CN100372893C

CN100372893C - Water absorbent resin composition and production method thereof

Info

Publication number: CN100372893C
Application number: CNB2005100768318A
Authority: CN
Inventors: 鸟井一司; 中村将敏; 大河内弘子
Original assignee: Nippon Shokubai Co Ltd
Current assignee: Nippon Shokubai Co Ltd
Priority date: 2004-06-18
Filing date: 2005-06-17
Publication date: 2008-03-05
Anticipated expiration: 2025-06-17
Also published as: CN1709980A

Abstract

The water absorbent resin composition and the production method thereof according to the present invention are characterized by including: water absorbent resin particles having an internal cross-linked structure obtained by polymerizing a water-soluble unsaturated monomer; a nitrogenous ketone compound (A) and a bivalent and/or trivalent and/or tetravalent water-soluble metal salt, wherein a total amount of the nitrogenous ketone compound (A) and the bivalent and/or trivalent and/or tetravalent water-soluble metal salt ranges from 0.01 to 100 parts by mass with respect to 100 parts by mass of the water absorbent resin particles, thereby providing a water absorbent resin composition, having an excellent absorption capacity represented by a centrifuge retention capacity (CRC), an absorbency against pressure of 4.83 kPa (AAP) etc., having excellent liquid permeability and liquid diffusion properties such as salt flow capacity (SFC), having excellent fluidity at the time of moisture absorption, having an excellent damage resistance property, effectively suppressing occurrence of dusts, hardly bringing about permeation of added metal compounds into water absorbent resin particles, hardly bringing about segregation of added metal compounds.

Description

Water absorbency resin composition and preparation method thereof

Technical field

The present invention relates to a kind of paper nappy and sanitary towel of being adapted at, water absorbency resin composition and the manufacture method thereof used in the sanitary materials such as so-called incontinence pad etc.

Background technology

At paper nappy and sanitary towel, in the sanitary materials such as incontinence pad, for absorbed body fluid, being extensive use of with hydrophilic fibre such as paper pulp and absorbent resin is the cartridge of composition material.

In recent years, such sanitary material is making progress aspect high-performance and the slimming to some extent, and the absorbent resin usage quantity of every sanitary material and absorbent resin all have the tendency of increase with respect to all shared ratios of the cartridge that absorbent resin and hydrophilic fibre constituted.In other words, by reducing the little hydrophilic fibre of volume density, and use the big absorbent resin of water absorbing properties excellence and volume density more, can improve the ratio of absorbent resin in cartridge, when not reducing water regain, realize the slimming of sanitary material.

Yet merely from the angle of storing liquid, this hydrophilic fibre ratio is lower and sanitary material that the absorbent resin ratio is higher is preferred, but being actually used under the situation such as diaper, considers distribution of liquid and diffusion, and nature can go wrong.For example, absorbent resin can become the softish gel after suction is more, cause so-called gel blockage phenomenon, thereby significantly reduce the diffustivity of liquid in the sanitary material.For fear of the problems referred to above, keep the absorption characteristic of cartridge, need the ratio of restriction hydrophilic fibre and absorbent resin naturally, the slimming of sanitary material is also needed boundary to some extent.

As suppressing gel blockage, obtain flooding the method with the absorbent resin of diffustivity excellence, known method is to add metallic compound (metal-salt and metallic cation etc.) in absorbent resin.

The technical scheme of adding metallic compound with aqueous solution state (for example, opened clear 62-7745 communique (open day: on January 14th, 1987) referring to the spy, the spy opened clear 63-270741 communique (open day: on November 8th, 1988), the spy opened clear 64-56707 communique (open day: on March 3rd, 1989), Te Kaiping 9-124879 communique (open day: on May 13rd, 1997), the spy opened the 2001-96151 communique (open day: April 10 calendar year 2001), international open WO98/49221 (open day: on November 5th, 1998), international open WO 2000/53644 (open day: on September 14th, 2000), international open WO2000/53664 (open day: on September 14th, 2000), international open WO2001/74913 (open day: October 11 calendar year 2001), among the US2002/0128618 (open day: on September 12nd, 2002)), metal ingredient is difficult to soak into fully the inside to absorbent resin.Therefore, only not fairly obvious to improve the liquid flow general character and diffusible effect by adjusting addition.In addition, soak into to absorbent resin inside, also can reduce and do not add the assimilation ratio depressed and add the assimilation ratio depressed etc. for making metal ingredient.

Absorbent resin and metallic compound are done add tackiness agents such as water after mixing again technical scheme (for example, on November 14th, 1986), among the international open WO98/48857 (open day: on November 5th, 1998)) spy opened clear 61-257235 communique (open day:, because metal ingredient is dissolved in the tackiness agent such as water, therefore can soak into inside, but the raising liquid flow general character and diffusible effect are not fairly obvious to absorbent resin.In addition, the damage that causes owing to impact in the manufacturing processed, friction etc. can cause the more problem of powder.

Summary of the invention

The purpose of this invention is to provide a kind of water absorbency resin composition and manufacture method thereof that contains water-absorbent besin particles and metallic compound, described water absorbency resin composition is excellence aspect the specific absorption that is kept expressions such as capacity (CRC) and the absorptive capacity under 4.83kPa pressure (AAP) by separating centrifuge, the liquid flow general character and diffustivity aspect excellence by expressions such as salt solution water conservancy diversion (SFC), mobile excellence during moisture absorption, the height of anti-the damageability, suppress the effect excellence of powder, be difficult for causing that the metallic compound of interpolation separates.

The inventor has carried out meticulous research, found that, by with water-absorbent tree month purport particle with mix as the divalent of metallic compound and/or the water-soluble polyvalent metal salt of 3 valencys and/or 4 valencys and nitrogenous ketone compound, preferably in water-absorbent besin particles, add the water-soluble polyvalent metal salt of divalent and/or 3 valencys and/or 4 valencys, and then mix nitrogenous ketone compound, and, with respect to water-absorbent besin particles, total usage quantity of the water-soluble polyvalent metal salt of divalent and/or 3 valencys and/or 4 valencys and nitrogenous ketone compound is in a spot of specified range less than equivalent, thereby can address the above problem, so far finish the present invention.

