbed structure.

The “water web-like water-absorbing polymer” as used herein refers to a water-absorbing polymer that is fixed to the fibers constituting the base material in a water web shape. The web-forming water-absorbing polymer penetrates the fibers constituting the base material, and the water-absorbing polymer is fixed to the fiber like a web by the portion where the penetrated fibers appear outside the water-absorbing polymer.
The web-like water-absorbing polymer may be scattered in islands on the base material to form a dispersed dispersion layer. May form a continuous layer scattered in islands. Preferred is a dispersion layer. Further, a dispersed layer and a continuous layer may be mixed.

When the web-like water-absorbing polymer forms a dispersion layer, the shape and size are not particularly limited, but the thickness is preferably 50 to 1000 μm, more preferably 80 μm to 800 μm, and more preferably 100 μm. More preferably, it is -500 micrometers. The average diameter is preferably 200 to 50000 μm, more preferably 300 μm to 30000 μm, and still more preferably 400 μm to 20000 μm.
Even when the webbed water-absorbing polymer forms a continuous layer, its shape and size are not particularly limited. The thickness is preferably 50 to 1000 μm, more preferably 80 μm to 800 μm, and still more preferably 100 μm to 500 μm. The average pore diameter is preferably 100 to 50000 μm, more preferably 200 μm to 30000 μm, and still more preferably 300 μm to 20000 μm. Further, the porosity is preferably 10% to 80%, more preferably 20% to 70%, and further preferably 30% to 60%.
In addition, the thickness and average diameter of the dispersed layer, and the average pore diameter and aperture ratio of the continuous layer are determined by a measurement method described later.

The “binder-particulate water-absorbing polymer” constituting the water-absorbing composite of the present invention refers to those in which water-absorbing polymer particles are bound to each other while maintaining a substantially spherical particle shape. At least one particle constituting the binder-particulate water-absorbing polymer embeds a part of the fibers constituting the substrate. The fiber may or may not penetrate the water-absorbing polymer. However, the water-absorbing polymer in the form of binder particles is firmly fixed to the substrate by embedding part of the fibers.
The overall shape and size of the water-absorbing polymer in the form of binder particles are not particularly limited. The water-absorbing polymer particles may be bound together in a bead shape or may be bound so that the whole becomes a lump. Preferred is an embodiment in which the water-absorbing polymer particles are bound so that the surface area is increased to some extent. A bead-like water-absorbing polymer and a block-shaped water-absorbing polymer may be mixed.
The length of the binding particulate water-absorbing polymer is preferably 100 μm to 5000 m, more preferably 200 μm to 4000 μm, and further preferably 300 μm to 3000 μm. The thickness is preferably 50 μm to 3000 μm, more preferably 100 μm to 2000 μm, and still more preferably 200 μm to 1000 μm. Furthermore, the average particle diameter of the water-absorbing polymer particles constituting the binder-particulate water-absorbing polymer is preferably 50 to 1000 μm, more preferably 100 μm to 800 μm, and further preferably 200 μm to 500 μm. preferable.

  The ratio of the web-like water-absorbing polymer and the binding particle-like water-absorbing polymer constituting the water-absorbing composite of the present invention is not particularly limited. It may consist of only one of them, or may be a mixture of both.

  A preferable ratio when both are present is 1 to 10,000 parts by weight of the water-absorbing polymer in the form of binder particles, more preferably 5 to 2000 parts by weight, more preferably 100 parts by weight of the web-like water-absorbing polymer. The amount is preferably 10 to 1000 parts by weight. Further, the positional relationship between the web-like water-absorbing polymer and the binder-particle-like water-absorbing polymer is not particularly limited. Preferred is an embodiment in which a web-like water-absorbing polymer is formed on a substrate, and a binder-particle-like water-absorbing polymer is further formed thereon. Further, an embodiment in which a water-absorbing polymer in the form of binder particles is formed in the pores of the water-absorbing water-absorbing polymer formed on the substrate is also preferable.

  The water-absorbing composite in which the water-absorbing polymer and the water-absorbing polymer particles, which are bonded to each other while maintaining the particle shape, are fixed on the substrate have a high water absorption rate. It has the characteristics. Although not bound by any theory, the reason why the water absorption speed is high is that the fibrous base material on the surface of the water-absorbent polymer and the base material on the back surface are bound particle-like water-absorbing polymer due to thinning, etc. described later. Having a structure that is close enough to induce capillary action of the liquid to be absorbed. It is thought that it is because.

  The liquid absorption can be performed from the back side or from the front side, but it is preferable that the liquid absorption side is hydrophobic and the opposite side is hydrophilic. This is presumably because the liquid-absorbing side diffuses the liquid evenly in a plane and also quickly diffuses to the opposite substrate. On the other hand, it is considered that the substrate on the opposite side has the action of absorbing and storing the liquid faster than the water-absorbing polymer and then distributing it to the water-absorbing polymer. Accordingly, the water absorption speed depends on the thickness of the individual base material and the water-absorbing polymer layer constituting the composite, but ultimately depends on the thickness of the water-absorbing composite. The thickness of the water-absorbent composite of the present invention is preferably 400-2500 μm, more preferably 500-2000 μm, and most preferably 600-1500 μm. If thickness is 400 micrometers or more, it will be easy to avoid that a water absorbing polymer will be physically restrained and a water absorption speed | rate will fall. If the thickness is 2500 μm or less, the fibrous base material on the surface of the water-absorbing polymer and the base material on the back surface are in contact with each other through the voids of the water-absorbing polymer in the form of binder particles, or the water-absorbing water-absorbing property. It is easy to form a state of contact through the voids or pores of the polymer, or at least close enough to induce capillary action of the liquid to be absorbed. The method for obtaining such a structure is not particularly limited, but it is generally preferable to use a compression molding method as described later.

(Water-absorbing polymer)
The water-absorbing polymer used in the present invention can be produced using the following polymerizable monomer and initiator.
The polymerizable monomer to be used is not limited as long as it provides a water-absorbing polymer. It is particularly preferable to use a polymerizable monomer whose polymerization is initiated by a redox initiator. This polymerizable monomer is usually preferably water-soluble.
A typical example of such a polymerizable monomer, which is also preferable for use in the present invention, is an aliphatic unsaturated carboxylic acid or a salt thereof. Specific examples include unsaturated monocarboxylic acids or salts thereof such as acrylic acid or salts thereof, methacrylic acid or salts thereof; or unsaturated dicarboxylic acids or salts thereof such as maleic acid or salts thereof, itaconic acid or salts thereof, etc. These may be used alone or in admixture of two or more. Among these, acrylic acid or a salt thereof, and methacrylic acid or a salt thereof are preferable, and acrylic acid or a salt thereof is particularly preferable.

As the polymerizable monomer that gives the water-absorbing polymer used in the present invention, an aliphatic unsaturated carboxylic acid or a salt thereof is preferable as described above. Therefore, as the aqueous solution of the polymerizable monomer, an aliphatic unsaturated carboxylic acid or a salt thereof is used. An aqueous solution containing as a main component is preferable. Here, “mainly composed of an aliphatic unsaturated carboxylic acid or a salt thereof” means that the aliphatic unsaturated carboxylic acid or a salt thereof is 50 mol% or more, preferably 80 mol% based on the total amount of the polymerizable monomer. % Is included.
As the salt of the aliphatic unsaturated carboxylic acid, a water-soluble salt such as an alkali metal salt, an alkaline earth metal salt, or an ammonium salt is usually used. The degree of neutralization is appropriately determined according to the purpose. In the case of acrylic acid, it is preferable that 20 to 90 mol% of the carboxyl group is neutralized with an alkali metal salt or an ammonium salt. When the degree of partial neutralization of the acrylic acid monomer is less than 20 mol%, the water absorbing ability of the water-absorbing polymer to be produced tends to be remarkably lowered.
For neutralization of the acrylic acid monomer, alkali metal hydroxides, bicarbonates, or ammonium hydroxides can be used, but preferred are alkali metal hydroxides. Sodium oxide and potassium hydroxide are mentioned.

In the present invention, in addition to the above aliphatic unsaturated carboxylic acids, polymerizable monomers copolymerizable therewith, such as (meth) acrylamide, (poly) ethylene glycol (meth) acrylate, 2 -Although it is a hydroxyethyl (meth) acrylate or a low water-soluble monomer, alkyl acrylates such as methyl acrylate and ethyl acrylate can be used in such an amount that does not deteriorate the performance of the resulting water-absorbing polymer. It can be copolymerized. In the present specification, the term “(meth) acryl” means both “acryl” and “methacryl”.
Of these polymerizable monomers, those that give a water-absorbing polymer are not used as auxiliary components for the aliphatic unsaturated carboxylic acid or a salt thereof, but the main monomer of “an aqueous solution of a polymerizable monomer that gives a water-absorbing polymer”. It can also be used as
An aliphatic unsaturated carboxylic acid or a salt thereof, particularly acrylic acid or a salt thereof may form a self-crosslinked polymer by itself, but a crosslinker can be used in combination to actively form a crosslinked structure. . When a crosslinking agent is used in combination, the water absorption performance of the generally formed water absorbing polymer is improved. Examples of the crosslinking agent include polyvinyl compounds copolymerizable with the polymerizable monomer, such as N, N′-methylenebis (meth) acrylamide, (poly) ethylene glycol di (meth) acrylates, and carboxylic acids. Water-soluble compounds having two or more functional groups capable of reacting with polyglycidyl ether such as ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether are preferably used. Of these, N, N′-methylenebis (meth) acrylamide is particularly preferred. The amount of the crosslinking agent used is 0.001 to 1% by weight, preferably 0.01 to 0.5% by weight, based on the charged amount of the polymerizable monomer.
The concentration of the polymerizable monomer in the polymerizable monomer aqueous solution containing the above-mentioned aliphatic unsaturated carboxylic acid or a salt thereof as a main component is 20% by weight or more, preferably 25% by weight or more. When the concentration is less than 20% by weight, the water absorption ability of the water absorbent polymer after polymerization tends to be insufficient. The upper limit is preferably about 80% by weight from the handling of the polymerization reaction solution.

As the polymerization initiator used in the present invention, those used in aqueous solution radical polymerization can be used. Examples of such initiators include inorganic and organic peroxides such as persulfates such as ammonium and alkali metals, particularly potassium, hydrogen peroxide, t-butyl peroxide, and acetyl peroxide.
Furthermore, initiators known as azo compounds can also be used. For example, 2,2′-azobis (2-amidinopropane) dihydrochloride, which shows water solubility to some extent, can be mentioned.
Polymerization is initiated by decomposition of the radical polymerization initiator. A commonly known technique is pyrolysis. Often, a polymerization initiator that has not been heated is added to the polymerizable monomer in the reaction solution that has been heated to the decomposition temperature of the polymerization initiator in advance to initiate the polymerization. Belongs.
The initiator preferably used in the present invention is a combination of an oxidizing agent and a reducing agent that forms a water-soluble redox system to some extent.

  Examples of the oxidizing agent include hydrogen peroxide, persulfates such as ammonium persulfate and potassium persulfate, t-butyl hydroperoxide, cumene hydroperoxide, ceric salt, permanganate, chlorite, Examples include hypochlorite. Among these, hydrogen peroxide is particularly preferable. The amount of these oxidizing agents used is 0.01 to 10% by weight, preferably 0.1 to 2% by weight, based on the polymerizable monomer.

  The reducing agent is capable of forming a redox system with the oxidizing agent, specifically, sulfites such as sodium sulfite and sodium bisulfite, sodium thiosulfate, cobalt acetate, copper sulfate, ferrous sulfate, L- Examples include ascorbic acid or L-ascorbic acid alkali metal salts. Among these, L-ascorbic acid or L-ascorbic acid alkali metal salt is particularly preferable. The amount of these reducing agents used is 0.001 to 10% by weight, preferably 0.01 to 2% by weight, based on the polymerizable monomer.

(Base material)
As the first substrate and the second substrate (hereinafter collectively referred to as “substrate”) constituting the water-absorbent composite of the present invention, a planar substrate can be used, and a plate, sheet, film, A fiber assembly can be used. Even if the substrate itself has a low form-maintaining property, the water-absorbing polymer may be fixed to develop the shape-maintaining property. In that sense, a soft and sparse material or a base material with a filament on a flat surface can be used.
The substrate to which the water-absorbing polymer is fixed is preferably a physical surface state in which the water-absorbing polymer is easily fixed, that is, moderately rough. In addition, a substrate having good water permeability, liquid permeability, water conductivity, and liquid conductivity is preferable from the viewpoint of water absorption, and a sparse substrate having continuous pores and continuous voids is preferable. From these viewpoints, a fibrous base material that is a fiber assembly is preferable, and among the fibrous base materials, paper, fluff pulp, cloth, or non-woven fabric is preferable, and fluff pulp and non-woven fabric are most preferable. Nonwoven fabrics can be used in which the fibers are produced by a known production method (such as an airlaid method, a wet laid method, a hydraulic entrainment method, a staple length fiber card bond method, or a solution spinning method).

The substrate preferably has a chemical affinity with the water-absorbing polymer so that the water-absorbing polymer is easily fixed. In water-absorbing applications, hydrophilic base materials are used because of the action of attracting water to the water-absorbing polymer (so-called water-conducting properties), but hydrophobic properties that increase water permeability and water diffusivity by repelling water. A substrate can also be used, and is appropriately selected depending on the configuration of the water-absorbent composite.
As the material of the fibrous base material, known materials described in “Fiber Handbook (raw material edition)” (Fiber Society of Japan, Maruzen, 1968) or “Fiber Handbook (Processing edition)” (Fiber Society of Japan, Maruzen, 1969) Can be used. Examples thereof include natural fibers such as plant fibers, animal fibers, and mineral fibers, and chemical fibers such as regenerated fibers, semi-synthetic fibers, synthetic fibers, and mineral fibers.

Examples of so-called hydrophilic fibers having large hydrophilicity include cellulose fibers such as pulp, rayon, cotton, and regenerated cellulose, and fibers such as polyamide and polyvinyl alcohol.
Examples of hydrophobic fibers include polyester, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyurea, polyurethane, polyfluoroethylene, and polycyanide vinylidene. Can be mentioned.

The fibers can be made from a single resin, but it is also possible to use fibers made from two or more resins. For example, a thermoplastic fiber in which a core fiber made of one resin is wrapped in a thermoplastic sheath made of different resins can be used. Examples of the sheath / core fiber obtained by combining the two types of resins used in the present invention include polyethylene / polypropylene, polyethyl acetate / polypropylene, polyethylene / polyester, polypropylene / polyester, polyester copolymer / polyester, and the like. Particularly preferred are fibers made of a polypropylene or polyester core, a polyester copolymer or a polyethylene sheath.
In particular, for hygiene materials, it is preferable to select pulp among hydrophilic fibers from the viewpoint of low irritation to the skin and soft touch.

The fiber diameter of the fibrous base material constituting the fiber is preferably 0.1 to 500 dtex, more preferably 0.1 to 100 dtex, even more preferably 1 to 50 dtex, and particularly preferably 1 to 10. Decitex. The average fiber length is preferably 50 to 100,000 μm. More preferably, it is 100-50,000 micrometers, More preferably, it is 500-30,000 micrometers. The shape may be linear, wavy, coiled, split, looped or star-shaped. The basis weight is 5 to 500 g / m ^2, further 10 to 200 g / m ^2, it is preferred in particular 20 to 150 g / m ^2.
The first base material and the second base material constituting the water-absorbing composite of the present invention may be base materials made of the same material or base materials made of different materials. Preferred materials for the substrate are fluff pulp and non-woven fabric.

II. Manufacturing method of water-absorbing composite The manufacturing method of the water-absorbing composite of the present invention is not particularly limited as long as it can manufacture a water-absorbing composite that satisfies the conditions described in the claims. Among various production methods, particularly according to the production method of the present invention, a water-absorbent composite can be produced efficiently. In the production method of the present invention, a droplet composed of a reaction mixture in which polymerization is started by mixing an aqueous solution of a polymerizable monomer that gives a water-absorbing polymer and a redox polymerization initiator is formed in the gas phase, and the polymerization is performed. The precursor droplet is dropped on the first substrate to produce a precursor composite, and the second substrate is in a state where the average polymerization rate of the polymerizable monomer on the first substrate is 10 to 80%. The step of laying is performed.

(Preparation of precursor composite)
In the production method of the present invention, a precursor composite is first prepared. Specifically, an aqueous solution of a polymerizable monomer that gives a water-absorbing polymer, for example, an aqueous solution of a polymerizable monomer that contains an aliphatic unsaturated carboxylic acid or a salt thereof as a main component, and a The polymerization of the monomer is started, and the reaction mixture containing the polymerizable monomer and the produced polymer after the start of the reaction is formed into droplets in the gas phase, and dispersed fibers supplied into the gas phase as necessary. Contact is made and the droplet is dropped onto the first substrate to form a precursor composite. As will be described later, similarly, the same droplet may be dropped on the second substrate to form a precursor composite.
One preferred method for polymerizing droplets in the gas phase is a first liquid comprising a polymerizable monomer aqueous solution containing one of an oxidizing agent and a reducing agent constituting the redox polymerization initiator and the other of the redox polymerization initiator. The polymerization is started by mixing in a gas phase a second liquid comprising an aqueous solution containing a polymerizable monomer as required.

As a specific means, for example, the first liquid and the second liquid are ejected from separate nozzles so that the crossing angle between the liquids flowing out from the nozzles is an angle of 15 degrees or more and collide in a liquid column state. There is a way. In this way, by causing the two liquids to collide with each other at an intersecting angle, a part of the outflow energy from the nozzle is used for mixing. The crossing angle between the first liquid and the second liquid flowing out from each nozzle is appropriately selected according to the properties of the polymerizable monomer to be used, the flow rate ratio, and the like. For example, if the linear velocity of the liquid is high, the crossing angle can be reduced.
In this case, the temperature of the first liquid is usually from room temperature to about 60 ° C., preferably from room temperature to about 40 ° C., and the temperature of the second liquid is also usually from room temperature to about 60 ° C., preferably from room temperature to about 40 ° C. ° C.
In this way, the respective aqueous solutions ejected from the nozzles collide in a liquid column state to combine both liquids. After the coalescence, a liquid column is formed and the state is maintained for a certain period of time. Thereafter, the liquid column is disassembled into droplets. The generated droplets undergo polymerization in the gas phase.

The size of the droplet is about 5 to 3,000 μm in diameter. In order for the polymerization of the droplets to proceed and to contact the fibers to form a suitable water-absorbing composite, the size of the droplets is preferably in the range of 50 to 1,000 μm. The spatial density of the droplets in the reactor is preferably 10 to 10,000 g / m ³ . If this upper limit is exceeded, a water-absorbing polymer that does not contact the fiber is produced, and if it is less than this lower limit, a fiber that does not contact the water-absorbing polymer is produced, resulting in a problem that the yield of the water-absorbing composite is relatively lowered.

  The gas phase gas that provides a reaction field for starting the polymerization and forming droplets during the polymerization is preferably inert to the polymerization such as nitrogen, helium, carbon dioxide, etc., but may be air. Also, there is no particular limitation on the humidity in the gas, including the case of only water vapor, but if the humidity is too low, the water in the polymerizable monomer aqueous solution evaporates before the polymerization proceeds, and the polymerizable monomer precipitates, As a result, there is a possibility that the polymerization rate is remarkably reduced or the polymerization is stopped midway. The temperature condition of the gas is room temperature or higher and 150 ° C. or lower, desirably 100 ° C. or lower. The gas flow direction may be either counter-current or co-current with respect to the liquid column and droplet traveling direction, but it is necessary to increase the residence time of the droplet in the gas phase, that is, increase the polymerization rate of the polymerizable monomer. In the case where it is necessary to increase the viscosity of the droplet, countercurrent (antigravity direction) is better.

(Base material laying)
Manufacturing a water-absorbing composite in which the water-absorbing polymer is fixed to both the first base material and the second base material by utilizing the adhesive force of the surface of the water-absorbing polymer of the precursor composite obtained by the manufacturing method. Is possible. This is because the surface of the reaction mixture has adhesive strength, and the reaction mixture and other substrates are firmly adhered to each other, and further chemically bonded as the polymerization proceeds, and further firmly fixed by drying. It is thought that. Specifically, the following embodiments are preferable.

1) First aspect According to the precursor composite preparation method, a precursor composite in which droplets are dropped on the first substrate and a precursor complex in which droplets are dropped on the second substrate are prepared. By bringing the water-absorbing polymer surfaces of these precursor composites into contact with each other and laying them, it is possible to obtain a water-absorbing composite having a multilayer structure having a water-absorbing polymer layer between the first substrate and the second substrate. it can. At this time, a 1st base material and a 2nd base material may consist of the same material and shape, and a material and / or a shape may differ.
2) Second embodiment According to the precursor composite preparation method, a precursor composite in which droplets are dropped on the first substrate is prepared, and a second substrate is further provided on the surface of the water-absorbing polymer of the precursor composite. By contacting and laying, a water-absorbing composite having a multilayer structure having a water-absorbing polymer layer between the first substrate and the second substrate can be obtained. Also in the second aspect, the first base material and the second base material may be made of the same material or shape, or may be different in material and / or shape.
Although it depends on the laying conditions, generally, from the viewpoint of strength against peeling, it is preferable to adopt the first embodiment because the adhesive strength becomes strong.

In the production method of the present invention, the average polymerization rate of the polymerizable monomer on the first substrate when laying the second substrate is 10 to 80%, preferably 15 to 65%, preferably 20% It is more preferably ˜60%, particularly preferably 25% to 55%. The weight ratio can be adjusted by controlling the distance at which droplets fall and the ambient temperature.
In the production method of the present invention, the moisture content of the polymerizable monomer on the first substrate when the second substrate is laid is preferably 25 to 80%, more preferably 30% to 75%. 35% to 70% is more preferable, and 40% to 65% is particularly preferable.

In order to lay within the range of these polymerization rates and moisture content, the second substrate should be laid generally within 60 minutes after the precursor composite is obtained under the conditions of atmospheric temperature of 0 to 40 ° C. It is preferable to lay within 30 minutes, and it is particularly preferable to lay within 20 minutes.
In laying the base material, it is possible to apply pressure so that the generated water-absorbing polymer is not damaged. A preferable pressure range is 0.0001 to 1 MPa, and more preferably 0.001 to 0.1 MPa. Although the method of pressurization is not particularly limited, pressurization can be performed by, for example, a flat press or roll press apparatus. Moreover, it can also pressurize in the other process substantially pressurized. Examples of such processes include a winding process, a laminating process, an embossing process, a printing process, and the like.

(Compression molding)
The water absorbent composite is preferably compression molded. For example, if a water-absorbing composite having a binding particle-like water-absorbing polymer and a web-like water-absorbing polymer is compression-molded, the fibrous base material on the surface of the water-absorbing polymer and the base material on the back surface become the binding particles. Contact through voids in the water-absorbing polymer, contact through voids or pores in the water-absorbing polymer, or at least close enough to induce capillary action of the liquid to be absorbed It becomes easy to form a state.
A preferable pressure range is 5 to 20 MPa, and more preferably 7 to 15 MPa.

(Other additional processes)
In the production of the water-absorbent composite of the present invention, as other additional steps, a residual monomer treatment step, a surface cross-linking step, a catalyst, a reducing agent, a deodorant, a human urine stabilizer, an antibacterial agent for imparting other functions. An additive addition step such as an agent and a neutralizing agent, a consolidation treatment step, and a recycling step may be added.

(1) Residual monomer treatment step The method of treating the residual monomer includes 1) a method of proceeding polymerization of the residual monomer, 2) a method of leading the residual monomer to another derivative, and 3) a method of removing the residual monomer. .
Examples of the method of proceeding the polymerization of the residual monomer of 1) include a method of further heating the water-absorbing composite, a method of heating after adding a catalyst or catalyst component that promotes the polymerization of the residual monomer to the water-absorbing polymer, Examples of the irradiation method include a method of irradiating electromagnetic radiation or particulate ionizing radiation.
In the method of further heating the water-absorbing composite, the water-absorbing composite is heat-treated at 100 to 250 ° C. to polymerize monomers remaining in the water-absorbing composite.
In the method of adding a catalyst or catalyst component that promotes the polymerization of residual monomer to the water-absorbing composite, for example, when polymerization is performed using a redox polymerization initiator, a radical generator often remains. Therefore, a reducing agent solution may be applied to the water-absorbing polymer. As the reducing agent, sodium sulfite, sodium hydrogen sulfite, L-ascorbic acid or the like used as a redox polymerization initiator may be used, and these are usually imparted to the water-absorbing complex as a 0.5 to 5% by weight aqueous solution. . The amount of the reducing agent applied is preferably 0.1 to 2% by weight based on the dry resin. Application | coating of a reducing agent solution can be performed by arbitrary methods, such as spraying using an atomizer and immersing in a reducing agent solution. The water-absorbing composite provided with the reducing agent is then heated to polymerize the monomer. Heating may be performed, for example, at 100 to 150 ° C. for about 10 to 30 minutes. Although the water content of the water-absorbing composite is reduced by this heating, if the water content is high, the water-absorbing composite is further dried with a dryer to obtain a product water-absorbing material.

In the method of irradiating the water-absorbing composite with ultraviolet rays, an ordinary ultraviolet lamp may be used, and the irradiation intensity, irradiation time, etc. vary depending on the type of fiber used, the amount of residual monomer impregnation, etc. 10 to 200 W / cm, preferably 30 to 120 W / cm, irradiation time 0.1 second to 30 minutes, and lamp-complex distance 2 to 30 cm. The water content in the water-absorbing composite at this time is generally 0.01 to 40 parts by weight, preferably 0.1 to 1.0 parts by weight, based on 1 part by weight of the polymer. The A water content of less than 0.01 parts by weight or more than 40 parts by weight is not preferable because it significantly affects the reduction of residual monomers. As an atmosphere when irradiating with ultraviolet rays, any of vacuum, presence of an inorganic gas such as nitrogen, argon, helium, or air can be used. The irradiation temperature is not particularly limited, and the object can be sufficiently achieved at room temperature. There is no restriction | limiting in particular also in the ultraviolet irradiation apparatus to be used, Arbitrary methods, such as the method of irradiating for a fixed time for a fixed time, or the method of irradiating continuously with a belt conveyor, can be used.
For the method of irradiating the water-absorbing composite, high-energy radiation such as accelerated electrons and gamma rays is used. The dose to be irradiated varies depending on the amount of residual monomer in the composite, the amount of water, and the like, but is generally 0.01 to 100 megarads, preferably 0.1 to 50 megarads. When the dose exceeds 100 megarads, the amount of water absorption becomes extremely small. When the dose is less than 0.01 megarad, the water absorption capacity and the water absorption speed intended in the present invention are large, and it is difficult to obtain a particularly small residual monomer. The water content of the water-absorbing composite at this time is generally 40 parts by weight or less, preferably 10 parts by weight or less, based on 1 part by weight of the polymer. If the amount of water exceeds 40 parts by weight, the effect of improving the water absorption rate is small, and particularly the reduction of the residual monomer is significantly affected. As an atmosphere for irradiating the composite with high energy radiation, any of vacuum, presence of an inorganic gas such as nitrogen, argon, helium, or air can be used. A preferable atmosphere is air. When irradiation is performed in the air, the water absorption capacity and the water absorption speed are large and the residual monomer is particularly small. Moreover, there is no restriction | limiting in particular in irradiation temperature, The objective can fully be achieved at room temperature.

  Examples of the method of introducing the residual monomer of 2) to other derivatives include a method of adding an amine, ammonia and the like, and a method of adding a reducing agent such as bisulfite, sulfite and pyrosulfite.

Examples of the method 3) for removing the residual monomer include extraction with an organic solvent and distillation. In the method of extraction with an organic solvent, the water-absorbing complex is immersed in a water-containing organic solvent to extract and remove residual monomers. As the water-containing organic solvent, ethanol, methanol, acetone or the like can be used, and the water content is preferably 10 to 99% by weight, particularly preferably 30 to 60% by weight. Generally, the higher the water content, the higher the ability to remove the residual monomer. However, when a water-containing organic solvent having a high water content is used, the energy consumption in the subsequent drying step increases. The time for immersing the complex in the water-containing organic solvent is usually about 5 to 30 minutes, and it is also preferable to adopt a means for promoting the extraction of the residual monomer such as shaking the complex. After the immersion treatment, it is usually treated with a dryer and dried.
As a method for distilling off the residual monomer, there is a method of treating the composite with superheated steam or a steam-containing gas. For example, the residual monomer in the water-absorbing polymer can be reduced by heating saturated steam at 110 ° C. to 120 to 150 ° C. and bringing the steam into contact with the composite as superheated steam. In this method, when water in the water-absorbing polymer evaporates as water vapor, it is considered that residual monomers are vaporized at the same time and escape from the water-absorbing polymer. According to this method, it is possible to both remove the residual monomer and dry the product.

(2) Surface cross-linking step For the purpose of improving the water absorption performance, the surface of the water-absorbing polymer can be cross-linked with a cross-linking agent. In general, it is known to improve the properties of resin particles by applying an appropriate amount of moisture together with a crosslinking agent to the surface of the powdery water-absorbing polymer particles and then heating to crosslink the surface. As a result of the formation of a crosslinked structure, it is considered that the shape can be maintained without inhibiting the swelling when water is absorbed and swollen. In this step, first, a solution of a surface cross-linking agent is applied to the water-absorbent composite. As the surface cross-linking agent, polyfunctional compounds that can be copolymerized with polymerizable monomers such as N, N′-methylenebis (meth) acrylamide and (poly) ethylene glycol di (meth) acrylate, (poly) ethylene glycol diglycidyl ether, etc. A compound having a plurality of functional groups capable of reacting with the carboxylic acid group is used. These surface cross-linking agents are usually used in an amount of 0.1 to 1% by weight, preferably 0.2 to 0.5% by weight, based on the water-absorbing composite. These surface cross-linking agents are diluted with water, ethanol, methanol, etc. in an amount of 0.1 to 1% by weight, particularly 0.2 to 0.5% by weight so as to be uniformly applied to the entire water-absorbent composite. % As a solution. The application of the cross-linking agent solution is usually preferably carried out by spraying the cross-linking agent solution onto the water-absorbing composite using a sprayer or applying the cross-linking agent solution with a roll brush. In addition, after providing a crosslinking agent solution excessively, you may make it remove excessive surplus crosslinking agent solution by squeezing lightly to such an extent that a resin particle is not crushed with a pressing roll, or blowing a wind. The application of the crosslinking agent solution may be performed at room temperature. The water-absorbing composite provided with the cross-linking agent solution is then heated to cause a cross-linking reaction to selectively form a cross-linked structure on the surface of the water-absorbing polymer. The conditions for the cross-linking reaction may be appropriately selected depending on the cross-linking agent to be used. Usually, the reaction is performed at a temperature of 100 ° C. or higher for 10 minutes or longer. In the present invention, an unsaturated carboxylic acid polymer crosslinked product is preferred as the water-absorbing polymer, and a partially neutralized acrylic acid polymer crosslinked product is particularly preferred.

(3) Addition process of additives Various additives can be added to the water-absorbent composite in order to impart a desired function depending on the intended use. Examples of these additives include a stabilizer for preventing polymer degradation and alteration due to the liquid to be absorbed, an antibacterial agent, a deodorant, a deodorant, a fragrance, and a foaming agent.
Among these, as stabilizers to prevent polymer degradation and alteration due to the liquid to be absorbed, excretion (ie human urine, feces), body fluid (human fluid, menstrual blood, secretion fluid, etc.) decomposition and alteration of the water-absorbing polymer Stabilizers to prevent are mentioned. Japanese Patent Laid-Open No. 63-118375 discloses a method of containing an oxygen-containing reducing inorganic salt and / or organic antioxidant in a polymer, Japanese Patent Laid-Open No. 63-153060 discloses a method of containing an oxidizing agent, JP 63-127754 A contains an antioxidant, JP 63-272349 A contains a sulfur-containing reducing agent, and JP 63-146964 A contains a metal chelating agent. JP-A 63-15266 discloses a method of containing a radical chain inhibitor, JP-A 1-275661 discloses a method of containing a phosphinic acid group- or phosphonic acid group-containing amine compound or a salt thereof, Japanese Laid-Open Patent Application No. 64-29257 discloses a method of containing a polyvalent metal oxide, Japanese Patent Application Laid-Open No. 2-255804, Japanese Patent Application Laid-Open No. 3-179008 discloses polymerization. A method in which the coexistence of a water-soluble chain transfer agents have been proposed. All of these can be used in the present invention. In addition, JP-A-6-306202, JP-A-7-53884, JP-A-7-62252, JP-A-7-113048, JP-A-7-145326, JP-A-7-145263, The materials and methods described in JP-A-7-228788 and JP-A-7-228790 can also be used. Specific examples include potassium oxalate titanate, tannic acid, titanium oxide, phosphinic acid amine (or salt thereof), phosphonic acid amine (or salt thereof), metal chelate and the like. Of these, stabilizers against human urine, human blood and menstrual blood are sometimes referred to as human urine stabilizer, human blood stabilizer and menstrual blood stabilizer, respectively.

  Antibacterial agents are used in order to prevent spoilage due to the absorbed liquid. As antibacterial agents, for example, “New development of bactericidal / antibacterial technology”, pages 17-80 (Toray Research Center (1994)), “Testing / evaluation methods and product design of antibacterial / antifungal agents”, pages 128-344 (NTT) S (1997)), Japanese Patent No. 2760814, Japanese Unexamined Patent Publication No. 39-179114, Japanese Unexamined Patent Publication No. 56-31425, Japanese Unexamined Patent Publication No. 57-25813, Japanese Unexamined Patent Publication No. 59-189854, JP 59-105448, JP 60-158861, JP 61-181532, JP 63-135501, JP 63-139556, JP 63-156540. JP-A-64-5546, JP-A-64-5547, JP-A-1-153748, JP-A-1-221242, JP-A-2-253. No. 47, JP-A-3-59075, JP-A-3-103254, JP-A-3-221141, JP-A-4-11948, JP-A-4-92664, JP-A-4-138165. JP-A-4-266947, JP-A-5-9344, JP-A-5-68694, JP-A-5-161671, JP-A-5-179053, JP-A-5-269164, Those introduced in JP-A-7-165981 can be appropriately selected.