In addition, known a kind of water-absorbing polymer composition, it is characterized in that, said composition contains alum, Tai-Ace S 150, at least a in exsiccated alum and the dry Tai-Ace S 150, (spy opens 2003-306609 communique (open day: on October 31st, 2003)) for urea and water-absorbing polymer, the purpose of this technical scheme is to make water-absorbing polymer to have germ resistance, deodorization, therefore, in the water-absorbing polymer composition, alum, Tai-Ace S 150, the total content of at least a and urea in exsiccated alum and the dry Tai-Ace S 150 be 50～95 weight % such a large amount of (promptly, this amount is more than the equimultiple of water-absorbing polymer weight), according to such proportion of composing, can't realize task of the present invention fully.

In addition, April 10 calendar year 2001), the spy opens flat 10-273602 communique (open day: on October 13rd, 1998)) (spy opened the 2001-96151 communique (open day: to known a kind of water absorbency resin composition that contains the metallic compound of absorbent resin and 4 valencys, performances such as the absorption characteristic of the water absorbency resin composition that is obtained by this technical scheme and the liquid flow general character are not ideal enough, thereby can't realize task of the present invention fully.

That is to say, the present invention relates to a kind of water absorbency resin composition, said composition comprises the water-absorbent besin particles with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer, the nitrogenous ketone compound (A) (but not containing carboxyl) with structure shown in the general formula (1) and the water-soluble polyvalent metal salt of divalent and/or 3 valencys and/or 4 valencys, it is characterized in that, with respect to 100 mass parts water-absorbent besin particles, nitrogenous ketone compound (A) is 0.01～100 mass parts with the total amount of the water-soluble polyvalent metal salt of divalent and/or 3 valencys and/or 4 valencys.

In addition, the present invention relates to a kind of manufacture method of water absorbency resin composition, this method comprises, in water-absorbent besin particles with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer, mix and have the nitrogenous ketone compound (A) (but not containing carboxyl) of structure shown in the general formula (1) and the water-soluble polyvalent metal salt of divalent and/or 3 valencys and/or 4 valencys, it is characterized in that, with respect to 100 mass parts water-absorbent besin particles, mixing total amount is the nitrogenous ketone compound (A) of 0.01～100 mass parts and the water-soluble polyvalent metal salt of divalent and/or 3 valencys and/or 4 valencys.

In addition, the present invention relates to a kind of manufacture method of water absorbency resin composition, it is characterized in that, in water-absorbent besin particles, mix the powder of the water-soluble polyvalent metal salt of the powder of nitrogenous ketone compound (A) (but not containing carboxyl) and divalent and/or 3 valencys and/or 4 valencys with structure shown in the general formula (1) with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer.

In addition, the present invention relates to a kind of manufacture method of water absorbency resin composition, it is characterized in that, the water-absorbent besin particles that will have the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer mixes with a kind of fraction, and this fraction contains the nitrogenous ketone compound (A) (but not containing carboxyl) of structure shown in (1) that has general formula and the water-soluble polyvalent metal salt of divalent and/or 3 valencys and/or 4 valencys.

In addition, the present invention relates to a kind of manufacture method of water absorbency resin composition, it is characterized in that the aqueous solution of the water-absorbent besin particles that will have an internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer and the nitrogenous ketone compound (A) (but not containing carboxyl) that contains the structure shown in (1) that has general formula and contain divalent and/or the aqueous solution of the water-soluble polyvalent metal salt of 3 valencys and/or 4 valencys mixes.

In addition, the present invention relates to a kind of manufacture method of water absorbency resin composition, it is characterized in that, to contain in the water-soluble polyvalent metal salt of nitrogenous ketone compound (A) (but not containing carboxyl) with structure shown in the general formula (1) and divalent and/or 3 valencys and/or 4 valencys any and mix with water-absorbent besin particles, another kind ofly do mixed with this water-absorbent besin particles with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer with aqueous solution form.

In addition, the present invention relates to a kind of granular water absorbency resin composition, this water absorbency resin composition comprises water-absorbent besin particles, wetting ability organic compound and the water-soluble polyvalent metal salt with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer, it is characterized in that the liquid velocity of diffusion (LDV) of said composition is 2.1～10.0mm/s.

The content of following discloses will make other purpose of the present invention, feature and advantage more clear obviously.In addition, by the reference the description of the drawings, scope of the present invention will be clearer.

The simple declaration of accompanying drawing

Fig. 1 is the apparatus structure sketch that is used to measure one of the water-retaining agent performance that the present invention relates to AAP.

Fig. 2 is the apparatus structure sketch that is used to measure one of the water-retaining agent performance that the present invention relates to SFC.

The preferred forms of invention

Below the present invention is described in detail, but scope of the present invention is not subjected to the restriction of these explanations, so long as in the scope of not damaging purport of the present invention, even also can be outside following example through suitably being implemented after changing.

In addition, in the following description, " divalent and/or 3 valencys and/or the 4 value water-soluble polyvalent metal salts " that contained in the water absorbency resin composition that the present invention relates to only are designated as water-soluble polyvalent metal salt.

[water-absorbent besin particles]

The water-absorbent besin particles that uses among the present invention is the particle that can obtain water-insoluble and water-swollen hydrogel formation property polymkeric substance (the following absorbent resin that also is referred to as) by the polymerization water-soluble unsaturated monomer, the specific absorption of its physiological saline (the NaCl solution of 0.90 quality %) be at least 5 times or more than, this particle is spherical or atypic particle shape.In addition, in the present invention, only water-absorbent besin particles is called absorbent resin.

Example as water-insoluble and water-swollen hydrogel formation property polymkeric substance, for example part neutralizes acrylic acid polymer (US4625001 crosslinked, US4654039, US5250640, US5275773, EP456136 etc.), crosslinked part neutral starch-acrylic acid-grafted polymkeric substance (US4076663), iso-butylene-maleic acid (US4389513), saponified (US4124748) of vinyl-acetic ester-acrylic copolymer, the hydrolysate (US3959569) of acrylamide (being total to) polymers, the hydrolysate of acrylonitrile polymer (US3935099) etc.