  Examples thereof include alkylpyridinium salts, benzalkonium chloride, chlorhexidine gluconate, pyridione zinc, silver-based inorganic powders, and the like. Representative examples of quaternary nitrogen-based antibacterial agents include methylbenzethonium chloride, benzalkonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, and hexadecyltrimethylammonium bromide. Examples of the heterocyclic quaternary nitrogen-based antibacterial agents include dodecylpyridinium chloride, tetradecylpyridinium chloride, cetylpyridinium chloride (CPC), tetradecyl-4-ethylpyridinium chloride, and tetradecyl-4-methylpyridinium chloride.

Other preferred antibacterial agents include bis-biguanides. These are described in detail in, for example, US Pat. Nos. 2,684,924, 2,990,425, 2,830,006 and 2,863,019. It is described in. The most preferred bis-biguanide is 1,6-bis (4-chlorophenyl) diguanide hexane, known as chlorohexidine and its water-soluble salts. Particularly preferred are chlorohexidine hydrochloride, acetate and gluconate.
Several other types of antibacterial agents are also useful. For example, carbanilides, substituted phenols, metal compounds, and rare earth salts of surfactants can be exemplified. The carbanilide includes 3,4,4′-trichlorocarbanilide (TCC, triclocarban) and 3- (trifluoromethyl-4,4′-dichlorocarbanilide (IRGASAN). Mention may be made of 5-chloro-2- (2,4-dichlorophenoxy) phenol (IRGASAN DP-300), which include graphite and tin salts such as zinc chloride, zinc sulfide and tin chloride. A rare earth salt of a surfactant is disclosed in European Patent Publication No. 10819. Examples of this type of rare earth salt include a lanthanum salt of a linear C10-18 alkylbenzene sulfonate.

  Further, deodorizers, deodorizers and fragrances are used to prevent or alleviate the unpleasant odor of the absorbed liquid. Examples of the deodorant, deodorant, and fragrance are “new deodorant / deodorant and technology and prospect” (Toray Research Center (1994)), JP-A-59-105448, JP-A-60-158861, JP-A-61-118132, JP-A-1-153748, JP-A-1-221242, JP-A-1-265156, JP-A-2-41155, JP-A-2-253847, Those introduced in Japanese Laid-Open Patent Publication No. 3-103254, Japanese Laid-Open Patent Publication No. 5-269164, and Japanese Laid-Open Patent Publication No. 5-277143 can be appropriately selected. Specifically, examples of the deodorizer and deodorizer include iron complexes, tea extraction components, and activated carbon. Examples of fragrances include fragrances (citral, cinnamic aldehyde, heliotopine, camphor, bornyl acetate) wood vinegar, paradichlorobenzene, surfactants, higher alcohols, terpene compounds (limonene, pinene, camphor, borneol, eucalyptol, Eugenol).

In order to increase the water absorption performance of the water-absorbing polymer, a foaming agent and a foaming aid can be used in combination to increase the porosity and the surface area. As the foaming agent and foaming aid, for example, those introduced in “Rubber / Plastic Compounding Chemicals” (Rubber Digest, 1989, pages 259 to 267) can be appropriately selected. Examples include sodium bicarbonate, nitroso compounds, azo compounds, sulfonyl hydrazides and the like.
Furthermore, a pH adjuster or a drug that keeps the skin weakly acidic can also be used. Specific examples include natural fruit acids (malic acid, succinic acid, citric acid, tartaric acid, lactic acid, etc.), alkali metal salts, alkaline earth metal salts (phosphoric acid, carbonic acid, etc.), and the like.

  These additives are appropriately added depending on the purpose and action mechanism in each step of manufacturing the water-absorbent composite. For example, it is appropriate to add the foaming agent in the production process of the water-absorbing polymer, and it is preferable to add it before or during the polymerization process. Human urine stabilizer, human blood stabilizer, antibacterial agent, deodorant, and fragrance can be added in the manufacturing process of the water-absorbing composite and the manufacturing process of the absorbent article. Moreover, you may add these additives in components other than the water absorbing composite which comprises an absorbent article.

(4) Consolidation treatment step In order to improve the density of the water-absorbent composite of the present invention and to improve the adhesion to the fibers to the water-absorbent polymer particles, the water-absorbent composite of the present invention may be subjected to a consolidation treatment. Good. The consolidation process can be performed by appropriately adjusting conditions such as pressure, temperature, and humidity using a press machine such as a flat plate press and a roll press. The pressure during the consolidation treatment may be within a range where the water-absorbing polymer particles are not broken. When the water-absorbing polymer particles are broken, the broken particle pieces are detached from the fibers and leaked from the absorbent product, which is the final product, or the water-absorbing gel is released from the fibers and leaks or moves during swelling. Performance will be reduced.
When heating at the time of a compaction process, it can heat to the temperature below the melting point of the fiber to be used. Heating to a temperature equal to or higher than the melting point is not preferable because the fibers bind to each other to form a network and the function of the composite may be impaired. When humidifying at the time of the consolidation treatment, it is usually possible to humidify using steam. By appropriately selecting the humidifying conditions, the density of the water-absorbing composite can be improved, and the fixing property of the water-absorbing polymer particles to the fibers can be improved.

(5) Thermal fusion process When the base material used for the water-absorbent composite of the present invention is thermoplastic, it can be partially fused at a molding temperature or higher. When a thermoplastic material is provided on both sides of the water-absorbent polymer, it can be made into a composite that is resistant to rubbing stress, with the base materials fixed by partially heating and pressing, such as dotted, linear, and grid-like. it can. It is also possible to heat-fix and fix other thermoplastic materials on the non-fixed surface of the thermoplastic substrate.

(6) Recycling process It is possible to provide a recycling process for reusing mill ends, surplus materials, utility, etc. in each process.

III. Absorbent articles (configuration)
The water-absorbent composite of the present invention can be used as an absorbent material for various absorbent articles.
The structure of the absorbent article that can be produced using the water-absorbent composite of the present invention can be appropriately determined according to the function and application required for the absorbent article. A typical absorbent article is constituted by appropriately combining the water-absorbent composite of the present invention with a water-absorbing core, and fluff pulp, tissue, non-woven fabric, polyolefin sheet and the like commonly used for absorbent articles.
In particular, in so-called paper diapers and sanitary napkins, a diffusion layer of a hydrophobic fiber nonwoven fabric such as polyethylene fiber, polypropylene fiber or polyester fiber may be used in order to improve the diffusibility of body fluids during use. The water-absorbing composite may be freely mixed with fluff pulp or the like.
Moreover, you may mix the powder water-absorbing polymer etc. which are marketed. In the case of mixing, the water-absorbing polymer drop-off rate measured according to the water-absorbing polymer drop-off rate measuring method described later can be mixed and used within a range of preferably 5% or less.

FIG. 13 can be referred to for a typical configuration example of a diaper that is an absorbent article. The structure of FIG. 13 includes a tissue 22, a densified water-absorbing composite 24, a tissue 25, and a water-permeable fibrous material (for example, water) on a water-impermeable sheet (for example, water-impermeable polyethylene sheet) 21. (Transparent polyester fiber nonwoven fabric) 26 is laminated in this order. After producing a laminated body, an absorbent article can be manufactured by applying pressure to bring each layer into close contact, and thermocompression-bonding the four sides after releasing the pressure. The aqueous liquid to be absorbed is absorbed from the water permeable polyester fiber nonwoven fabric 26 side and absorbed by the water absorbent composite 24.
As shown in the structure of FIG. 13, by disposing a fibrous base material such as a tissue 25 or a water-permeable polyester fiber nonwoven fabric 26 on the upper part of the water-absorbing composite 24, the aqueous liquid can be absorbed quickly. Can do. Moreover, it is possible to make it difficult to release the absorbed aqueous liquid even when pressure is applied to the absorbent article.
Furthermore, by inserting a material imparting bulkiness such as fluff pulp into the absorbent article, the touch to the skin can be improved and the applicability to the body can be enhanced. Basis weight of the material giving bulkiness is preferably 80~250g / m ^2, and more preferably 100~220g / m ^2. The material imparting bulkiness is preferably provided between the water-absorbing composite 24 and a substrate such as the water-impermeable polyethylene sheet 21, but the water-absorbing composite 24 may be sandwiched from above and below. However, when sandwiching from above and below, it is preferable that the lower basis weight is larger.

(Thinner)
When manufacturing a thin absorbent article, it is preferable to make the water-absorbent composite of the present invention thin. Specifically, the bulk density of the water-absorbent composite of the present invention is preferably in the range of 0.20 to 1.10 g / cm ³ , and is preferably in the range of 0.20 to 0.85 g / cm ^3. It is more preferable. The density after thinning can be adjusted by conditions such as pressurization, heating, and humidification of the water-absorbent composite. The thickness after thinning is preferably 0.2 to 20 mm, more preferably 0.2 to 10 mm, and further preferably 0.2 to 5 mm.
As a method for reducing the thickness, for example, a pressure treatment method using a press machine can be mentioned. As a press machine, a flat plate press machine, a roll press machine, etc. can be used. The pressure is selected so that the water-absorbing polymer is not broken. If the water-absorbing polymer is broken, it will be detached from the fiber and leaked from the absorbent article, or the water-absorbing gel may be detached from the fiber and leaked or moved during swelling, thereby reducing the performance of the absorbent article.

In addition to the pressure treatment, the water-absorbent composite can be subjected to heat treatment and humidification treatment as necessary. The heating temperature in the case of heating can be selected below the melting point of the fiber to be used. When heated at a temperature equal to or higher than the melting point, the fibers are bound together to form a network, resulting in a result different from the object of the present invention. In the case of humidification, a method of spraying water on the water-absorbing composite, a method of supplying it as steam, or the like can be employed. The humidification amount can be appropriately selected depending on the content of the water-absorbing polymer particles and the like, but is usually 500 g or less per 1 m ² , preferably 300 g or less per 1 m ² , more preferably 100 g or less per 1 m ² . If the amount of humidification is too much, the water-absorbing polymer particles are softened and crushed, the fibers are bound to each other to form a network, and the result of the present invention is different from that of the present invention. Is not economical because it must be distilled off. When supplying with steam, the steam pressure should be lower than 10 MPa, and preferably lower than 1 MPa. Steam feed rate, the content of the water-absorbing polymer particles, can be appropriately selected by moistening time, etc., normally less than 1 m ² per 300 kg / hr, preferably 1 m ² per 100 kg / hr or less, more preferably 1 m ² 50 kg / hr or less per unit. The treatment time is usually 1 hour or less, preferably 30 minutes or less, more preferably 20 minutes or less. If the amount of supplied steam is too large, the water-absorbing polymer absorbs moisture and softens and collapses, or fibers are bound together to form a network, resulting in a result different from the purpose of the present invention. This is not economical because a large amount of water must be distilled off later. Further, the absorbent article can be humidified by adding water by spraying or the like.

(Use)
The water-absorbent composites of the present invention include “high water-absorbing resin technology and market” (Technomart, 1981) “high water-absorbing polymer” (Fumiyoshi Masuda, Kyoritsu Shuppan, 1987), “Production of Functional Polymer Gels” And applications "(Irie Masahiro, CMC, 1987)," Development Trends of Superabsorbent Resins and Their Application Development "(Eizo Omori, Techno Forum, 1987)," Development of New Applications for Superabsorbent Polymers "(CMC 1993) Industrial Materials (Vol.42 No.4, 1994) “Latest Trends in Polymer Gels” (Michihiro Shibayama, Satoshi Sugawara, CMC, 2004), “Superabsorbent Polymers Science and Technology” (FL Bucholz & NA Peppas, American Chemical Society, 1993), “Modern Superabsorbent Polymer Technology” (FL Bucholz & AT Graham, Wiley-VCH, 1998). For example, children's disposable diapers, adult disposable diapers, incontinence pads, sanitary materials such as sanitary products, absorbent sheets such as waste water, retaining sheets, cold insulation, water-stopping materials, sealing materials, industrial materials such as anti-condensation agents for construction, Soil water retention agent, water retention sheet for seedlings, freshness retention agent such as vegetables, agricultural and horticultural materials such as water retention agent, low friction material, mud additive / lubricant / waste mud treatment agent, void filler, fire extinguishing agent / fireproof material, etc. Can be suitably used.

Examples of water-absorbing articles that can be produced preferably using the water-absorbing composite of the present invention include, for example, Japanese Utility Model Laid-Open No. 5-5117, Japanese Utility Model Laid-Open No. 5-5119, Japanese Patent Application Laid-Open No. 5-31134, Japanese Patent Application Laid-Open No. 5-31134. JP-A-5-31138, JP-A-5-38350, JP-A-5-49659, JP-A-5-68693, JP-A-5-68694, JP-A-5-76564, JP-A-5-56564. No. 765666, JP-A-5-76567, JP-A-5-92023, JP-A-5-103813, JP-A-5-111509, JP-A-5-33720, JP-A-5-123357. JP-A-5-123360, JP-A-5-137552, JP-A-5-154175, JP-A-5-48924, JP-A-5-16 No. 661, JP-A-5-176953, JP-A-5-53627, JP-A-5-56119, JP-A-5-56120, JP-A-5-200064, JP-A-5-208033 No. 5-62227, JP-A-5-228172, JP-A-5-228173, JP-A-5-230251, JP-A-5-230252, JP-A-5-237148, JP-A-5-237149, JP-A-5-237150, JP-A-5-239278, JP-A-5-285172, JP-A-5-82421, JP-A-5-317358, JP-A-5-37358 JP-A-5-317359, JP-A-6-910, JP-A-6-5614, JP-A-6-30964, JP-A-6-3. No. 998, JP-A-6-38999, JP-A-6-11724, JP-A-6-70953, JP-A-6-70955, JP-A-6-70956, JP-A-6-70958. JP-A-6-78949, JP-A-6-98909, JP-A-6-114084, JP-A-6-121810, JP-A-6-125935, JP-A-6-126871 JP-A-6-133999, JP-A-6-142134, JP-A-6-142135, JP-A-6-158501, JP-A-6-166111, JP-A-6-166937, JP-A-6-166937 JP-A-6-169948, JP-A-6-169949, JP-A-6-178788, JP-A-6-178785, JP-A-6 JP-A No.-200465, JP-A-6-205806, JP-A-6-218008, JP-A-6-218809, JP-A-6-233793, JP-A-6-237957, JP-A-6-237957 JP-A-6-245951, JP-A-6-255006, JP-A-6-261924, JP-A-6-277252, JP-A-6-287886, JP-A-6-296663. JP-A-6-75445, JP-A-6-304202, JP-A-6-304203, JP-A-6-315502, JP-A-6-316334, JP-A-6-327712, JP-A-7-1635, JP-A-7-16259, JP-A-7-24003, JP-A-7-24007 JP-A-7-24008, JP-A-7-40494, JP-A-7-67914, JP-A-7-100187, JP-A-7-117125, JP-A-7-1119012, Japanese Unexamined Patent Publication Nos. 7-27540, 7-136211, 7-171179, 7-178133, 7-179637, 7-184957, 7 JP-A-189197, JP-A-7-213552, JP-A-7-231913, JP-A-7-246216, JP-A-7-255576, JP-A-7-255579, JP-A-7-265343. 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JP-A-298455, JP-A-2004-298467, JP-A-2004-298492, JP-A-2004-298504, JP-A-2004-305471, JP-A-2004-305763, JP-A-2004-316601. JP, 2004-324038, JP 2004-329302, JP 2004-329510, JP 2004-329511, JP 2004-337314, JP 2004-337384. , JP2004-3373 No. 85, JP-A No. 2004-337386, JP-A No. 2004-337387, JP-A No. 2004-337388, JP-A-8-500494, JP-A-8-500502, JP-A-8 No. -500544, No. 8-501006, No. 8