The water-absorbent besin particles that preferably constitutes of the water-absorbent besin particles of Shi Yonging in the present invention by polyacrylic acid (salt) class cross-linked polymer, this cross-linked polymer is to obtain by the monomer that polymerization contains vinylformic acid and/or its salt, with vinylformic acid and/or acrylate as structural unit.Polyacrylic acid among the present invention (salt) class cross-linked polymer obtains by the following monomer of polymerization: in the entire infrastructure unit, this monomer contains 50 moles of % or above vinylformic acid and/or its salt, be preferably 70 moles of % or more than, more preferably 90 moles of % or more than.In addition, preferred 50～90 moles of % of the acidic-group in the polymkeric substance are neutralized, and more preferably have 60～80 moles of % to be neutralized, and salt for example is an alkali metal salts such as sodium, potassium, lithium, ammonium salt and amine salt etc.Be preferably sodium salt.Can carry out under the free state before polymerization for forming the neutralization that salt carried out, also can carry out under the state of polymer in polymerization process and after the polymerization, can also carry out together.

As polyacrylic acid (salt) the class cross-linking copolymer that water-absorbent besin particles of the present invention preferably uses, also can be the polymkeric substance that in being used as the monomer (vinylformic acid and/or its salt) of principal constituent, obtains with other monomer copolymerization of choosing wantonly.As other monomeric example, for example be anionic property unsaturated monomer and salt thereof such as methacrylic acid, toxilic acid, vinyl sulfonic acid, styrene sulfonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic acid, 2-(methyl) acrylamide ethyl sulfonic acid, 2-(methyl) acrylamide propanesulfonic acid; Acrylamide, Methacrylamide, N-ethyl (methyl) acrylamide, N-n-propyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, poly-(methyl) vinylformic acid glycol ester of methoxyl group, polyethyleneglycol (methyl) acrylate, vinyl pyridine, N-vinyl pyrrolidone, N-acryl piperidines, N-acryl tetramethyleneimine, N-vinyl acetamide etc. contain the unsaturated monomer of nonionic hydrophilic group; (methyl) vinylformic acid-N, N-dimethylamino ethyl ester, (methyl) vinylformic acid-N, N-diethylamino ethyl ester, (methyl) vinylformic acid-N, N-dimethylamino propyl ester, (methyl) vinylformic acid-N, cationic unsaturated monomers such as N-dimethylamino propyl ester and quaternary ammonium salt thereof.Monomeric usage quantity beyond vinylformic acid and/or its salt is preferably all monomeric 0～30 mole of %, more preferably is 0～10 mole of %.

The water-absorbent besin particles that uses among the present invention is the cross-linked polymer with internal crosslinking structure.

In the water-absorbent besin particles that the present invention uses, introduce the method for crosslinking structure, for example, the method of not using linking agent and introducing by self-crosslinking, and by making the internal crosslinking agent that has 2 or above polymerizability unsaturated group and/or 2 or above reactive group in the per molecule carry out method that copolymerization or reaction introduce etc.The preferred employing makes internal crosslinking agent carry out the method for copolymerization or reaction.

Example as internal crosslinking agent, for example, N, N '-methylene-bis (methyl) acrylamide, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, three (methyl) vinylformic acid glyceryl ester, the vinylformic acid glyceral methacrylate, the trimethylolpropane tris of oxyethane modification (methyl) acrylate, tetramethylolmethane (methyl) acrylate, Dipentaerythritol (methyl) acrylate, the trishydroxymethyl urate, triallyl isocyanurate, the triallyl phosphoric acid ester, triallylamine, poly-(methyl) allyloxy paraffinic hydrocarbons, (gathering) ethylene glycol diglycidylether, glycerin diglycidyl ether; Ethylene glycol, polyoxyethylene glycol, 1, polyalcohols such as 4-butyleneglycol, propylene glycol, glycerine, tetramethylolmethane; Quadrol, polymine, (methyl) vinylformic acid glycidyl ether etc.This internal crosslinking agent can only use a kind of, also can use 2 kinds or more than.Wherein, consider the water absorption character of the water-absorbent besin particles that obtains, preferably need to use compound as internal crosslinking agent with 2 or above polymerisable unsaturated group, in whole monomers, the usage quantity of this internal crosslinking agent is preferably 0.005～3 mole of %, more preferably 0.01～1.5 mole of %.

When polymerization, can also add hydrophilic macromolecules such as starch-Mierocrystalline cellulose, starch-cellulosic derivative, polyvinyl alcohol, polyacrylic acid (salt), the crosslinked body of polyacrylic acid (salt), and Hypophosporous Acid, 50 chain-transfer agents such as (salt).

For the absorbent resin that obtains using among the present invention refers to particle, when polymerization is the monomer of main component with above-mentioned vinylformic acid and/or its salt, can carry out mass polymerization, inverse suspension polymerization, precipitation polymerization, angle from aspect of performance and easy controlled polymerization, preferably above-mentioned monomer is formed the aqueous solution, carry out aqueous solution polymerization.The for example record to some extent in US4625001, US4769427, US4873299, US4093776, US4367323, US4446261, US4683274, US4690996, US4721647, US4738867, US4748076, EP1178059 etc. of described polymerization process.

When the beginning polymerization, can use Potassium Persulphate, ammonium persulphate, Sodium Persulfate, tert-butyl hydroperoxide, hydrogen peroxide, 2, radical polymerization initiators such as 2 '-azo two (2-amidine propane) dihydrochloride, ultraviolet ray and electron beam etc. can the activatory rays.In addition, using under the radical polymerization initiator situation, also can mix reductive agents such as using S-WAT, sodium bisulfite, ferrous sulfate, L-xitix to carry out reductionoxidation polymerization.Whole relatively monomers, the usage quantity of this polymerization starter is preferably 0.001～2 mole of %, more preferably 0.01～0.5 mole of %.

The normally unsetting broken shape of shape of the water-absorbent besin particles that obtains by above-mentioned polymerization, spherical, fibrous, bar-shaped, closely spherical, flats etc., because the water-absorbent besin particles that uses among the present invention is a particulate state, the particle of the unsetting broken shape that obtains by pulverizing after if use is dry, effect of the present invention can get a greater increase, and is preferred so therefore.

The water-absorbent besin particles that uses among the present invention has preferably carried out surface-crosslinked processing at its surf zone.

Surface-crosslinked processing can be undertaken by using surface crosslinking agent, also can be undertaken by other known surface cross-linking treatment method.

As the surface crosslinking agent that can be used for surface-crosslinked processing, for example have the organic surface crosslinking agent and the polyvalent metal compounds of 2 functional groups that can react with the functional group in the water-absorbent besin particles, particularly carboxyl at least.For example, ethylene glycol, glycol ether, propylene glycol, triglycol, Tetraglycol 99, polyoxyethylene glycol, 1, ammediol, dipropylene glycol, 2,2,4-trimethylammonium-1, the 3-pentanediol, polypropylene glycol, glycerine, Polyglycerine, 2-butylene-1, the 4-glycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 2-cyclohexanedimethanol, 1, the 2-hexalin, TriMethylolPropane(TMP), diethanolamine, trolamine, poly(propylene oxide), ethylene oxide-propylene oxide block copolymer, polyol compound such as tetramethylolmethane and Sorbitol Powder, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, the glycerine polyglycidyl ether, two glycerine polyglycidyl ethers, the poly-glycerine polyglycidyl ether, propylene glycol diglycidylether, epoxy compounds such as polypropylene glycol diglycidyl ether and glycidyl ether; Polyamine compounds such as quadrol, Diethylenetriamine, three second tetramines, tetraethylene-pentamine, five second hexamines and polymine and inorganic salt thereof or organic salt (for example azetidine salt etc.); 2, multicomponent isocyanate compounds such as 4-benzylidene vulcabond and hexamethylene diisocyanate; 1, Duo Yuan oxazoline compounds such as 2-Ya Yi Ji bisoxazoline; Carbonic acid derivativess such as urea, Thio Urea, guanidine, Dyhard RU 100,2-oxazolidone; 1,3-dioxane pentadiene-2-ketone, 4-methyl isophthalic acid, 3-dioxolane-2-ketone, 4,5-dimethyl-1,3-dioxolane-2-ketone, 4,4-dimethyl-1,3-dioxolane-2-ketone, 4-ethyl-1,3-dioxolane-2-ketone, 4-methylol-1,3-dioxolane-2-ketone, 1,3-diox-2-ketone, 4-methyl isophthalic acid, 3-diox-2-ketone, 4,6-dimethyl-1,3-diox-2-ketone and 1, alkylene carbonate ester cpds such as 3-dioxane-2-heptanone; Halogenated epoxide and polyamine adductss (for example カイメ Application (registered trademark) of ば Ha-キュレス production) thereof such as Epicholorohydrin, epibromohydrin and Alpha-Methyl Epicholorohydrin; Silane coupling agent such as γ-Huan Yangbingyangbingjisanjiayangjiguiwan and γ-An Jibingjisanyiyangjiguiwan; Oxetane compounds such as 3-methyl-3-oxetane methanol, 3-ethyl-3-oxetane methanol, 3-butyl-3-oxetane methanol, 3-methyl-3-trimethylene oxide ethanol, 3-ethyl-3-trimethylene oxide ethanol, 3-butyl-3-trimethylene oxide ethanol, 3-chloromethyl-3-methyl trimethylene oxide, 3-chloromethyl-3-ethyl trimethylene oxide, polynary oxetane compound etc.This surface crosslinking agent can only use a kind of, also can be with 2 kinds or above being used in combination.Wherein, from safe, the wetting ability angle that can increase the water-absorbent besin particles surface is set out, and polyvalent alcohol is preferred.In addition, by using polyvalent alcohol, the affinity of the water-soluble polyvalent metal salt on water-absorbent besin particles surface is better, by the interaction on polyvalent alcohol residue and divalent, 3 valencys and/or 4 value water-soluble polyvalent metal salt surfaces, divalent, 3 valencys and/or 4 value water-soluble polyvalent metal salts can be present in the water-absorbent besin particles surface more equably.

With respect to the solids component of the water-absorbent besin particles of 100 mass parts, the usage quantity of surface crosslinking agent is preferably 0.001～5 mass parts.

In the time of surface crosslinking agent and water-absorbent besin particles blended, can also make water.With respect to the solids component of 100 mass parts water-absorbent besin particles, the usage quantity of water is preferably greater than 0.5 and less than 10 mass parts, more preferably 1 mass parts～5 mass parts.

When blending surface linking agent and its aqueous solution, also can use hydrophilic organic solvent and as the third material of mixed aid.

When using hydrophilic organic solvent, for example, can enumerate lower alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol; Ketones such as acetone; Ethers such as diox, tetrahydrofuran (THF), methoxyl group (gathering) methylene glycol; ∈-hexanolactam, N, amidess such as dinethylformamide; Sulfoxide classes such as dimethyl sulfoxide (DMSO); Ethylene glycol, glycol ether, propylene glycol, triglycol, Tetraglycol 99, polyoxyethylene glycol, 1, ammediol, dipropylene glycol, 2,2,4-trimethylammonium-1,3-pentanediol, poly-pentanediol, glycerine, Polyglycerine, 2-butylene-1,4-glycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,2-cyclohexanedimethanol, 1, polyvalent alcohols such as 2-hexalin, TriMethylolPropane(TMP), diethanolamine, trolamine, poly(propylene oxide), ethylene oxide-propylene oxide block copolymer, tetramethylolmethane and Sorbitol Powder etc.The usage quantity of hydrophilic organic solvent depends on kind and particle diameter, the water ratio etc. of water-absorbent besin particles, and the solids component with respect to the water-absorbent besin particles of 100 mass parts is preferably 10 mass parts or following, more preferably 0.1 mass parts～5 mass parts.What exist as the third material in addition, can be disclosed mineral acid, organic acid, polyamino acid etc. among the EP0668080.This mixed aid also can play surface crosslinking agent, and preferably those can not make the material that the water absorbing properties of surface-crosslinked back water-absorbent besin particles reduces.Boiling point is lower than 150 ℃ volatility alcohols and can vapors away when surface-crosslinked processing, can not stay residue, is special ideal therefore.