No. 503638, No. 8-504112, No. 8-504136, No. 8-504355, No. 8-504637, No. 8-504640, No. 8-507232, No. 8-508425, No. 8-508426, No. 8-508527, No. 8-508862, No. 8- No. 510149, No. 8-510150, No. 8-510664, No. 8-510665, No. 8-510667, No. 8-510668, No. No. 8-510669, No. 8-510940, No. 8-511706, No. 8-511708, No. 8-511724, No. 9-50 No. 032, No. 9-500558, No. 9-500559, No. 9-501335, No. 9-501847, No. 9-502635, No. No. 9-502892, No. 9-502897, No. 9-503934, No. 9-504207, No. 9-504488, No. 9-506280 No. 9, Special Table No. 9-506535, Special Table No. 9-506656, Special Table No. 9-506806, Special Table No. 9-507405, Special Table No. 9-507408, Special Table No. 9-507409, No. 9-507411, No. 9-507413, No. 9-507768, No. 9-507772, No. 9-50854 No. 9, Special Table No. 9-508548, Special Table No. 9-509343, Special Table No. 9-509456, Special Table No. 9-509592, No. 9-509901, Special Table No. 9-510511, No. 9-510634, No. 9-510635, No. 9-511664, No. 9-511929, No. 9-512454 JP, 10-502005, JP 10-502006, JP 10-502281, JP 10-502550, JP 10-502843, JP No. 10-502954, No. 10-503400, No. 10-503683, No. 10-503687, No. 10-503686, No. 1 No. 0-503953, No. 10-50395 / S, No. 10-504266, No. 10-504741, No. 10-505262, No. 10-506302 No.10, No.10-507944, No.10-508221, No.10-508771, No.10-509340, No.10-509361, No.10-509361 No. 10-509365, No. 10-511277, No. 10-511279, No. 10-511869, No. 10-511870, No. 10-512033 Japanese Patent Publication No. 10-512472, No. 10-512475, No. 10-512790, No. 10-513380, No. No. 11-500027, No. 11-500328, No. 11-500640, No. 11-500988, No. 11-501857, No. 11-501872 No. 11/502126, No. 11-502427, No. 11-503052, No. 11-504252, No. 11-504546, No. 11-504546, No. 11-504841, No. 11-505568, No. 11-506039, No. 11-506503, No. 11-506803, No. 11-506810 No. 11-507955, No. 11-506958, No. 11-506998, No. 11-507137 No. 11-507287, No. 11-507613, No. 11-508002, No. 11-509117, No. 11-509127, No. 11 No. -509796, No. 11-510071, No. 11-510083, No. 11-510088, No. 11-511007, No. 11-511671, No. 11-511671, No. 11-512001, No. 11-512328, No. 11-512331, No. 11-513067, No. 11-513295, No. 11- No. 513916, No. 11-513927, No. 11-514253, No. 11-514895, 2000-5000. No. 7, No. 2000-500987, No. 2000-500993, No. 2000-501962, No. 2000-502268, No. 2000-502649, No. 2000-502921 Gazette, special table 2000-504982, gazette 2000-504986, special table 2000-505700, special table 2000-505713, special table 2000-506036, special table 2000-506047, Special Table 2000-506565, Special Table 2000-507126, Special Table 2000-508551, Special Table 2000-508930, Special Table 2000-509109, Special Table 2000-510027, Special Table No. 2000-510349, Special Table 200 No. 0-510370, Special Table 2000-510375, Special Table 2000-512200, Special Table 2000-551272, Special Table 2000-512888, Special Table 2000-513645, Special Table 2000- No. 513954, No. 2000-513960, No. 2001-500025, No. 2001-500402, No. 2001-5000002, No. 2001-502210, No. 2001-502939. Gazette, special table 2001-505453, special table 2001-505803, special table 2001-506153, special table 2001-506532, special table 2001-507588, special table 2001-507589, Special Table 2001-507602 No. 2001-508329, No. 2001-508345, No. 2001-508482, No. 2001-508487, No. 2001-513364, No. 2001-514338, No. 2001-514930, No. 2001-51598, No. 2001-517488, No. 2001-518355, No. 2001-518418, No. 2001-518419, No. 2001. -520082, JP-T 2001-522543, JP-T 2001-523990, JP-T 2001-526917, JP-T 2001-526936, JP-T 2001-526937, JP-T 2002-502717 No., Special Table 2002-5 No. 3979, No. 2002-504384, No. 2002-506136, No. 2002-508038, No. 2002-508039, No. 2002-509203, No. 2002-509461. Gazette, special table 2002-509737 gazette, special table 2002-50976 gazette, special table 2002-513737 gazette, special table 2002-514912 gazette, special table 2002-515295 gazette, special table 2002-515296 gazette, JP 2002-515776, JP 2002-515826, JP 2002-515835, JP 2002-515926, JP 2002-516802, JP 2002-518095, JP 2002-518096, Special Table No. 2002-518097, No. 2002-521092, No. 2002-522117, No. 2002-523140, No. 2002-523141, No. 2002-523142, No. 2002 No. 524171, No. 2002-526297, No. 2002-527198, No. 2002-528173, No. 2002-528229, No. 2002-528232, No. 2002-530130. Gazette, special table 2002-530152, special table 2002-530153, special table 2002-530215, special table 2002-53123, special table 2002-532147, special table 2002-532194, Special Table 2002-53219 Gazette, special table 2002-532196, special table 2002-532197, special table 2002-532350, special table 2002-533243, special table 2002-532040, special table 2002-536499 No. 2002-538849, No. 2002-539851, No. 2002-540977, No. 2002-541918, No. 2002-541979, No. 2002-541983, Table 2002-541982, Special Table 2002-543922, Special 2002-543923, Special 2002-543924, Special 2003-500115, Special 2003-500166, Special 2003 -501209, Special Table 200 No.-501211, No. 2003-501559, No. 2003-501558, No. 2003-502190, No. 2003-503106, No. 2003-503108, No. 2003-503156. Gazette, special table 2003-503783, special table 2003-508095, special table 2003-510132, special table 2003-510165, special table 2003-510206, special table 2003-511534 No. 2003-511578, No. 2003-512193, No. 2003-513159, No. 2003-514134, No. 2003-514619, No. 2003-515390, Table 2003-515467 No. 2003-516807, No. 2003-516955, No. 2003-51584, No. 2003-517950, No. 2003-518525, No. 2003-518567, No. Table 2003-518957, Special Table 2003-519297, Special Table 2003-519535, Special Table 2003-520627, Special 2003-521266, Special 2003-521339, Special 2003 No. 521955, No. 2003-521969, No. 2003-522204, No. 2003-522600, No. 2003-522597, No. 2003-522598, No. 2003-522599. Gazette, special table 2003-52 No. 470, No. 2003-524661, No. 2003-524687, No. 2003-526390, No. 2003-526406, No. 2003-526466, No. 2003-526535. Gazette, special table 2003-527147, special table 2003-527152, special table 2003-527153, special table 2003-527928, special table 2003-527929, special table 2003-528164, Special table 2003-528649 gazette, Special table 2003-528650 gazette, Special table 2003-528655 gazette, Special table 2003-5281992 gazette, Special table 2003-529399 gazette, Special table 2003-529400 gazette, Special table 2003-529398 Publication, Special Table No. 003-529681, No. 2003-530243, No. 2003-530904, No. 2003-530906, No. 2003-530963, No. 2003-53644, and No. 2003. No. 532554, Special Table 20


No. 03-532754, No. 2003-533236, No. 2003-533247, No. 2003-533282, No. 2003-533598, No. 2003-534041, No. 2003. No. 534042, No. 2003-534401, No. 2003-534829, No. 2003-535627, No. 2003-535648, No. 2003-535650, No. 2003-535994. Gazette, special table 2004-500169, special table 2004-500491, gazette 2004-500493, special table 2004-500908, special table 2004-500932, gazette 2004-504106, Special table 2004-505670 No. 2004-506820, No. 2004-508426, No. 2004-509657, No. 2004-510463, No. 2004-511648, No. 2004-512963, Special table 2004-512862 gazette, Special table 2004-513672 gazette, Special table 2004-513680 gazette, Special table 2004-515292 gazette, Special table 2004-515314 gazette, Special table 2004-516175 gazette, Special table No. 2004-516561, No. 2004-518835, No. 2004-518487, No. 2004-518829, No. 2004-520856, No. 2004-520869, No. 2004 No. 520961, Special Table 2004 No. 22486, No. 2004-523598, No. 2004-524867, No. 2004-524929, No. 2004-525672, No. 2004-528898, No. 2004-528915 Gazette, special table 2004-528938, special table 2004-530008, special table 2004-530061, special table 2004-530486, special table 2004-530487, special table 2004-530802, Special table 2004-531287, Special table 2004-53336, Special table 2004-53348, Special table 2004-532657, Special table 2004-532713, Special table 2004-532758, Special table 2004-532901, Special No. 2004-532939, No. 2004-533886, No. 2004-533946, No. 2004-534089, No. 2004-53496, No. 2004-536239, No. 6 No. 1702, No. 6-14946, No. 6-14947, No. 6-14948, No. 6-26963, No. 6-38814, No. 6-21464. No. 6, No. 6-23287, No. 6-41541, No. 6-87874, No. 7-12367, No. 7-12371, No. 7-16508 No. 7-7942, No. 7-7943, No. 7-28889, No. 7-28891 No. 7-28892, No. 7-30512, No. 7-13702, No. 7-38867, No. 7-44939, No. 7-51141, Japanese Patent Publication No. 7-59243, Japanese Patent Publication No. 7-67475, Japanese Patent Publication No. 7-91964, Japanese Patent Publication No. 7-91765, Japanese Utility Model Publication No. 7-42422, Japanese Patent Publication No. 7-93937, Japanese Patent Publication No. 7-114786, No. 8-4019, No. 8-22355, (hereinafter referred to as Japanese Patent No. 2514294, No. 2514295, No. 2536934, No. 2536936) , Japanese Patent No. 2511442, Japanese Patent No. 2541523, Japanese Patent No. 2545005, Japanese Patent No. 2549090, Japanese Patent No. 2521954, Japanese Patent No. 2571282, Japanese Patent No. 2577094, Japanese Patent No. 2577095, Japanese Patent No. 2523701, Japanese Patent No. 2583320, Japanese Patent No. 2589383, Japanese Patent No. 2590058, Japanese Patent No. 2590058 Japanese Patent No. 2528661, Japanese Patent No. 2528982, Japanese Patent No. 2602861, Japanese Patent No. 2619595, Japanese Patent No. 2623429, Japanese Patent No. 2633837, Japanese Patent No. 2635139, Japanese Patent No. 2635599, Japanese Patent No. 2545279 Gazette, Japanese Patent No. 2647857, Japanese Patent No. 2647858, Japanese Patent No. 2672866, Japanese Patent No. 2676201, Japanese Patent No. 2680378, Japanese Patent No. 2559049, Japanese Patent No. 2698683 No. 2,702,852, No. 2,716,729, No. 2,726,441, No. 2,566,364, No. 2,741,816, No. 2,742,821, No. 2,569,646, No. 2,769,196, Japanese Patent No. 2777178, Japanese Patent No. 2786624, Japanese Patent No. 2778416, Japanese Patent No. 2804270, Japanese Patent No. 2800841, Japanese Patent No. 2801618, Japanese Patent No. 2790875, Japanese Patent No. 2787460, Japanese Patent No. 2787460 Japanese Patent No. 2809480, Japanese Patent No. 2809491, Japanese Patent No. 2810290, Japanese Patent No. 2810501, Japanese Patent No. 2810772, Japanese Patent No. 2810780, Japanese Patent No. 2582932, Japanese Patent No. 281234 No. 2, Patent No. 2818592, Patent No. 2820850, Patent No. 2823402, Patent No. 2585130, Patent No. 2826185, Patent No. 2831663, Patent No. 2831677, Patent No. 2834312 Patent No. 2834898, Patent No. 2837419, Patent No. 2843074, Patent No. 2843116, Patent No. 2843123, Patent No. 2846448, Patent No. 2849179, Patent No. 2849204, Patent Japanese Patent No. 2850982, Japanese Patent No. 2851642, Japanese Patent No. 2585372, Japanese Patent No. 2858660, Japanese Patent No. 2859725, Japanese Patent No. 2859735, Japanese Patent No. 2859743, Japanese Patent No. 259 No. 175, Japanese Patent No. 2868946, Japanese Patent No. 2872729, Japanese Patent No. 2872851, Japanese Patent No. 2875504, Japanese Patent No. 2876215, Japanese Patent No. 2876216, Japanese Patent No. 2878700, No. 2880189 Gazette, Japanese Patent No. 2880241, Japanese Patent No. 2888603, Japanese Patent No. 2889347, Japanese Patent No. 2889348, Japanese Patent No. 2828943, Japanese Patent No. 2895094, Japanese Patent No. 2899273, Japanese Patent No. 2990143, Japanese Patent No. 2902121, Japanese Patent No. 2907916, Japanese Patent No. 290792, Japanese Patent No. 2908877, Japanese Patent No. 2909877, Japanese Patent No. 2909882, Japanese Patent No. 2928665, Patent No. 2 No. 941290, Japanese Patent No. 2942069, Japanese Patent No. 2947880, Japanese Patent No. 2952175, Japanese Patent No. 295617, Japanese Patent No. 2955624, Japanese Patent No. 2955222, Japanese Patent No. 2955223, Japanese Patent No. 2963289 Gazette, Japanese Patent No. 2968006, Japanese Patent No. 2971887, Japanese Patent No. 2974693, Japanese Patent No. 2997424, Japanese Patent No. 2974771, Japanese Patent No. 2974866, Japanese Patent No. 2974970, Japanese Patent No. 2983297, Japanese Patent No. 2996403, Japanese Patent No. 2999664, Japanese Patent No. 2998986, Japanese Patent No. 2999886, Japanese Patent No. 2602584, Japanese Patent No. 3012411, Japanese Patent No. 3012475, Japanese Patent No. 3014400, Japanese Patent No. 3015070, Japanese Patent No. 3015091, Japanese Patent No. 3016978, Japanese Patent No. 3017340, Japanese Patent No. 30212227, Japanese Patent No. 3029853, Japanese Patent No. 3032212, Japanese Patent No. 3032304 Gazette, Japanese Patent No. 3032308, Japanese Patent No. 3058533, Japanese Patent No. 3058572, Japanese Patent No. 30614485, Japanese Patent No. 30615507, Japanese Patent No. 3065756, Japanese Patent No. 3065883, Japanese Patent No. 3081747 , Japanese Patent No. 3083662, Japanese Patent No. 3086141, Japanese Patent No. 3087711, Japanese Patent No. 3091249, Japanese Patent No. 3091361, Japanese Patent No. 3091365, Japanese Patent No. 3091397 , Japanese Patent No. 3093413, Japanese Patent No. 3096208, Japanese Patent No. 3098034, Japanese Patent No. 3098039, Japanese Patent No. 3101010, Japanese Patent No. 3105263, Japanese Patent No. 3107234, Japanese Patent No. 3107821, Patent Japanese Patent No. 3119372, Japanese Patent No. 3119876, Japanese Patent No. 3121083, Japanese Patent No. 2606778, Japanese Patent No. 312760, Japanese Patent No. 3130447, Japanese Patent No. 3130454, Japanese Patent No. 3130453, Japanese Patent No. 3131062 Gazette, Japanese Patent No. 3133932, Japanese Patent No. 3144533, Japanese Patent No. 3145370, Japanese Patent No. 3145371, Japanese Patent No. 3149158, Japanese Patent No. 3149191, Japanese Patent No. 3155351 Gazette, Japanese Patent No. 3155368, Japanese Patent No. 3156251, Japanese Patent No. 3157580, Japanese Patent No. 3157581, Japanese Patent No. 3161638, Japanese Patent No. 3161695, Japanese Patent No. 3167688, Japanese Patent No. 3169341 Patent No. 3175107, Patent No. 3175551, Patent No. 3175934, Patent No. 3181626, Patent No. 3182040, Patent No. 3183363, Patent No. 3183365, Patent No. 31833838, Patent Japanese Patent No. 3187110, Japanese Patent No. 3190565, Japanese Patent No. 3190757, Japanese Patent No. 3305341, Japanese Patent No. 3305360, Japanese Patent No. 3205690, Japanese Patent No. 3209352, Japanese Patent No. 3215 No. 62, Japanese Patent No. 3217214, Japanese Patent No. 3217289, Japanese Patent No. 3217317, Japanese Patent No. 3219247, Japanese Patent No. 3220190, Japanese Patent No. 3322494, Japanese Patent No. 3322833, Japanese Patent No. 3230582 Gazette, Japanese Patent No. 3321784, Japanese Patent No. 3238404, Japanese Patent No. 3242586, Japanese Patent No. 3249158, Japanese Patent No. 3253620, Japanese Patent No. 3254050, Japanese Patent No. 3255919, Japanese Patent No. 3258909, Japanese Patent No. 3260767, Japanese Patent No. 3260863, Japanese Patent No. 3265308, Japanese Patent No. 3271909, Japanese Patent No. 3272721, Japanese Patent No. 3279582, Japanese Patent No. 3288717, Patent No. 3 No. 88919, Japanese Patent No. 3288920, Japanese Patent No. 3291018, Japanese Patent No. 3299964, Japanese Patent No. 3302973, Japanese Patent No. 3305208, Japanese Patent No. 3307951, Japanese Patent No. 3308486, Japanese Patent No. 3308540 Gazette, Japanese Patent No. 3310894, Japanese Patent No. 3316197, Japanese Patent No. 3317836, Japanese Patent No. 3320723, Japanese Patent No. 3323092, Japanese Patent No. 3327939, Japanese Patent No. 3330956, Japanese Patent No. 3331075, Japanese Patent No. 3335627, Japanese Patent No. 3343189, Japanese Patent No. 334501, Japanese Patent No. 3345012, Japanese Patent No. 3348871, Japanese Patent No. 3351663, Japanese Patent No. 3352689, Patent Japanese Patent No. 3354135, Japanese Patent No. 3356357, Japanese Patent No. 3356420, Japanese Patent No. 3356421, Japanese Patent No. 3357518, Japanese Patent No. 336253, Japanese Patent No. 3363312, Japanese Patent No. 3369177, Japanese Patent No. 3369184 issue