For more uniform mixing water-absorbent besin particles and surface crosslinking agent, when mixing water-absorbent besin particles and surface crosslinking agent, the water-soluble inorganic bases (preferred as alkali salt, ammonium salt, alkali metal hydroxide, ammonium or its oxyhydroxide) of non-crosslinked and irreducibility territory metal-salt pH buffer reagent (preferred supercarbonate, dihydrogen phosphate, hydrophosphate etc.) are coexisted as wherein.Its usage quantity depends on the kind of water-absorbent besin particles and particle diameter etc., with respect to the solids component of 100 mass parts water-absorbent besin particles, is preferably 0.005～10 mass parts, more preferably 0.05～5 mass parts.

There is no particular limitation to the blending means of mixing water-absorbent besin particles and surface crosslinking agent, for example, in hydrophilic organic solvent, flood water-absorbent besin particles, itself and the surface crosslinking agent of optional dissolved in water and/or hydrophilic organic solvent are carried out the blended method, thereby the surface crosslinking agent that water-absorbent besin particles directly sprays or dropping is dissolved in water and/or the hydrophilic organic solvent is carried out blended method etc.

After mixing water-absorbent tree purport particle and surface crosslinking agent, preferably add processing usually, carry out crosslinking reaction then.Above-mentioned heat treated temperature is preferably 40 ℃～250 ℃, more preferably 150 ℃～250 ℃ by the surface crosslinking agent decision of using.If heat treated temperature is lower than 40 ℃, can causes adding the absorption characteristics of depressing such as specific absorption and be difficult to be fully improved.If heat treated temperature surpasses 250 ℃, then note the situation that causes various performances reductions owing to the deterioration of water-absorbent besin particles.Heat treatment time is preferably 1 minute～and 2 hours, more preferably 5 minutes～1 hour.

When water-absorbent besin particles of the present invention is heat-treated, heat-treating methods, for example EP530517, EP603292, international open WO95/05856 etc. put down in writing, the method that again water-absorbent besin particles is heated after drying.

Particle diameter and size distribution to the water-absorbent besin particles that uses among the present invention have no particular limits, if particles used particle diameter is less, and the size distribution of small particle size composition is more, and then absorptive character such as specific absorption are significantly improved, and are preferred therefore.

The mass median diameter of the water-absorbent besin particles that uses among the present invention is preferably 100～600 μ m, more preferably 200～500 μ m.If mass median diameter is outside the scope of 100～600 μ m, then the liquid flow general character and diffustivity significantly reduce, and absorption rate also significantly reduces, and when for example using in diaper, can cause the leakage of liquid.In addition, can obtain the particulate of the water-absorbent besin particles of 300 μ m or following particle diameter by granulation, thereby can carry out the granularity adjustment to the water-absorbent besin particles that obtains, also can use such water-absorbent besin particles, this particle is that the granulation thing that mixes a part of particulate in the unsetting broken shape particle of the primary particle that pulverizing obtains obtains.Under the granulation principle condition of mixing a part of water-absorbent besin particles, can obtain the more excellent water absorbency resin compositions of absorption characteristic such as absorption speed, kapillary specific absorption.The combined amount of the granulation thing of particulate be preferably 5 quality % or more than, more preferably 10 quality % or more than, more preferably 15 quality % or more than.

As the manufacture method of particulate granulation thing, can use the known technology of regeneration of particle.For example can use the method (US6228930) of the particulate mixing after drying of warm water and water-absorbent besin particles; the particulate that makes water-absorbent besin particles with carry out polymeric method (US5264495) after monomer solution mixes; in the particulate of water-absorbent besin particles, add entry; process for granulating (EP844270) on specific carrier then; make the particulate of water-absorbent besin particles form very moistening non-crystalline gel; carry out drying then; the method of pulverizing (US4950692); make the particulate and the polymeric gel of water-absorbent besin particles carry out blended method (US5478879) etc., preferably use the above-mentioned method that makes warm water and the particulate mixing after drying of water-absorbent besin particles.In addition, particle diameter is directly represented by the fractionated sieve mesh.

The water-absorbent besin particles that the present invention uses, its separating centrifuge keep capacity (CRC) be preferably 5 (g/g) or more than, more preferably 10 (g/g) or more than, more preferably 20 (g/g) or more than, be preferably especially 25 (g/g) or more than.There is no particular limitation to higher limit, be preferably 50 (g/g) or below, more preferably 45 (g/g) or below, more preferably 40 (g/g) or below.When separating centrifuge kept capacity (CRC) less than 10 (g/g), absorbed dose was not suitable for sanitary materials such as diaper very little.In addition, when separating centrifuge keeps capacity (CRC) greater than 50 (g/g), then be difficult to obtain the water absorbency resin composition of liquid flow general character excellence.

The water-absorbent besin particles that the present invention uses, its absorptive capacity under the 4.83kPa pressure (AAP) be preferably 18 (g/g) or more than, more preferably 20 (g/g) or more than, more preferably 22 (g/g) or more than.If the absorptive capacity under 4.83kPa pressure (AAP) less than 18 (g/g), then is difficult to obtain the water absorbency resin composition of liquid flow general character excellence.

The salt solution water conservancy diversion (SFC) of the water-absorbent besin particles that uses among the present invention is preferably 10 (* 10 ^-7Cm ³Sg ^-1) or more than, more preferably 30 (* 10 ^-7Cm3sg ^-1) or more than, more preferably 50 (* 10 ^-7Cm ³Sg ^-1) or more than.When salt solution water conservancy diversion (SFC) less than 10 (* 10 ^-7Cm ³Sg ^-1) time, even add water-soluble polyvalent metal salt and nitrogenous ketone compound (A), also can't improve the liquid flow general character.

The water soluble amount of the water-absorbent besin particles that uses among the present invention is preferably 35 quality % or following, more preferably 25 quality % or following, more preferably 15 quality % or following.Surpass under the 35 quality % situations in the water soluble amount, gel-strength dies down, liquid flow general character deterioration.In addition, when using for a long time in diaper, absorption characteristic (CRC, AAP etc.) can reduce ageingly.

[water absorbency resin composition]

The present invention relates to a kind of water absorbency resin composition, this water absorbency resin composition comprises the water-absorbent besin particles with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer, nitrogenous ketone compound (A) (but not containing carboxyl) and the water-soluble polyvalent metal salt that contains structure shown in the general formula (1), it is characterized in that, with respect to 100 mass parts water-absorbent besin particles, nitrogenous ketone compound (A) is 0.01～100 mass parts with the total amount of the water-soluble polyvalent metal salt of divalent, 3 valencys and/or 4 valencys.

The present invention relates to a kind of water absorbency resin composition, this water absorbency resin composition comprises water-absorbent besin particles, wetting ability organic compound and the water-soluble polyvalent metal salt with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer, it is characterized in that liquid velocity of diffusion (LDV) is 2.1～10.0mm/s.

In addition, preferred divalent of above-mentioned water-soluble polyvalent metal salt and/or 3 valencys.

As the wetting ability organic compound, for example water miscible organic compound.There is no particular limitation to it, particularly, and the surface crosslinking agent of enumerating more than for example, nitrogenous ketone compound (A), organic acid etc.The wetting ability organic compound particularly preferably is nitrogenous ketone compound (A).The wetting ability organic compound can only use a kind, also can be with 2 kinds or above being used in combination.

The solubleness of wetting ability organic compound in 1atm, 25 ℃ of following 100g water be preferably 10g or more than, more preferably 20g or more than, more preferably 40g or more than.

The molecular weight of wetting ability organic compound is preferably 45～10000g/ mole, more preferably 59～1000g/ mole, more preferably 60～150g/ mole.

In the water absorbency resin composition that the present invention relates to, with respect to 100 mass parts water-absorbent besin particles, the total amount of wetting ability organic compound and water-soluble polyvalent metal salt is 0.01～100 mass parts, be preferably 0.05～50 mass parts, more preferably 0.1～10 mass parts is preferably 0.5～5 mass parts especially.If the total amount of wetting ability organic compound and water-soluble polyvalent metal salt is less than 0.01 mass parts, then the liquid flow general character and diffustivity and blocking rate to improve effect abundant inadequately, if greater than 100 mass parts, then absorption characteristic such as CRC and AAP can significantly reduce.

In the water absorbency resin composition that the present invention relates to, the mass ratio of the content of wetting ability organic compound and the content of water-soluble polyvalent metal salt is preferably 1: 10～and 10: 1, more preferably 3: 7～7: 3.If the mass ratio of wetting ability organic compound content and water-soluble polyvalent metal salts contg is outside 1: 10～10: 1 scope, then the liquid flow general character and diffustivity and blocking rate to improve effect abundant inadequately, and absorption characteristics such as CRC and AAP can significantly reduce.

In the water absorbency resin composition that the present invention relates to,, preferably at least a portion on water-absorbent besin particles surface, apply wetting ability organic compound and water-soluble polyvalent metal salt in order to give full play to effect of the present invention.In addition, more preferably this coating is not that all surfaces to water-absorbent besin particles applies.If apply all surfaces of water-absorbent besin particles, then absorption rate (for example, separating centrifuge keeps capacity (CRC) and the absorptive capacity under 4.83kPa pressure (AAP) etc.) can significantly reduce.

In the water absorbency resin composition that the present invention relates to, the wetting ability organic compound preferably contains polyvalent alcohol (material of enumerating in the above-mentioned surface crosslinking agent).

In the water-absorbent tree resin combination that the present invention relates to, the wetting ability organic compound preferably contains nitrogenous ketone compound (A).

As previously mentioned, the water-absorbent besin particles with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer has preferably carried out surface-crosslinked processing.

Nitrogenous ketone compound (A) is the nitrogenous ketone compound (A) (but not containing carboxyl) with structure shown in the general formula (1), for example, and diazanyl acid alkyl esters such as alkyl carbamates such as Urethylane, urethanum, carbazic acid ethyl ester; The compound that the nitrogen of amide group such as fatty acid amides such as methane amide, ethanamide, propionic acid amide, N,N-dimethylacetamide, N-methylacetamide is replaced by alkyl; Acrylic amides such as (methyl) acrylamide, N-N-isopropylacrylamide, N,N-DMAA; The 2-oxazolidone; 3-methyl-2-oxazolidone, 3-alkyl-2-oxazolidone, 4-methyl-2-oxazolidone, 4-alkyl-2-oxazolidine ketones such as 2-oxazolidone; 2, oxazolidinedione classes such as 5-oxazolidinedione; 2-Pyrrolidone classes such as 2-Pyrrolidone, 3-hydroxymethyl-2-Pyrrolidone, 3-alkyl-2-Pyrrolidone, 4-alkyl-2-Pyrrolidone, 5-alkyl-2-Pyrrolidone; 2, pyrrolidine-diones classes such as 5-pyrrolidine-diones; Urea and/or its derivative with structure shown in the general formula (2), or the like.The urea and/or its derivative that preferably have structure shown in the general formula (2).Being eager to excel owing to have the nitrogenous ketone compound (A) that the interaction ratio of the urea of structure shown in the general formula (2) and/or its derivative and water-soluble polyvalent metal salt has a structure shown in the general formula (1), is preferred therefore.

The preferably water miscible material of nitrogenous ketone compound (A) (urea and/or its derivative that preferably have structure shown in the general formula (2)), solubleness in 1atm and 25 ℃ of following 100g water be preferably 10g or more than, more preferably 20g or more than, more preferably 40g or more than.

The molecular weight of nitrogenous ketone compound (A) (urea and/or its derivative that preferably have structure shown in the general formula (2)) is preferably 45～10000g/ mole, more preferably 59～1000g/ mole, more preferably 60～150g/ mole.

Nitrogenous ketone compound (A) (urea and/or its derivative that preferably have structure shown in the general formula (2)) preferred security height, stable material.