Gazette, Japanese Patent No. 3373211, Japanese Patent No. 3375635, Japanese Patent No. 3380568, Japanese Patent No. 3382742, Japanese Patent No. 3383497, Japanese Patent No. 3385035, Japanese Patent No. 3385183, Japanese Patent No. 3385190, Japanese Patent No. 3386074, Japanese Patent No. 3386721, Japanese Patent No. 3390723, Japanese Patent No. 3392421, Japanese Patent No. 2607820, Japanese Patent No. 3399668, Japanese Patent No. 34006166, Japanese Patent No. 3403120, Japanese Patent No. 3403120 Japanese Patent No. 3407906, Japanese Patent No. 3407910, Japanese Patent No. 340878, Japanese Patent No. 3408086, Japanese Patent No. 3411912, Japanese Patent No. 3414494, Japanese Patent No. 3414741, Japanese Patent No. 34168 No. 9, Japanese Patent No. 3417572, Japanese Patent No. 3417579, Japanese Patent No. 3420481, Japanese Patent No. 3420774, Japanese Patent No. 3421045, Japanese Patent No. 3423810, Japanese Patent No. 3425348, Japanese Patent No. 3429688 Gazette, Japanese Patent No. 3431167, Japanese Patent No. 3431169, Japanese Patent No. 3434296, Japanese Patent No. 3434823, Japanese Patent No. 3437769, Japanese Patent No. 3437800, Japanese Patent No. 34440091, Japanese Patent No. 3442837, Japanese Patent No. 3442929, Japanese Patent No. 3442943, Japanese Patent No. 3447951, Japanese Patent No. 3449523, Japanese Patent No. 3453301, Japanese Patent No. 3457003, Japanese Patent No. 3457333, Patent No. 34 Patent No. 7417, Japanese Patent No. 3457481, Japanese Patent No. 3459257, Japanese Patent No. 3462240, Japanese Patent No. 3462302, Japanese Patent No. 3462303, Japanese Patent No. 3464587, Japanese Patent No. 3466184, Japanese Patent No. 3467376 Gazette, Japanese Patent No. 3467428, Japanese Patent No. 3467429, Japanese Patent No. 3468769, Japanese Patent No. 3469290, Japanese Patent No. 3469300, Japanese Patent No. 3469385, Japanese Patent No. 3474193, Japanese Patent No. 3474194, Japanese Patent No. 3474662, Japanese Patent No. 3447477, Japanese Patent No. 3474701, Japanese Patent No. 3478826, Japanese Patent No. 3479114, Japanese Patent No. 3481635, Japanese Patent No. 3484037, Patent No. Japanese Patent No. 3488269, Japanese Patent No. 3490102, Japanese Patent No. 3490291, Japanese Patent No. 3490477, Japanese Patent No. 3490608, Japanese Patent No. 3495229, Japanese Patent No. 3497701, Japanese Patent No. 3498035, Japanese Patent No. 3506700, Japanese Patent No. 3506708, Japanese Patent No. 3507710, Japanese Patent No. 3510089, Japanese Patent No. 3511398, Japanese Patent No. 3511435, Japanese Patent No. 3511461, Japanese Patent No. 3515834, Japanese Patent No. 3515910, Japanese Patent No. 3515910 No. 3515932, Japanese Patent No. 3519025, Japanese Patent No. 3519082, Japanese Patent No. 3522594, Japanese Patent No. 3522640, Japanese Patent No. 3523867, Japanese Patent No. 3524026, Japanese Patent No. 3524026 Japanese Patent No. 527031, Japanese Patent No. 3527457, Japanese Patent No. 3532195, Japanese Patent No. 3532196, Japanese Patent No. 3532302, Japanese Patent No. 3532575, Japanese Patent No. 3533359, Japanese Patent No. 3534754, Japanese Patent No. 3534757 Gazette, Japanese Patent No. 3534768, Japanese Patent No. 3534906, Japanese Patent No. 3535958, Japanese Patent No. 3537610, Japanese Patent No. 354050, Japanese Patent No. 3540053, Japanese Patent No. 3541144, Japanese Patent No. 35404041, Patent No. v3544091, Patent No. 3545064, Patent No. 3548027, Patent No. 3552997, Patent No. 3553435, Patent No. 3554344, Patent No. 3555764, Patent Japanese Patent No. 3556304, Japanese Patent No. 3556362, Japanese Patent No. 3556582, Japanese Patent No. 3558828, Japanese Patent No. 3559031, Japanese Patent No. 3560514, Japanese Patent No. 3563688, Japanese Patent No. 3564157, Japanese Patent No. 3566012 Gazette, 3566461, patent 3666709, patent 3568146, patent 3568593, patent 3568646, patent 3568668, patent 3573737, patent 3576034, patent Japanese Patent No. 3576087, Japanese Patent No. 3579034, Japanese Patent No. 3580922, Japanese Patent No. 3583151, Japanese Patent No. 3583370, Japanese Patent No. 3587777, Japanese Patent No. 3587831, Japanese Patent No. 3587831 Japanese Patent No. 3590971, Japanese Patent No. 3591542, Japanese Patent No. 3591545, Japanese Patent No. 3591574, Japanese Patent No. 3592606, Japanese Patent No. 3594095, Japanese Patent No. 3594096, Japanese Patent No. 3594099, Japanese Patent No. 3594103 No. 3,594,860, JP-A-3-287870, JP-A-4-218502, JP-A-62-222810, JP-A-62-222811, JP-A-62-253309. JP, 62-62829, JP 62-97978, JP 62-9779, JP 62-133183, JP 62-133184, JP JP-A-62-225507, JP-A-63-1638, JP-A-63-3505 No. 63-57617, No. 63-260906, No. 63-291909, No. 63-291908, No. 1-121308, No. 1-No. No. 121307, JP-A-1-121306, JP-A-63-43930, JP-A-2-34607, JP-A-1-318022, JP-A-4-372636, JP-A-3-21385. JP-A-4-133728, JP-A-4-90739, JP-A-62-286725, JP-A-63-267370, JP-A-63-10667, JP-A-63. JP-A-186712, JP-A-63-295251, JP-A-63-270801, JP-A-63-294716, JP-A-64-646. 2 JP, Hei 1-231940, JP-A No. 1-243927, JP-A No. 2-30522, JP-can be exemplified those described in JP-A-2-153731 Patent Publication.

Among water-absorbing articles that can be produced preferably using the water-absorbing composite of the present invention, as diapers, for example, JP-A-10-5277, JP-A-10-5278, JP-A-10-28701 are disclosed. JP-A-10-028703, JP-A-10-28704, JP-A-10-33591, JP-A-10-52454, JP-A-10-52455, JP-A-10-57413, JP-A-10-57414, JP-A-10-57415, JP-A-10-80446, JP-A-10-85257, JP-A-10-95481, JP-A-10-118120, JP-A-10-118120 10-127694, JP-A-10-137287, JP-A-10-137288, JP-A-10-137 No. 89, JP-A-10-137292, JP-A-10-165437, JP-A-10-165439, JP-A-10-179633, JP-A-10-179634, JP-A-10-201790. JP, 10-2111236, JP 10-298801, JP 10-314220, JP 11-19129, JP 11-56904, JP 11-137601, JP-A-11-137602, JP-A-11-140705, JP-A-11-140706, JP-A-11-146895, JP-A-11-155905, JP-A-11-155906, JP-A-11-155906 JP-A-11-188055, JP-A-11-188058, JP-A-11-18 No. 059, JP-A-11-188060, JP-A-11-188061, JP-A-11-188062, JP-A-11-235357, JP-A-11-244326, JP-A-11-244331. JP-A-11-253488, JP-A-11-253589, JP-A-11-262503, JP-A-11-285510, JP-A-11-285511, JP-A-11-313852, JP 2000-79141 A, JP 2000-083999 A, JP 2000-102561, JP 2000-107226, JP 2000-140006, JP 2000-140010, JP JP 2000-140018, JP-A 2000-152958 JP, 2000-157570, JP, 2000-166969, JP, 2000-279448, JP, 2000-288020, JP, 2000-288021, JP, 2000-354760, JP, 2001. -46430, JP-A-2001-46431, JP-A-2001-57993, JP-A-2001-104372, JP-A-2001-145664, JP-A-2001-155762 and JP-A-2001-198157. No. 1, JP-A-2001-252302, JP-A-2001-258931, JP-A-2001-258933, JP-A-2001-293029, JP-A-2001-333931, JP-A-2001-346830 JP 2002-45392 A JP 2002-45401 A, JP 2002-65733 A, JP 2002-65734 A, JP 2002-78734 A, JP 2002-111040 A, JP 2002-2001113 A, JP JP 2002-200116, JP 2002-209938, JP 2002-209939, JP 2002-209940, JP 2002-224160, JP 2002-263135, JP 2002-2002. Nos. 291797, 2002-360629, 2003-61997, 2003-70834, 2003-79664, 2003-79666, 2003-93440 Gazette, JP2003-93444, JP 003-102778, JP-A 2003-10279, JP-A 2003-102780, JP-A 2003-144486, JP-A 2003-144492, JP-A 2003-164477, JP-A 2003- No. 235892, JP-A 2003-299694, JP-A 2003-310663, JP-A 2003-319972, JP-A 2004-344, JP-A 2004-481, JP-A 2004-8301 JP, 2004-16441, JP 2004-49707, JP 2004-49709, JP 2004-49763, JP 2004-49764, JP 2004-49765, JP 2004-57412 A, JP 2004-5741 A No. 3, JP-A No. 2004-57414, JP-A No. 2004-57415, JP-A No. 2004-57416, JP-A No. 2004-73885, JP-A No. 2004-81365, JP-A No. 2004-81617. JP, 2004-81618, JP, 2004-105696, JP, 2004-105697, JP, 2004-105698, JP, 2004-105704, JP, 2004-141270, JP-A-2004-141499, JP-A-2004-141532, JP-A-5-3889, JP-A-5-3891, JP-A-5-7221, JP-A-5-9525, JP-A-5-9525 JP-A-5-9531, JP-A-5-42181, JP-A-5-15933, JP-A-5-15933. No. 15934, JP-A-5-15935, JP-A-5-64651, JP-A-5-20724, JP-A-5-21934, JP-A-5-21935, JP-A-5-76565. Japanese Utility Model Laid-Open No. 5-35121, Japanese Utility Model Laid-Open No. 5-35126, Japanese Patent Application Laid-Open No. 5-123355, Japanese Patent Application Laid-Open No. 5-123361, Japanese Utility Model Laid-Open No. 5-37219, Japanese Utility Model Laid-Open No. 5-37224, JP-A-5-137744, JP-A-5-137754, JP-A-5-146467, JP-A-5-44115, JP-A-5-44116, JP-A-5-51327, JP-A-5-135327 JP-A-5-184622, JP-A-5-184623, JP-A-5-192366, JP-A-5-192368, JP-A-5-5 127, JP-A-5-200059, JP-A-5-200068, JP-A-5-200069, JP-A-5-214195, JP-A-5-222107, JP-A-5-65321 JP, 5-65322, JP-A-5-228178, JP-A-5-245168, JP-A-5-247708, JP-A-5-261126, JP-A-5-277149, JP-A-5-279742, JP-A-5-78216, JP-A-5-285008, JP-A-5-285170, JP-A-5-285171, JP-A-5-285174, JP JP-A-5-293134, JP-A-5-293138, JP-A-5-305109, JP-A-5-309111 JP-A-5-86320, JP-A-5-317356, JP-A-5-317357, JP-A-5-317361, JP-A-5-317362, JP-A-5-317363, Japanese Utility Model Laid-Open Nos. 5-317364, 5-321110, 5-91639, 5-91642, 5-91643, 5-93427, and Utility 5 -93428, JP-A-6-204, JP-A-6-14949, JP-A-6-16834, JP-A-6-5615, JP-A-6-7717, JP-A-6-7725 No. 6, JP-A-6-30962, JP-A-6-30963, JP-A-6-9616, JP-A-6-9620, JP-A-6-9621. No. 6-9625, JP-A-6-39000, JP-A-6-11722, JP-A-6-11723, JP-A-6-11725, JP-A-6-57501, JP-A-6-57502, JP-A-6-16404, JP-A-6-63072, JP-A-6-63073, JP-A-6-63074, JP-A-6-63076, JP-A-6-63077, JP-A-6-17724, JP-A-6-17726, JP-A-6-78951, JP-A-6-78954, JP-A-6-21622, JP-A-6-21622, No. 21623, No. 6-21624, No. 6-21626, No. 6-31723, No. 6-31725, No. 6-3461. No. 6-34618, JP-A-6-192911, JP-A-6-197925, JP-A-6-200114, JP-A-6-52818, JP-A-6-209968. JP-A-6-210166, JP-A-6-218007, JP-A-6-228443, JP-A-6-228864, JP-A-6-58933, JP-A-6-61227, JP-A-6-254116, JP-A-6-254119, JP-A-6-257017, JP-A-6-277250, JP-A-6-277251, JP-A-6-280171, JP-A-6 -285113, JP-A-6-296638, JP-A-6-296646, JP-A-6-75441, JP-A-6 JP-A-75442, JP-A-6-75444, JP-A-6-304199, JP-A-6-304200, JP-A-6-304201, JP-A-6-77719, JP-A-6-77722. No. 6-81519, JP-A-6-327713, JP-A-6-327714, JP-A-6-330443, JP-A-7-329, JP-A-7-24005. No. 7-7514, No. 7-7620, No. 7-47097, No. 7-13322, No. 7-13323, No. 7-80023, Special Japanese Utility Model Laid-Open No. 7-80024, Japanese Patent Application Laid-Open No. 7-88133, Japanese Patent Application Laid-Open No. 7-96005, Japanese Patent Application Laid-Open No. 7-100188, Japanese Utility Model Publication No. 7-22725 JP-A-7-22727, JP-A-7-116191, JP-A-7-116193, JP-A-7-132126, JP-A-7-27524, JP-A-7-148200, Japanese Unexamined Patent Publication No. 7-34814, Japanese Unexamined Patent Publication No. 7-171180, Japanese Unexamined Patent Publication No. 7-184946, Japanese Unexamined Patent Publication No. 7-184947, Japanese Unexamined Patent Publication No. 7-184955, Japanese Unexamined Patent Publication No. 7-184955, and Japanese Unexamined Patent Publication No. 7. No.-216753, JP-A-7-227403, JP-A-7-231914, JP-A-7-255773, JP-A-7-255774, JP-A-7-255775, JP-A-7-265357. No. 7, JP-A-7-275294, JP-A-7-289583, JP-A-7-289484, JP-A-7. No. 289585, JP-A-7-289586, JP-A-7-289987, JP-A-7-289588, JP-A-7-300754, JP-A-7-44425, JP-A-7-308341 JP-A-7-308343, JP-A-7-313550, JP-A-7-313552, JP-A-7-328067, JP-A-7-328069, JP-A-8-668, JP-A-8-10285, JP-A-8-24290, JP-A-8-24291, JP-A-8-33677, JP-A-8-56984, JP-A-8-60512, JP-A JP-A-8-66424, JP-A-8-71103, JP-A-8-84746, JP-A-8-112306, JP-A-8-1. No. 12308, JP-A-8-112309, JP-A-8-112122, JP-A-8-117278, JP-A-8-126663, JP-A-8-150173, JP-A-8-150174 Japanese Patent Laid-Open No. 8-154971, Japanese Patent Laid-Open No. 8-1