Particularly, have the urea of structure shown in the general formula (2) and/or its derivative for example preferably: urea; N-methyl urea, N-ethyl urea, N, N '-dimethyl urea, ethylidene urea, N, N-dimethyl urea etc. combines the urea derivative of alkyl on the nitrogen of urea; Hydroxycarbamide, N, N '-dihydroxyl urea, N-hydroxy-n '-methyl urea, N-hydroxy-n-methyl urea etc. combine the urea derivative of hydroxyl on the nitrogen of urea; Amino urea, N-amino-N '-methyl urea, N-amino-N-methyl urea etc. combine amino urea derivative on the nitrogen of urea; Hydroxymethyl urea; Cyano methyl urea; Nitro urea; The formamido group hydrazine; The carbonic acid hydrazine; Formyl urea; Formamido group-1-azacyclopropane; N, N '-two boryl urea etc. combines the urea derivative of boron on the nitrogen of urea; Oxygen silicon base urea etc. combines the urea derivative 1 of silicon, 3-diaza-2-cyclobutanone on the nitrogen of urea; Nitro urea; 2-propynyl urea; Phosphoranyl urea; Vinyl urea; Methylene radical urea; Formyl cyano group acid amides (カ Le ボニソシア Na チジ Star Network アミ De); 1,2,4-oxygen diaza-3-cyclobutanone; Amino methyl urea; Ethynyl urea etc.More preferably: urea; N-methyl urea, N-ethyl urea, N, N '-dimethyl urea, ethylidene urea, N, N-dimethyl urea etc. combines the urea derivative of alkyl on the nitrogen of urea; Hydroxycarbamide, N, N '-dihydroxyl urea, N-hydroxy-n '-methyl urea, N-hydroxy-n-methyl urea etc. combine the urea derivative of hydroxyl on the nitrogen of urea.Further preferably: urea; N-methyl urea, N-ethyl urea, N, N '-dimethyl urea, ethylidene urea, N, N-dimethyl urea etc. combines the urea derivative of alkyl on the nitrogen of urea.Wherein, because the interaction of urea and water-soluble polyvalent metal salt is strong especially, and also stronger with the affinity of water, be particularly preferred therefore.

In addition, when in the aqueous solution, mixing with water-soluble polyvalent metal salt, the urea and/or the preferably stable homogeneous solution of its derivative that have the ketone compound that contains nitrogen (A) of structure shown in the general formula (1) and have structure shown in the general formula (2).

Water-soluble polyvalent metal salt is the valent metal-salt with divalent, 3 valencys and/or 4 valencys, and is preferably pulverous.Consider that the water absorbency resin composition that the present invention relates to will be used for the cartridge that sanitary material such as diaper is used, therefore can not carry out water absorbency resin composition painted, the preferred employing to the low material of human toxicity tree.

For the effect that makes water-soluble polyvalent metal salt can more effectively continue when absorbing liquid for a long time, preferably in the pure water of normal temperature, dissolve the water-soluble polyvalent metal salt that obtains with 5 quality % or above concentration, more preferably use with 10 quality % or more than, the further preferably material that obtains with 20 quality % or above dissolving.

The water-soluble polyvalent metal salt of operable divalent and/or 3 valencys for example is among the present invention: aluminum chloride, poly aluminium chloride, Tai-Ace S 150, aluminum nitrate, bisulphate aluminium potassium, bisulphate aluminium sodium, potassium alum, ammonium alum, sodium alum, sodium aluminate, calcium chloride, nitrocalcite beggar, magnesium chloride, sal epsom, magnesium nitrate, zinc chloride, zinc sulfate, zinc nitrate, iron(ic) chloride (III), Cerium II Chloride (III), ruthenium chloride (III), Yttrium trichloride (III), chromium chloride (III) etc.In addition, from the solvability angle of absorption liquids such as urine, the also preferred salt that contains crystal water that uses.Particularly preferably be aluminum compound, wherein, preferably aluminum chloride, poly aluminium chloride, Tai-Ace S 150, aluminum nitrate, bisulphate aluminium potassium, bisulphate aluminium sodium, potassium alum, ammonium alum, sodium alum, sodium aluminate, particularly preferably be Tai-Ace S 150,18 hydrazine aluminum sulfate salt, 14-18 hydrazine aluminum sulfate salt etc. contain that the powder of crystal water is best suited for using.These materials can only use a kind, also can be with 2 kinds or above being used in combination.

In addition, the water-soluble polyvalent metal salt of operable 4 valencys for example is among the present invention: 8 hydration basic zirconium chlorides, zirconium carbonate ammonium, potassium zirconium carbonate, sodium zirconium carbonate, hydration zirconium sulfate, acetic acid zirconium, zirconium nitrate, basic zirconium chloride, trolamine titanium, lactic acid titanium.In addition, from the solvability angle of absorption liquids such as urine, the also preferred salt that contains crystal water that uses.More preferably 8 hydration chlorine zirconium chlorides, hydration zirconium sulfate.These materials can only use a kind, also can be with 2 kinds or above being used in combination.

Operable water-soluble polyvalent metal salt is preferably granular among the present invention, and from the Combination angle, its particle diameter preferably particle diameter than water-absorbent besin particles is little.Mass median diameter is preferably 500 μ m or following, more preferably 400 μ m or following.From performance perspective, further preferable particle size be 150 μ m or following particle account for whole water-soluble polyvalent metal salts 20 quality % or more than, most preferably account for 30 quality % or more than.

In the water absorbency resin composition that the present invention relates to, with respect to 100 mass parts water-absorbent besin particles, the total amount of nitrogenous ketone compound (A) and water-soluble polyvalent metal salt is 0.01～100 mass parts, be preferably 0.05～50 mass parts, more preferably 0.1～10 mass parts is preferably 0.5～5 mass parts especially.If the total amount of nitrogenous ketone compound (A) and water-soluble polyvalent metal salt is less than 0.01 mass parts, then the liquid flow general character and diffustivity and blocking rate to improve effect abundant inadequately, if greater than 100 mass parts, then absorption characteristic such as CRC and AAP can significantly reduce.

In the water absorbency resin composition that the present invention relates to, the mass ratio of nitrogenous ketone compound (A) content and water-soluble polyvalent metal salts contg is preferably 1: 10～and 10: 1, more preferably 3: 7～7: 3.If the mass ratio of nitrogenous ketone compound (A) content and water-soluble polyvalent metal salts contg is outside 1: 10～10: 1 scope, then the liquid flow general character and diffustivity and blocking rate to improve effect abundant inadequately, and absorption characteristics such as CRC and AAP can significantly reduce.