No. 5,4973, JP-A-8-154974, JP-A-8-164164, JP-A-8-173477, JP-A-8-176338, JP-A-8-182704, JP-A-8-191851 JP-A-8-191857, JP-A-8-191858, JP-A-8-191860, JP-A-8-196559, JP-A-8-196565, JP-A-8-215239, JP-A-8-215240, JP-A-8-215241, JP-A-8-215247, JP-A-8-218272, JP-A-8-229072, JP-A-8-266572, JP-A-8-265572 JP-A-8-280725, JP-A-8-280727, JP-A-8-289902, JP-A-8-3179. No. 0, JP-A-8-322876, JP-A-8-322877, JP-A-8-322878, JP-A-8-336557, JP-A-9-563, JP-A-9 -564, JP-A-9-3222, JP-A-9-3227, JP-A-9-19452, JP-A-9-24063, JP-A-9-28730, JP-A-9-38138 JP, 9-38139, JP 9-51913, JP 9-56746, JP 9-56747, JP 9-66071, JP 9-75385. JP, 9-75393, JP 9-75394, JP 9-77901, JP 9-84826, JP 9-94266, JP -99006, JP-A-9-99007, JP-A-9-99010, JP-A-9-212, JP-A-9-103447, JP-A-9-103448, JP-A-9-117474 No. 9, JP-A-9-122175, JP-A-9-122176, JP-A-9-131364, JP-A-9-132814, JP-A-9-135863, JP-A-9-140742 JP-A-9-154882, JP-A-9-154883, JP-A-9-154848, JP-A-9-154858, JP-A-9-154886, JP-A-9-154888, No. 9-173370, JP-A-9-175504, JP-A-9-182769, JP-A-9-191908 JP-A-9-192169, JP-A-9-201382, JP-A-9-206330, JP-A-9-215709, JP-A-9-224973, JP-A-9-243622, JP 9-248316, JP 9-253122, JP 9-253123, JP 9-253124, JP 9-253125, JP 9-253130, JP JP-A-9-262250, JP-A-9-262251, JP-A-9-262252, JP-A-9-273061, JP-A-9-276611, JP-A-9-276334, JP-A-9- No. 285484, JP-A-9-285485, JP-A-9-285487, JP-A-9-28589, JP-A-9-285490, JP-A-9-286085, JP-A-9-290000, JP-A-9-290002, JP-A-9-291485, JP-A-9-294472, JP-A-9 JP-A-295754, JP-A-9-299401, JP-A-9-299403, JP-A-9-299404, JP-A-9-300004, JP-A-9-302319, JP-A-9-308510. JP, 9-308648, JP 9-308649, JP 9-313527, JP 9-313533, JP 9-31535, JP 9-322911. JP-A-10-5277, JP-A-10-5278, JP-A-10-14978, JP-A-10- No. 4060, JP-A-10-24066, JP-A-10-28701, JP-A-10-28703, JP-A-10-28704, JP-A-10-33591, JP-A-10-43234 JP-A-10-43237, JP-A-10-43238, JP-A-10-52454, JP-A-10-52455, JP-A-10-57413, JP-A-10-57414, JP-A-10-57415, JP-A-10-66709, JP-A-10-71172, JP-A-10-71173, JP-A-10-75980, JP-A-10-77354, JP-A-10-77354 JP-A-10-77566, JP-A-10-80443, JP-A-10-80444, JP-A-10-8044 No. 6, No. 10-80, No. 10-81, No. 10-85254, No. 10-85255, No. 10-85257, No. 10-95481 JP, 10-99371, JP 10-99373, JP 10-99375, JP 10-108877, JP 10-109819, JP 10-118114, JP-A-10-118115, JP-A-10-118120, JP-A-10-121301, JP-A-10-127687, JP-A-10-127689, JP-A-10-127694, JP-A-10-127694 10-137287, JP-A-10-137288, JP-A-10-137289, JP-A-10-1 7291, JP-A-10-137292, JP-A-10-146359, JP-A-10-151153, JP-A-10-155434, JP-A-10-165437, JP-A-10-165439. JP-A-10-179633, JP-A-10-179634, JP-A-10-179635, JP-A-10-179039, JP-A-10-192338, JP-A-10-192339, JP-A-10-192342, JP-A-10-201790, JP-A-10-21235, JP-A-10-2111236, JP-A-10-23479, JP-A-10-258082, JP-A-10-280882 JP-A-10-263010, JP-A-10-272154, JP-A-1 -272157, JP-A-10-277092, JP-A-10-286279, JP-A-10-295725, JP-A-10-295727, JP-A-10-298321, JP-A-10-298801. JP, 10-314220, JP 10-314225, JP 10-328234, JP 10-328236, JP 10-328237, JP 10-329903. JP-A-10-337304, JP-A-11-4853, JP-A-11-19129, JP-A-11-28223, JP-A-11-56904, JP-A-11-76299. JP-A-11-99165, JP-A-11-99172, JP-A-11- No. 99173, JP-A-11-99174, JP-A-11-99177, JP-A-11-99178, JP-A-11-100045, JP-A-11-104170, JP-A-11-104171 JP, 11-104172, JP 11-104173, JP 11-104180, JP 11-104181, JP 11-106524, JP 11-107007, JP-A-11-113958, JP-A-11-128267, JP-A-11-128268, JP-A-11-128806, JP-A-11-137601, JP-A-11-137602, JP-A-11-137602 11-140705, JP-A-11-140706, JP-A-11-1 No. 6895, JP-A-11-155905, JP-A-11-155906, JP-A-11-169403, JP-A-11-178854, JP-A-11-188055, JP-A-11-188057 Gazette, JP-A-11-188058, JP-A-11-188059, JP-A-11-188060, JP-A-11-188061, JP-A-11-188062, JP-A-11-206808, JP-A-11-206809, JP-A-11-216159, JP-A-11-216161, JP-A-11-235357, JP-A-11-244326, JP-A-11-244331, JP-A-11-243331 11-253476, JP-A-11-253488, JP-A-1 No. 253489, JP-A-11-262503, JP-A-11-267145, JP-A-11-267154, JP-A-11-276520, JP-A-11-276521, JP-A-11-276524. JP-A-11-285510, JP-A-11-285511, JP-A-11-285513, JP-A-11-299823, JP-A-11-299824, and JP-A-11-299826. JP-A-11-299828, JP-A-11-299829, JP-A-11-299832, JP-A-11-301727, JP-A-11-309166, JP-A-11-313852, Kaihei 11-318976, JP-A-11-332899, JP JP-A-11-332910, JP-A-11-332911, JP-A-11-332912, JP-A-11-332913, JP-A-11-342156, JP-A-11-347063, JP-A-11 JP-A-347064, JP-A 2000-265, JP-A 2000-5230, JP-A 2000-5231, JP-A 2000-14697, JP-A 2000-14702, JP-A 2000-33099. No. 2000, No. 2000-15, No. 2000-42028, No. 2000-42029, No. 2000-51268, No. 2000-60899, No. 2000-79140. JP, 2000-79141, JP, 2000-83955, JP, 2000 No. 83999, JP-A 2000-93457, JP-A 2000-102560, JP-A 2000-102561, JP-A 2000-107222, JP-A 2000-107223, JP-A 2000-107225 JP, JP-A 2000-107226, JP-A 2000-107528, JP-A 2000-116705, JP-A 2000-126227, JP-A 2000-140004, JP-A 2000-140006, JP 2000-140010, JP 2000-140017, JP 2000-140018, JP 2000-140019, JP 2000-152958, JP 2000-157570, JP No. 2000-166969, Special JP 2000-178866 A, JP 2000-189454 A, JP 2000-189457 A, JP 2000-189461 A, JP 2000-189462 A, JP 2000-197660 A, JP 2000-2000 A. 198865, JP2000-225143, JP2000-225144, JP2000-232993, JP2000-254168, JP2000-254169, JP2000-254172 JP, 2000-254174, JP 2000-254175, JP 2000-254176, JP 2000-262553, JP 2000-262555, JP 2000-262556, JP2000-26255 No. 8, JP-A 2000-271165, JP-A 2000-271166, JP-A 2000-279443, JP-A 2000-279448, JP-A 2000-288012, JP-A 2000-288013 Gazette, JP 2000-288015 A


JP, 2000-288016, JP 2000-288020, JP 2000-288021, JP 2000-288023, JP 2000-296148, JP 2000-296149, JP 2000-296150, JP 2000-300604, JP 2000-300605, JP 2000-316897, JP 2000-316898, JP 2000-316902, JP JP 2000-316903, JP 2000-316904, JP 2000-325394, JP 2000-333986, JP 2000-333990, JP 2000-342622, 2000- No. 342623, JP-A 2000- 42626, 2000-342627, 2000-354606, 2000-354607, 2000-354760, 2001-8957, 2001-8962 Japanese Patent Laid-Open No. 2001-8970, No. 2001-8968, No. 2001-17469, No. 2001-19777, No. 2001-20167, No. 2001-20168, JP 2001-46426, JP 2001-46430, JP 2001-46431, JP 2001-54536, JP 2001-57993, JP 2001-61888, JP JP 2001-61889, JP 2001-61890, JP 2 No. 01-70340, JP-A-2001-70342, JP-A-2001-70345, JP-A-2001-79035, JP-A-2001-79036, JP-A-2001-87309, JP-A-2001-2001. JP 87310, JP 2001-87314, JP 2001-87313, JP 2001-95836, JP 2001-95838, JP 2001-95840, JP 2001-104372. JP, JP-A-2001-105504, JP-A-2001-112816, JP-A-2001-112817, JP-A-2001-114226, JP-A-2001-120593, JP-A-2001-120595, JP 2001-137280 A, JP 2001-13 7281, JP 2001-137282, JP 2001-137287, JP 2001-137288, JP 2001-137289, JP 2001-145663, JP 2001-145664. Gazette, JP 2001-145665, JP 2001-145666, JP 2001-145661, JP 2001-149406, JP 2001-149409, JP 2001-149407, JP 2001-157690 A, JP 2001-157691 A, JP 2001-157692 A, JP 2001-161746 A, JP 2001-161747 A, JP 2001-161748 A, JP. 2001-170106, JP JP-A-2001-170107, JP-A-2001-171029, JP-A-2001-178770, JP-A-2001-178777, JP-A-2001-178777, JP-A-2001-187086, JP-A-2001-2001. No. 190592, JP-A-2001-190593, JP-A-2001-198157, JP-A-2001-204764, JP-A-2001-204765, JP-A-2001-212175, JP-A-2001-224628 JP, JP-A-2001-245922, JP-A-2001-252302, JP-A-2001-258931, JP-A-2001-258933, JP-A-2001-258938, JP-A-2001-261062, JP 2001-26936 A JP, JP 2001-269369, JP 2001-276128, JP 2001-286504, JP 2001-286505, JP 2001-293029, JP 2001-293030. JP, 2001-309938, JP, 2001-314441, JP, 2001-314444, JP, 2001-318067, JP, 2001-321399, JP, 2001-327521, JP 2001-333931 A, JP 2001-340370 A, JP 2001-340380 A, JP 2001-340181 A, JP 2001-340383 A, JP 2001-346827 A, JP 2001 2001 A. No. 346830, JP 2001 JP-A-346828, JP-A-2001-353180, JP-A-2002-631, JP-A-2002-632, JP-A-2002-642, JP-A-2002-647, JP-A-2002-648. JP, JP 2002-649, JP 2002-7573, JP 2002-11041, JP 2002-17780, JP 2002-22687, and JP 2002-22688. JP-A-2002-35022, JP-A-2002-35028, JP-A-2002-35029, JP-A-2002-35031, JP-A-2002-45392, JP-A-2002-45397, JP 2002-45398, JP 2002-45401 A, JP 2002-52043 A JP-A-2002-53202, JP-A-2002-65730, JP-A-2002-65731, JP-A-2002-65732, JP-A-2002-65733, JP-A-2002-65734, JP 2002-65739, JP 2002-65740, JP 2002-65745, JP 2002-67199, JP 2002-73805, JP 2002-78734, JP 2002 -85451, JP-2002-84552, JP-2002-95692, JP-2002-95694, JP-2002-95695, JP-2002-95696, JP-2002-102278. JP, 2002-102279, JP 2002-10 No. 280, No. 2002-102282, No. 2002-102283, No. 2002-111040, No. 2002-113041, No. 2002-119534, No. 2002-126002 JP, 2002-126003, JP 2002-136542, JP 2002-136543, JP 2002-136546, JP 2002-138364, JP 2002-143214, JP 2002-148263, JP 2002-153502, JP 2002-153503, JP 2002-153504, JP 2002-153505, JP 2002-153507, JP 2002-153508, JP-A-2 002-159460, JP-A 2002-159525, JP-A 2002-159527, JP-A 2002-159528, JP-A 2002-159529, JP-A 2002-159530, JP-A 2002-2002. No. 165832, JP-A No. 2002-165834, JP-A No. 2002-165835, JP-A No. 2002-172098, JP-A No. 2002-172130, JP-A No. 2002-172131, JP-A No. 2002-172132 JP, 2002-172134, JP 2002-172136, JP 2002-172137, JP 2002-172139, JP 2002-177329, JP 2002-178428, JP2002-191637 JP, 2002-200112, JP 2002-200113, JP 2002-200116, JP 2002-209934, JP 2002-209935, JP 2002-209936, JP2002-209938, JP2002-209939, JP2002-209940, JP2002-209941, JP2002-2224093, JP2002-224160, JP JP 2002-233549 A, JP 2002-233550 A, JP 2002-238945 A, JP 2002-238950 A, JP 2002-248127 A, JP 2002-248128 A, JP 2002-248128 A. No. 253607, JP 2002 No. 253608, JP-A No. 2002-253609, JP-A No. 2002-263135, JP-A No. 2002-272781, JP-A No. 2002-272784, JP-A No. 2002-272784, JP-A No. 2002-272785 JP, 2002-273808, JP 2002-278491, JP 2002-282303, JP 2002-291997, JP 2002-291799, JP 2002-291801, JP 2002-291803 A, JP 2002-301103 A, JP 2002-301104 A, JP 2002-306532 A, JP 2002-306534 A, JP 2002-315778 A, JP 2002-315780, JP2002-320635, JP2002-320637, JP2002-325793, JP2002-325795, JP2002-325797, JP2002-330994, JP JP 2002-333448, JP 2002-336302, JP 2002-345890, JP 2002-355270, JP 2002-360629, JP 2002-360631, JP 2002-2002. 369841, JP2003-4734, JP2003-10244, JP2003-12490, JP2003-19153, JP2003-24380, JP2003-24377 Gazette, JP2003-24379A, JP 2003-24381, JP 2003-24918, JP 2003-33394, JP 2003-33396, JP 2003-33400, JP 2003-38554, JP 2003-2003. No. 38559, No. 2003-38570, No. 2003-41470, No. 2003-47629, No. 2003-47631, No. 2003-52502, No. 2003-58759. 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No. 03-135524, No. 2003-144486, No. 2003-14489, No. 2003-144490, No. 2003-144492, No. 2003-144494, No. 2003- No. 153943, JP-A No. 2003-153944, JP-A No. 2003-153948, JP-A No. 2003-153949, JP-A No. 2003-153950, JP-A No. 2003-153951, JP-A No. 2003-153902 JP, 2003-153594, JP 2003-153955, JP 2003-159279, JP 2003-164477, JP 2003-164487, JP 2003-180737, JP 2003-180746 A JP, 2003-180747, JP 2003-180745, JP 2003-180750, JP 2003-199784, JP 2003-199785, JP 2003-199789, JP 2003-199791 A, JP 2003-199792 A, JP 2003-204987 A, JP 2003-204988 A, JP 2003-204990 A, JP 2003-210507 A, JP JP 2003-210518 A, JP 2003-210520 A, JP 2003-220092 A, JP 2003-235891 A, JP 2003-235892 A, JP 2003-245307 A, and JP 2003-2003 A. No. 250835, JP 2003-2003 No. 50837, No. 2003-260083, No. 2003-260084, No. 2003-265511, No. 2003-265520, No. 2003-265523, No. 2003-265528. Gazette, JP2003-265529, JP2003-265530, JP2003-275236, JP2003-275241, JP2003-275243, JP2003-275244, JP 2003-275245, JP 2003-275246, JP 2003-285890, JP 2003-286642, JP 2003-290279, JP 2003-290278, JP 2003-290282 Publication, Special JP 2003-290286, JP-A-20 / 290287, JP-2003-2902043, JP-2003-292640, JP-2003-99689, JP-2003-29992, JP 2003-299893, JP 2003-299694, JP 2003-305080, JP 2003-305082, JP 2003-305083, JP 2003-310663, JP 2003 JP-A-3319972, JP-A-2003-325563, JP-A-2003-39749, JP-A-2003-339770, JP-A-2003-339771, JP-A-2004-344, JP-A-2004-481 JP, JP 2004-648, JP 2 No. 004-8301, JP-A 2004-16441, JP-A 2004-24304, JP-A 2004-24307, JP-A 2004-24308, JP-A 2004-24310, JP-A 2004-2004. No. 24434, JP-A No. 2004-33549, JP-A No. 2004-41307, JP-A No. 2004-41310, JP-A No. 2004-41311, JP-A No. 2004-42913, JP-A No. 2004-42922 JP, 2004-49707, JP 2004-49709, JP 2004-49762, JP 2004-49763, JP 2004-49764, JP 2004-49765, JP 2004-57412 A, JP 2004-57413 A, JP-A-2004-57414, JP-A-2004-57415, JP-A-2004-57416, JP-A-2004-57640, JP-A-2004-65300, JP-A-2004-65301, JP-A-2004-2004 No. 65924, JP-A No. 2004-65929, JP-A No. 2004-73297, JP-A No. 2004-73985, JP-A No. 2004-81365, JP-A No. 2004-81369, JP-A No. 2004-81575 JP, JP-A-2004-81617, JP-A-2004-81618, JP-A-2004-89491, JP-A-2004-89614, JP-A-2004-91996, JP-A-2004-105315, JP 2004-105376 A, JP 2004-10547 A JP, 2005-105668, JP 2004-105696, JP 2004-105597, JP 2004-105698, JP 2004-105704, JP 2004-121363. JP-A-2004-121382, JP-A-2004-121388, JP-A-2004-121389, JP-A-2004-121392, JP-A-2004-121831, JP-A-2004-121871, JP-A-2004-123171, JP-A-2004-124303, JP-A-2004-129878, JP-A-2004-136852, JP-A-2004-141177, JP-A-2004-141257, JP-A-2004 -141270, JP2004 -141499, JP-A-2004-141532, JP-A-2004-141634, JP-A-2004-141636, JP-A-2004-141638, JP-A-2004-141640, JP-A-2004-141642 JP, 2004-141642, JP-A 2004-149970, JP-A 2004-154250, JP-A 2004-154561, JP-A 2004-1559591, JP-A 2004-155952 JP, 2004-159820, JP, 2004-163127, JP, 2004-166999, JP, 2004-1667025, JP, 2004-167026, JP, 2004-168448, JP, No. 2004-168449 JP, 2004-174210, JP, 2004-180728, JP, 2004-180950, JP, 2004-181014, JP, 2004-187873, JP, 2004-188060, JP JP 2004-194466 A, JP 2004-194805 A, JP 2004-194815 A, JP 2004-194820 A, JP 2004-195244 A, JP 2004-195254 A, JP 2004-2004 A. No. 201719, No. 2004-208784, No. 2004-208836, No. 2004-209170, No. 2004-215694, No. 2004-215696, No. 2004-216172. JP, 2004-22 No. 939, JP-A 2004-223023, JP-A-2004-223123, JP-A-2004-223124, JP-A-2004-229695, JP-A-2004-229696, JP-A-2004-236826 Gazette, JP-A-2004-249079, JP-A-2004-255164, JP-A-2004-255166, JP-A-2004-2611200, JP-A-2004-261354, JP-A-2004-261442, JP, 2004-267257, JP, 2004-267335, JP, 2004-267356, JP, 2004-275352, JP, 2004-275558, JP, 2004-283263, JP, JP 2004-285549, JP-A-2 JP-A-2004-290400, JP-A-2004-290646, JP-A-2004-290695, JP-A-2004-298362, JP-A-2004-298394, JP-A-2004-298395, JP-A-2004-2004. No. 298401, JP-A-2004-298413, JP-A-2004-298456, JP-A-2004-29859, JP-A-2004-298499, JP-A-2004-305506, JP-A-2004-305596 JP, 2004-305597, JP 2004-305598, JP 2004-305599, JP 2004-305600, JP 2004-305601, JP 2004-305761, JP2004-305766 Gazette, JP-A No. 2004-307771, JP-A No. 2004-307772, JP-A No. 2004-321460, JP-A No. 2004-332159, JP-T-8-500062, JP-A-8-5000025 Gazette, special table hei 8-502177, special table hei 8-502181, special table hei 8-502182, special table 8-502183, special table 8-504474, special table No. 8-504607, No. 8-507699, No. 8-508423, No. 8-508424, No. 8-508427, No. 8-508428. No. 8-508553, No. 8-508657, No. 8-509786, No. 8-510670, No. 8-5 No. 0798, No. 8-510942, No. 8-511443, No. 8-511444, No. 8-511703, No. 8-511704, No. Table No. 8-511973, No. 8-511974, No. 8-512076, No. 9-501588, No. 9-501850, No. 9-503829 No. 9, Special Tables Nos. 9-504471, No. 9-504715, No. 9-505218, No. 9-505219, No. 9-505222, Special Tables No. 9-505223, No. 9-505225, No. 9-505227, No. 9-506531, No. 9-506798, No. 9-50693 No. 9, No. 9-507091, No. 9-507766, No. 9-5008035, No. 9-508423, No. 9-508424, No. No. 9-508426, No. 9-508546, No. 9-509350, No. 9-510889, No. 9-511536, No. 9-512504. No.10, No.10-500330, No.10-500590, No.10-501146, No.10-501433, No.10-501717, Special table No. 10-502000, No. 10-502023, No. 10-502423, No. 10-503668, No. 10-504987, No. 10 No. 0-504988, No. 10-505261, No. 10-506303, No. 10-506333, No. 10-506440, No. 10-506552 No. 10-508218, No. 10-508521, No. 10-509348, No. 10-509353, No. 10-509356, No. 10 No. 509362, No. 10-509624, No. 10-509625, No. 10-509748, No. 10-509754, No. 10-509895, No. 10-509896, No. 10-509898, No. 10-509915, No. 10-510199, No. 10-510733, No. 10-511130, No. 10-511275, No. 10-511280, No. 10-51592, No. 10-512170 No. 10/512174, No. 10-512


No. 183, No. 10-512316, No. 10-512493, No. 10-512768, No. 10-512795, No. 10-513076, No. No. 10-513135, No. 11-500048, No. 11-500763, No. 11-500794, No. 11-500936, No. 11-500950 Publication No. 11-501275, No. 11-501362, No. 11-501683, No. 11-501996, No. 11-502541, No. 11-502541, Special Table No. 11-502730, No. 11-502738, No. 11-502741, No. 11-503032, and No. 11- No. 03034, No. 11-503177, No. 11-503594, No. 11-503958, No. 11-504048, No. 11-504049, No. No. 11-504684, No. 11-505137, No. 11-506966, No. 11-507096, No. 11-507097, No. 11-507286. No.11, No. 11-507864, No. 11-508156, No. 11-508789, No. 11-509455, No. 11-510082, No. No. 11-510416, No. 11-511197, No. 11-511696, No. 11-512945, No. 11 No. 1-513366, No. 11-513647, No. 11-513926, No. 11-514054, No. 11-514897, No. 2000-500352, JP 2000-500712, JP 2000-502744, JP 2000-502941, JP 2000-503244, 2000-503578, 2000-503582, JP No. 2000-504970, No. 2000-504974, No. 2000-504975, No. 2000-504579, No. 2000-505161, No. 2000-505682, No. 2000- No. 505692, Special Table 2000-505704, Special Table No. 2000-505708, No. 2000-506426, No. 2000-507127, No. 2000-508933, No. 2000-509432, No. 2000-509633, No. 2000- No. 509672, No. 2000-510031, No. 2000-510194, No. 2000-510365, No. 2000-510371, No. 2000-510518, No. 2000-510755. Gazette, special table 2000-511125, special table 2000-512166, special table 2000-513408, special table 2000-513602, special table 2000-513619, special table 2000-513627, Special table 2000-51363 No. 2000, 513636, No. 2000-513638, No. 2000-513539, No. 2001-501518, No. 2001-504730, No. 2001-505624. No. 2001-507595, No. 2001-507736, No. 2001-507735, No. 2001-509420, No. 2001-513396, No. 2001-513455, No. Table 2001-515753, Table 2001-517121, Table 2001-517487, Table 2001-517541, Table 2001-517992, Table 2001-519304, Table 2001 -519302, Special Table 200 No. 521590, No. 2001-52183, No. 2001-5211994, No. 2001-522644, No. 2001-522697, No. 2001-522700, No. 2001-523537. Gazette, special table 2001-523597, special table 2001-523708, special table 2001-523713, special table 2001-523714, special table 2001-524351, special table 2001-524621 No. 2001-526333, No. 2001-526984, No. 2001-526985, No. 2001-526986, No. 2001-527162, No. 2001-526163, Table 2002-500222 gazette No. 2002-501880, No. 2002-502632, No. 2002-502633, No. 2002-502634, No. 2002-503517, No. 2002-503521, Table 2002-505911, Special Table 2002-505912, Special Table 2002-505917, Special 2002-505916, Special 2002-506682, Special 2002-506683, Special 2002 No.-506889, No. 2002-507236, No. 2002-507559, No. 2002-507903, No. 2002-507909, No. 2002-507910, No. 2002-507911. No., Special Table 2002-50 No. 913, No. 2002-507914, No. 2002-508221, No. 2002-508223, No. 2002-508922, No. 2002-509252, No. 2002-509457. Gazette, special table 2002-509451, special table 2002-510993, special table 2002-511001, special table 2002-511002, special table 2002-511003, special table 2002-511004, Special Table 2002-511144, Special Table 2002-520208, Special Table 2002-512901, Special 2002-512909, Special 2002-513636, Special 2002-53643, Special Table 2002-513723 gazette, special table No. 002-515294, No. 2002-51596, No. 2002-516153, No. 2002-516368, No. 2002-516715, No. 2002-516716, No. 2002 No. 516768, No. 2002-517586, No. 2002-519104, No. 2002-519105, No. 2002-519109, No. 2002-519106, No. 2002-519110. 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Gazette, special table 2003-523780, special table 2003-52391, special table 2003-523842, special table 2003-524440, special table 2003-524438, special table 2003-524441, Special Table 2003-524442, Special Table 2003-524535, Special 2003-525646, Special 2003-526387, Special 2003-526464, Special 2003-526468, Special 2003-526534, Special Table 2 No. 03-527140, No. 2003-527139, No. 2003-527201, No. 2003-527202, No. 2003-527249, No. 2003-527877, No. 2003. No. 528654, No. 2003-528694, No. 2003-529687, No. 2003-530966, No. 2003-530965, No. 2003-530967, No. 2003-530968. Gazette, special table 2003-530969, special table 2003-53640, special table 2003-53937, special table 2003-532432, special table 2003-532438, special table 2003-532803, Special table 2003-533280 Gazette, special table 2003-534098 gazette, special table 2003-534466 gazette, special table 2003-535649 gazette, special table 2003-535966 gazette, special table 2004-500133 gazette, special table 2004-500965 gazette, JP 2004-501254, JP 2004-505671, JP 2004-505672, JP 2004-505726, JP 2004-507323, JP 2004-507384, JP No. 2004-508142, No. 2004-508144, No. 2004-510472, No. 2004-510500, No. 2004-510867, No. 2004-510868, No. 2004 No. 51363, Special Table 2004 No. 512098, Special Table No. 2004-512553, Special Table No. 2004-515266, Special Table No. 2004-515272, Special Table No. 2004-517698, Special Table No. 2004-519265, Special Table No. 2004-519270 Gazette, Special Table 2004-52


No. 0861, No. 2004-521775, No. 2004-523374, No. 2004-525661, No. 2004-525668, No. 2004-525730, No. 2004-526826. 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Japanese Patent No. 4649, Japanese Patent No. 3434695, Japanese Patent No. 3437183, Japanese Patent No. 3437419, Japanese Patent No. 3439269, Japanese Patent No. 33441976, Japanese Patent No. 34441982, Japanese Patent No. 3446808, Japanese Patent No. 3447872 Gazette, Japanese Patent No. 3447873, Japanese Patent No. 3447950, Japanese Patent No. 3447953, Japanese Patent No. 3453096, Japanese Patent No. 3455247, Japanese Patent No. 3457650, Japanese Patent No. 3458555, Japanese Patent No. 3467405, Japanese Patent No. 3467414, Japanese Patent No. 3470122, Japanese Patent No. 3470123, Japanese Patent No. 34711999, Japanese Patent No. 3472020, Japanese Patent No. 3472301, Japanese Patent No. 3474556, Patent No. No. 474797, Japanese Patent No. 3478722, Japanese Patent No. 3479382, Japanese Patent No. 3479383, Japanese Patent No. 3479388, Japanese Patent No. 3479395, Japanese Patent No. 348267, Japanese Patent No. 3488506, Japanese Patent No. 3492188 Gazette, Japanese Patent No. 3492205, Japanese Patent No. 3492242, Japanese Patent No. 3492359, Japanese Patent No. 3499992, Japanese Patent No. 3493211, Japanese Patent No. 3494653, Japanese Patent No. 3497815, Japanese Patent No. 3500356, Japanese Patent No. 3501809, Japanese Patent No. 3502379, Japanese Patent No. 3508044, Japanese Patent No. 3510057, Japanese Patent No. 3510093, Japanese Patent No. 3510119, Japanese Patent No. 3510125, No. 3510133, Japanese Patent 3510145, Japanese Patent 3510149, Japanese Patent 3510150, Japanese Patent 3510159, Japanese Patent 3511187, Japanese Patent 3511488, Japanese Patent 3514448, Japanese Patent No. 3514448 Japanese Patent No. 3515918, Japanese Patent No. 3519019, Japanese Patent No. 3519192, Japanese Patent No. 3519267, Japanese Patent No. 352396, Japanese Patent No. 3522540, Japanese Patent No. 3527010, Japanese Patent No. 3527368, Japanese Patent No. 3527435 Publication, Japanese Patent No. 3527437, Japanese Patent No. 3527488, Japanese Patent No. 3532202, Japanese Patent No. 3533285, Japanese Patent No. 3535984, Japanese Patent No. 3541054, Japanese Patent No. 3541157 No. 3544961, Japanese Patent No. 3547925, Japanese Patent No. 3550041, Japanese Patent No. 35500053, Japanese Patent No. 3550056, Japanese Patent No. 3550058, Japanese Patent No. 33550063, Japanese Patent No. 3557133, Japanese Patent No. 3557141, Japanese Patent No. 3558734, Japanese Patent No. 3558801, Japanese Patent No. 3560348, Japanese Patent No. 3560504, Japanese Patent No. 3556374, Japanese Patent No. 3565995, Japanese Patent No. 3573487, Japanese Patent No. 3573487 Japanese Patent No. 3573497, Japanese Patent No. 3575990, Japanese Patent No. 3576003, Japanese Patent No. 3576045, Japanese Patent No. 3578800, Japanese Patent No. 3578802, Japanese Patent No. 3578822, Japanese Patent No. 358341. Gazette, Japanese Patent No. 3585616, Japanese Patent No. 3586256, Japanese Patent No. 3589528, Japanese Patent No. 3589539, Japanese Patent No. 3590618, Japanese Patent No. 3591556, Japanese Patent No. 3592591, Japanese Patent No. 3592592 And those described in Japanese Patent No. 3592599.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<Example 1>
(Raw material preparation)
125 parts by weight of 80% by weight aqueous acrylic acid solution, 57.3 parts by weight of 48.5% by weight aqueous sodium hydroxide solution, 6.4 parts by weight of water, 0.15 cross-linking agent (N, N′-methylenebisacrylamide) Part A and 5.0 parts by weight of a 30% by weight aqueous hydrogen peroxide solution were added to prepare Solution A. The monomer concentration of Solution A was 60% by weight, and the degree of neutralization was 50 mol%.
Similarly, 125 parts by weight of 80% by weight acrylic acid aqueous solution, 57.3 parts by weight of 48.5% by weight sodium hydroxide aqueous solution, 9.9 parts by weight of water, 0 crosslinker (N, N′-methylenebisacrylamide) 0 Solution B was prepared by adding 15 parts by weight and 1.5 parts by weight of L-ascorbic acid. The monomer concentration and neutralization degree of solution B were the same as solution A.

(polymerization)
The prepared solution A and solution B were mixed using the nozzle shown in FIG. The inner diameters of the nozzles in FIG. 1 are all 0.13 mm, and five nozzles for each solution are arranged at 1 cm intervals. The crossing angle between the solution A and the solution B flowing out from the nozzle was set to 30 degrees, and the distance between the nozzle tips was set to 4 mm. Each solution was heated to 40 ° C. and supplied with a pump so as to flow out at a flow rate of 5 m / sec.
Solution A and Solution B merge at the intersection of the extension lines of each nozzle pair, form a liquid column of about 10 mm, and then form liquid droplets in the gas phase (in air, at a temperature of 50 ° C.). ) Fell. The droplets fall on a base material (fluff pulp with a basis weight of 100 g / m ² ) moving horizontally at 0.10 m / min 2 m below the confluence of the solution, and the mixture under polymerization is fluffed. A precursor composite adhering to the pulp was formed.

(Base material laying)
The polymer surfaces of the precursor composite were bonded together and pressed using a stainless steel plate coated with Teflon (registered trademark). The table shows the results of measuring the time from when the precursor composite was obtained to the start of laying the base material (laying start time), the temperature at the time of laying, the applied pressure, the polymerization rate and the moisture content immediately before laying the base material.

(Drying process)
A sample obtained by laying the base material was dried with warm air at 120 ° C. for 30 minutes and then cooled to room temperature to obtain a water-absorbing composite.

(Compression molding)
Further, the obtained water-absorbing composite was cut into a rectangle of 40 cm × 20 cm, sandwiched between two smooth stainless plates of the same size having a thickness of 3 mm, left to stand at room temperature for 5 minutes under a load of 10 MPa from both sides, The pressure was released to obtain a water-absorbing composite. The layer structure of the obtained water-absorbing composite was as shown in FIG. The performance of this water-absorbing composite is shown in the table.

<Example 2>
A water-absorbing composite was produced in the same manner as in Example 1 except that the temperature in the gas phase in (Polymerization) was changed to 40 ° C. The layer structure of the obtained water-absorbing composite was as shown in FIG. The performance of this water-absorbing composite is shown in the table.

<Example 3>
As in Example 1, a precursor composite in which the mixture being polymerized adhered to the fluff pulp was prepared, and at the same time, the substrate was made into a polyester nonwoven fabric (fiber diameter 67 dtex, weight 40 g / m ² ) under the same polymerization conditions. A modified precursor composite was prepared. The polymer surfaces of these two precursor composites were bonded together and pressed using a stainless steel plate. Furthermore, the same (drying process) and (compression molding) as in Example 1 were performed to produce a water-absorbing composite. The layer structure of the obtained water-absorbing composite was as shown in FIG. The performance of this water-absorbing composite is shown in the table.

<Example 4>
In the same manner as in Example 1, three precursor composites in which the mixture being polymerized adhered to the fluff pulp were prepared, two of which were bonded to each other, and the remaining one was bonded to the polymer surface that was further bonded. . Furthermore, the same (drying process) and (compression molding) as in Example 1 were performed to produce a water-absorbing composite. The layer structure of the obtained water-absorbing composite was as shown in FIG. The performance of this water-absorbing composite is shown in the table.

<Example 5>
A water-absorbing composite was produced in the same manner as in Example 1 except that the polymer surface was bonded to the back surface of the other precursor composite instead of the polymer surfaces of the precursor composite when the base material was laid. . The layer structure of the obtained water-absorbing composite was as shown in FIG. The performance of this water-absorbing composite is shown in the table.

<Example 6>
A water-absorbing composite was produced in the same manner as in Example 1 except that the substrate laying conditions were changed as shown in Table 1. The layer structure of the obtained water-absorbing composite was as shown in FIG. The performance of this water-absorbing composite is shown in the table.

<Comparative Example 1>
A water-absorbing composite was produced in the same manner as in Example 1 except that the base material laying conditions in Example 1 were changed as shown in Table 1. The performance of this water-absorbing composite is shown in the table.

<Comparative example 2>
A water-absorbing composite was produced in the same manner as in Example 1 except that normal temperature pure water was sprayed at the time of laying the base material and the water content in the polymer was changed as shown in Table 1. The performance of this water-absorbing composite is shown in the table.

<Comparative Example 3>
A water-absorbing composite was produced in the same manner as in Example 1 except that the temperature in the gas phase during (polymerization) was changed to 5 ° C. The performance of this water-absorbing composite is shown in the table.

<Measurement Method 1> Measurement of Polymerization Rate and Water Content Immediately before Laying the Substrate The polymerization rate and water content of the polymerizable monomer of the precursor composite were determined by the following procedure.
(Polymerization rate)
About 5 cm square of the precursor composite was immersed in about 150 g of methanol at room temperature for 12 hours to sufficiently extract the monomer. The amount of monomer in methanol was determined by liquid chromatography, and its weight was defined as Mm. On the other hand, the precursor composite after immersion was dried under reduced pressure at 110 ° C. for 3 hours, and its weight was defined as Mc. Moreover, the base material of the same quality and the same dimension comprised was immersed in about 150 g of methanol at room temperature for 12 hours, and then dried under reduced pressure at 110 ° C. for 3 hours, and the weight was defined as Ms. The polymerization rate was calculated from the respective weights according to the following formula.
Mc-Ms
Polymerization rate (%) = ――――――――――― x 100
Mm + Mc-Ms

(Moisture content)
Using an infrared moisture meter (Infrared moisture meter FD-100 (dry heat source: 280W annular ceramic sprayed sheathed heater) manufactured by Kett Science Laboratory Co., Ltd.), about 7 cm square precursor composite was heated at 110 ° C. for 30 minutes and weighed. . At this time, the weight of the sample before heating is W1, and the weight of the sample after heating is W2. A substrate of the same quality and the same size constituting the precursor composite was heated and weighed at 110 ° C. for 30 minutes using the same infrared moisture meter. The substrate weight after drying at this time is defined as W0. The water content P (%) was calculated by the following formula.
W1-W0
Moisture content P (%) = ―――――――― × 100
W2-W0

<Measuring method 2> Shape and dimensions of water-absorbing polymer (average particle diameter of water-absorbing particles)
The average diameter of primary particles of ten randomly selected water-absorbing particles in the water-absorbing polymer in the form of binder particles was defined as the average particle diameter of the water-absorbing particles. The primary particle size of the water-absorbing particles was determined using a SEM plane photograph of the sample.

(Shape of water-absorbing polymer)
When the web-like polymer is scattered in islands on the base material and dispersed, it is judged as a “water-like dispersion layer”, and the web-like polymer continues on the base in the sea state, and the openings are island-like. In the case of being scattered in, it was determined as a “water web-like continuous layer”.

(Dimension measurement of webbed water-absorbing polymer)
(1) In the case of a web-like dispersion layer The thickness of 10 randomly chosen web-like dispersion layers was measured using a dial gauge, and the average value was taken as the thickness of the web-like dispersion layer. The average of the average of the short diameter and the long diameter of each of the ten randomly selected webbed dispersion layers was taken as the average diameter of the webbed dispersion layer. The minor axis and the major axis were determined using SEM plan photographs of the samples.

(2) In the case of webbed continuous layer The thickness of 10 randomly selected webbed continuous layers was measured using a dial gauge, and the average value was taken as the thickness of the webbed continuous layer. An arithmetic average of 10 averages of the short diameter and long diameter of each of the aperture portions in 10 randomly selected continuous web layers was defined as the average pore diameter of the continuous web layer. Moreover, a hole area rate points out the percentage of the total area of a hole part in a webbed continuous layer fixed area. The short diameter, the long diameter, and the aperture area were determined using SEM plane photographs of the samples.

<Measurement method 3> Shape and dimensions of water-absorbing composite (thickness of water-absorbing composite)
A sample was cut into 5 cm × 5 cm and measured in the same manner as the thickness measurement of the diffusion layer in accordance with JIS 1-1096, and the average value of five samples was obtained.

(Binder particle / water web weight ratio)
A sample was cut into 5 cm × 5 cm, and the water-absorbing polymer was cut out from the base material using a stainless steel small knee-shaped scissors scissors (FST 14063-09), and the fixed base piece and fibers were trimmed and removed. Furthermore, using a digital optical microscope (VH-8000, manufactured by Keyence Corporation), the water-absorbing polymer collected while carefully observing the binder-like polymer and water web using stainless steel bone scissors anti-type scissors (FST 14077-10). The polymer was cut and collected, and the weight of each polymer was measured to determine the weight part of the binder particulate polymer with respect to 100 parts by weight of the web-like polymer.

<Measurement method 4> Performance of water-absorbent composite (measurement method of water retention ability (CRC))
The water absorbent composite dried at 110 ° C. for 30 minutes was cut so that the weight of the water absorbent polymer fixed to the water absorbent composite was about 1 g, and the weight (W ₁ ) was measured. This was put in a 250 mesh nylon bag (20 cm × 10 cm) and immersed in 500 ml of physiological saline (concentration: 0.9% by weight) at room temperature for 30 minutes. The nylon bag was then pulled up, suspended for 15 minutes and drained, and then dehydrated at 90 G for 90 seconds using a centrifuge. Further, the same substrate used for the production of the water-absorbing composite was dried at 110 ° C. for 30 minutes in the same manner as described above, then cut into the same size as the water-absorbing composite, and the weight (W ₂ ) was measured. . This was placed in a 250 mesh nylon bag (20 cm × 10 cm) in the same manner as described above, and immersed in 500 ml of physiological saline (concentration: 0.9% by weight) at room temperature for 30 minutes. The nylon bag was then pulled up, suspended for 15 minutes and drained, and then dehydrated at 90 G for 90 seconds using a centrifuge. The weight (W ₃ ) of the nylon bag containing the water-absorbing composite after dehydration and the weight (W ₄ ) of the nylon bag containing the base material after dehydration were measured. The water retention capacity S was calculated according to the following formula. Here, the units of W _{1 to} W ₄ are all g.
W ₃ −W ₄
S = ――――――――――
W ₁ −W ₂

(Measurement method of water absorption capacity under pressure (AUL))
(1) 20 g / cm ² load The water absorption capacity under pressure (AUL) was measured according to the following procedure using the apparatus shown in FIG. The measuring device includes a metal cylinder 12 (inside diameter 25.4 mmφ) whose bottom is closed with a metal mesh (# 100), a columnar weight 14 slightly smaller than the inside diameter of the cylinder, and a petri dish 13.
1) The water-absorbing composite dried at 110 ° C. for 30 minutes was punched with a punch (25 mmφ) to prepare a sample disk 11 for measurement (25 mmφ).
2) The weight Sd (g) of the sample disk 11 for measurement and the weight Td (g) of the cylinder 12 with a wire mesh were measured.
3) 25 g of artificial urine at room temperature was placed in the petri dish 13 (100 mmφ).
4) The sample disk 11 for measurement was inserted into the cylindrical tube 12 with a wire mesh with the base material side facing the wire mesh side.
5) A 100 g weight was placed on the measurement sample disk. At this time, care was taken that the weight and the cylinder were in contact with each other, and friction was not generated when the weight was lifted by water absorption.
6) The measurement sample disk 11 and the cylinder 12 in which the weight 14 was inserted were gently immersed in the petri dish 13 with the wire net facing down.
7) Water was absorbed for 1 hour.
8) The cylinder 12 was gently removed from the petri dish 13.
9) The cylinder 12 was gently placed on the filter paper (# 424), and the water adhering to the cylinder 12 was wiped off.
10) The weight 14 was removed (the water-absorbing polymer adhering to the weight 14 was moved to the cylinder 12 side).
11) The weight Tw (g) of the cylinder 12 was measured.
12) The weight Sw (g) of the sample disk 11 for measurement after water absorption was calculated | required by the following formula.
Sw = Tw−Td
13) In place of the water-absorbing composite, the same substrate as that used for the production of this water-absorbing composite was used, and a reference sample disk was prepared and a water absorbing operation was performed in the same manner as described above. The weight Nd (g) of the reference sample disk and the weight Mw (g) of the cylinder after water absorption were measured, and the weight Nw (g) of the reference sample disk after water absorption was determined by the following formula.
Nw = Mw−Td
14) Pressurized water absorption capacity (AUL) was calculated according to the following formula.
Pressurized water absorption capacity (AUL) (g / g) = (Sw−Nw) / (Sd−Nd)

Artificial urine having the following composition was used.
19.4 g of urea
Sodium chloride 8.0g
Calcium chloride (anhydrous) 0.6g
Magnesium sulfate (7 hydrate) 2.05g
970g of pure water

(2) 50 g / cm ² load The same measurement as in (1) was carried out except that a 250 g weight was used instead of the 100 g weight used in 5) of (1) above.

(Water absorption time)
(1) A water absorbent composite having a size of 5 cm × 5 cm was cut out from the water absorbent composite.
(2) 10 ml of pure water was charged into a glass petri dish having a diameter of 10 cm.
(3) The water-absorbing composite was immersed in pure water in the petri dish, and the time (seconds) until at least one bottom of the petri dish was exposed to the air was measured to obtain the water absorption time.

(Water absorption polymer drop-off rate of water-absorbent composite)
(1) A water-absorbing composite having a size of 10 cm × 10 cm was cut out (all four sides were opened), and the weight was measured. The total amount of water-absorbing polymer was determined from the structure of the water-absorbing composite. As shown in FIG. 7, the square of the water-absorbent composite 60 cut into a standard mesh sieve (inner frame dimensions: inner diameter 150 mm, depth 45 mm, 20 mesh) 61 defined by JISZ8801 was fixed to the center with a tape 62. .
(2) In this way, in the product manufactured by Tokyo Shinohara Manufacturing Co., Ltd., model number SS-S-228 type low tap type shaker (JIS Z8815) 65 shown in FIG. .
(3) The number of impulses was set to 165 times / minute, the number of rotations was set to 290 times / minute, the weight of the water-absorbing polymer dropped off from the water-absorbing composite after 60 minutes of shaking was measured, and the drop-off rate was obtained from the following formula. .
Weight of dropped water-absorbing polymer (g)
Dropout rate (%) = ――――――――――――――――――― × 100
Total water-absorbing polymer amount (g)

(Gel drop-off rate of water-absorbing composite)
When the force acting so as to rub the water-absorbing composite was repeatedly applied, the dropping rate of the water-absorbing gel of the water-absorbing composite was measured by the following procedure.
(1) As shown in FIG. 9, a sample (water-absorbing composite) 52 is placed on a surface smoothing table 51, and a cylinder 53 having an inner diameter of 40 mm is attached to the center and is surrounded by the cylinder 53. An acrylic plate 55 (100 × 100 × 10 mm, total weight 150 g) provided with seven through-holes 54 having a diameter of 5 mm at substantially equal intervals was placed in the portion. The disk 56 was not used.
(2) 150 ml of artificial urine was placed in the cylinder 53 and absorbed by the water-absorbent composite.
(3) After complete water absorption, it was allowed to stand at room temperature for 30 minutes, and as shown in FIG. 10, 72 cm from the center 71 of the water-absorbent composite 70 was cut out, and the weight of the cut-out portion (sample 73) was measured.
(4) After the measurement, as shown in FIG. 11, this sample 73 is placed on the center of a 20 cm × 20 cm acrylic plate 74, and a load (3 kg) 75 having the same bottom area (10 cm × 10 cm) as the cut sample is applied. It was mounted so as not to protrude according to the shape.
(5) Set the sample so that the cut end of the sample is perpendicular to the moving direction of the shaker (model number “MS-1” manufactured by Inoue Seieido Co., Ltd.), shake the integral sample, amplitude 50 mm, frequency 80 times / minute And shaken for 30 minutes.
(6) The load after shaking was removed, the weight of the water-absorbing gel dropped from the sample was measured, and the gel drop-off rate was calculated using the following formula.
Extruded gel amount (g)
Gel drop-off rate (%) = ――――――――――――――― x100
Gel amount before extrusion (g)

(Flexibility of water-absorbing composite)
Cut the water-absorbent composite into 2cm x 25cm, store it at 25 ° C and humidity at 50 ° C all day and night, and then measure the stiffness by the following procedure using the heart loop method used for the relatively soft fabric of JIS L-1096. did.
(1) A sample piece 42 was attached to a horizontal bar grip 41 shown in FIG. 12 in a heart loop shape so that the effective length of the sample piece 42 was 20 cm.
(2) After 1 minute, the distance L (cm) between the top of the horizontal bar and the lowest point of the loop was measured. Five samples were measured, and the average value was determined to be bending resistance.

(Peel test)
(1) A water-absorbing complex having a size of 5 cm × 5 cm was cut out and used as a sample.
(2) The base material outside the sample was pinched with one finger and the other base material was pinched with the other finger and slowly peeled off.
(3) The peeled state was observed visually.

(Water absorption peel test)
(1) A water absorbent composite having a size of 5 cm × 5 cm was cut out from the water absorbent composite.
(2) 10 ml of pure water was charged into a glass petri dish having a diameter of 10 cm.
(3) The water-absorbing composite was immersed in pure water in a petri dish for 10 minutes to obtain a water-absorbing sample.
(4) The outer substrate of the water-absorbing sample was pinched with one finger, and the other outer substrate was pinched with the other finger and slowly peeled off.
(5) The peeled state was observed visually.

The water-absorbing composite of the present invention has a high water absorption rate, and the water-absorbing polymer is uniformly fixed to the fiber before and after water absorption, and has a moderate flexibility. Moreover, according to the manufacturing method of the water absorptive complex of this invention, the water absorptive complex which has such a characteristic can be manufactured efficiently. In particular, since the water-absorbent composite of the present invention is coated with a base material with a water-absorbing polymer having adhesiveness, adhesiveness, and hygroscopicity, it can be prevented from adhering to a contact or sliding part such as a winding roller. , Line operability is excellent.
Therefore, the water-absorbent composite of the present invention is suitable for the production of sanitary materials such as disposable diapers and sanitary products, industrial materials necessary for absorption and retention of wastewater, agricultural materials such as freshness-retaining agents such as vegetables and water-retaining agents. Can be used. Moreover, the manufacturing method of the water absorptive complex of this invention can be implemented using an industrial manufacturing system, and is suitable also for mass production. Therefore, the present invention has high industrial applicability.

It is a perspective view of the nozzle used by the Example and the comparative example. 3 is a cross-sectional view showing a layer configuration of a water-absorbent composite of Example 2. FIG. 3 is a cross-sectional view showing a layer configuration of a water-absorbent composite of Example 3. FIG. 6 is a cross-sectional view showing a layer structure of a water-absorbent composite of Example 4. FIG. 6 is a cross-sectional view showing a layer structure of a water-absorbent composite of Example 5. FIG. It is the schematic which shows the measuring apparatus of the water absorption ability under pressure. It is a figure which shows the positional relationship of the sample at the time of measuring a water absorptive polymer drop-off rate. It is a perspective view which shows a low tap type shaking machine. It is sectional drawing of the measuring apparatus of a gel drop-off rate. It is a top view which shows the cutout part of a sample. It is sectional drawing which shows the state at the time of shaking in a gel drop-off rate measurement. It is the perspective view (a) which shows a bending / flexibility measuring apparatus, and the figure (b) which shows a sample attachment state. It is sectional drawing which shows the specific example of the laminated body using a water absorbing composite.

Explanation of sign

DESCRIPTION OF SYMBOLS 1 Substrate 2 Water-absorbing polymer 11 Sample disk for measurement 12 Cylinder with wire mesh 13 Petri dish 14 Weight 21 Water-impermeable sheet 22 Tissue 24 Water-absorbing composite 25 Tissue 26 Water-permeable fibrous material 41 Grasp 42 Sample piece 51 Surface smoothness Table 52 Water-absorbing composite 53 Cylindrical 54 Through hole 55 Acrylic plate 56 Disc 60 Water-absorbing composite 61 Standard mesh screen 62 Tape 65 Low-tap shaker 70 Water-absorbing composite 71 Center 72 Cut line 73 Sample 74 Acrylic plate 75 load

Claims (12)

It has a multilayer structure having a water-absorbing polymer layer between a first substrate and a second substrate, and the water-absorbing polymer layer is fixed to both the first substrate and the second substrate. Water-absorbing composite. The water absorbent polymer according to claim 1, wherein the water absorbent polymer constituting the water absorbent polymer layer has at least one of the following structures.
1) A bound particulate structure that is bound to each other while maintaining the particle shape
2) Webbed structure The water-absorbing composite according to claim 1 or 2, wherein the water-absorbing polymer particles constituting the binder-particulate water-absorbing polymer have an average particle size of 50 to 1000 µm. The water-absorbing polymer layer according to any one of claims 1 to 3, wherein the water-absorbing polymer layer has a web-like dispersion layer having a thickness of 50 to 1000 µm and an average diameter of 200 to 50000 µm. 4. The water-absorbing polymer layer has a web-like continuous layer having a thickness of 50 to 1000 [mu] m, an average pore diameter of 100 to 50000 [mu] m, and an open area ratio of 10 to 80%. A water-absorbent composite according to claim 1. The water-absorbing composite according to any one of claims 1 to 5, wherein at least one of the first substrate and the second substrate is a fibrous substrate. Forming in the gas phase droplets composed of a reaction mixture in which polymerization is initiated by mixing an aqueous solution of a polymerizable monomer that gives a water-absorbing polymer and a redox polymerization initiator, and forming the droplets of the polymerizable monomer It is dropped on the first base material, and the step of laying the second base material in a state where the average polymerization rate of the polymerizable monomer on the first base material is 10 to 80% is performed. The manufacturing method of the water absorptive complex in any one of 1-6. The method for producing a water-absorbing composite according to claim 7, wherein a pressure of 0.0001 to 1 MPa is applied when the second base material is laid. A sanitary material using the water-absorbent composite according to any one of claims 1 to 6. A diaper using the water-absorbent composite according to claim 1. The industrial material using the water absorptive complex in any one of Claims 1-6. Agricultural material using the water-absorbent composite according to any one of claims 1 to 6.

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