In the water absorbency resin composition that the present invention relates to,, preferably at least a portion surface of water-absorbent besin particles, apply above-mentioned nitrogenous ketone compound (A) and water-soluble polyvalent metal salt for giving full play to effect of the present invention.In addition, more preferably not that all surfaces to water-absorbent besin particles applies.If apply all surfaces of water-absorbent besin particles, then absorption rate (for example, separating centrifuge keeps capacity (CRC) and the absorptive capacity under 4.83kPa pressure (AAP) etc.) can significantly reduce.

The mass median diameter of the water absorbency resin composition that the present invention relates to is preferably 100～600 μ m, more preferably 200～500 μ m.If mass median diameter is outside the scope of 100～600 μ m, then the liquid flow general character and diffustivity significantly reduce, and absorption rate also significantly reduces, and when for example using in diaper, can cause the leakage of liquid.

The water absorbency resin composition that the present invention relates to, in it is all, preferable particle size be the particle of 150～850 μ m account for 90 quality % or more than, more preferably particle diameter be the particle of 150～600 μ m account for 90 quality % or more than.

In the water absorbency resin composition that the present invention relates to, the logstandard deviation of size-grade distribution (σ ξ) is preferably 0.25～0.45, and more preferably 0.27～0.43, most preferably be 0.30～0.40mm/s.The logstandard deviation of size-grade distribution (σ ξ) is the width degree of expression size-grade distribution.(σ ξ) is more little for the logstandard deviation of size-grade distribution, means that then the amplitude of size-grade distribution is narrow more.When the logstandard deviation (σ ξ) of size-grade distribution less than 0.25 the time because size-grade distribution is narrow, the diffusion flow general character and the capillary siphoning equilibrium of forces of liquid may variation.And greater than 0.45 o'clock, the problem of usability aspect then can appear, the diffusion flow general character of liquid and capillary siphoning equilibrium of forces also may variation.

The separating centrifuge of the water absorbency resin composition that the present invention relates to keep capacity (CRC) be preferably 5 (g/g) or more than, more preferably 10 (g/g) or more than, more preferably 15 (g/g) or more than, especially be preferably 20 (g/g) or more than, be preferably especially 25 (g/g) or more than.There is no particular limitation to higher limit, be preferably 50 (g/g) or below, more preferably 40 (g/g) or below, more preferably 35 (g/g) or below.When separating centrifuge kept capacity (CRC) less than 5 (g/g), absorbed dose was very few, is not suitable for use in sanitary materials such as diaper.In addition, when separating centrifuge kept capacity (CRC) greater than 50 (g/g), gel-strength died down, and can't obtain the water absorbency resin composition of liquid flow general character excellence.

The water absorbency resin composition that the present invention relates to the absorptive capacity under the 4.83kPa pressure (AAP) be preferably 10 (g/g) or more than, more preferably 15 (g/g) or more than, more preferably 20 (g/g) or more than.If the absorptive capacity under 4.83kPa pressure (AAP) less than 10 (g/g), for example is used under the diaper situation, return wet amount, promptly so-called Re-wet increases, and can cause erythrosis.

The salt solution water conservancy diversion (SFC) of the water absorbency resin composition that the present invention relates to is preferably 30 (* 10 ^-7Cm ³Sg ^-1) or more than, more preferably 70 (* 10 ^-7Cm ³Sg ^-1) or more than, more preferably 100 (* 10 ^-7Cm ³Sg ^-1) or more than, be preferably 130 (* 10 especially ^-7Cm ³Sg ^-1) or more than.When salt solution water conservancy diversion (SFC) less than 30 (* 10 ^-7Cm ³Sg ^-1) time, the water-absorbent besin particles concentration in diaper cores be 30 quality % or more than, be preferably under 50 quality % or the above situation, the absorption rate of urine may be slack-off, thereby leak.

The water soluble amount of the water absorbency resin composition that the present invention relates to is preferably 35 quality % or following, more preferably 25 quality % or following, more preferably 15 quality % or following.When water soluble amount during greater than 35 quality %, gel-strength dies down, liquid flow general character variation.In addition, when using for a long time in diaper, specific absorption (CRC, AAP etc.) can reduce ageingly.

The water absorbency resin composition that the present invention relates to suppresses the effect excellence of dust.The generation of dust is preferably 1.00mg/m ³Or below, 0.30mg/m more preferably ³Or below.

The blocking rate of the water absorbency resin composition that the present invention relates to (BR) excellence.Blocking rate (BR) be preferably 35% or below, more preferably 10% or below.

The water absorbency resin composition that the present invention relates to preferably has excellent liquid velocity of diffusion (LDV).LDV is the parameter of expression " liquid imbedibility ".In the performance of absorbent commodity such as paper nappy and sanitary towel or water-absorbing body, LDV relates to the speed of liquid diffusion in the water-absorbing body, especially relates to the speed of absorption initial stage liquid.That is to say that when being actually used in diaper etc., the water absorbency resin composition of LDV excellence can significantly improve the liquid diffustivity.In the water absorbency resin composition that the present invention relates to, the lower value of LDV be preferably 2.1mm/s or more than, more preferably 2.3mm/s or more than, most preferably be 2.5mm/s or more than.In addition, in the water absorbency resin composition that the present invention relates to, the higher limit of LDV is not particularly limited, is preferably 10mm/s or following, more preferably 5mm/s or following.The numerical range of the LDV of the water absorbency resin composition that the present invention relates to can be carried out appropriate combination with higher limit and lower value and obtained.As numerical range more specifically, the liquid velocity of diffusion (LDV) of the water absorbency resin composition that the present invention relates to is preferably 2.1～10mm/s, 2.3～10mm/s more preferably, and more preferably 2.5～10mm/s most preferably is 2.5～5mm/s.

[manufacture method of water absorbency resin composition]

There is no particular limitation for the manufacture method of the water absorbency resin composition that comprises water-absorbent besin particles with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer, nitrogenous ketone compound (A) and water-soluble polyvalent metal salt, for example preferred following manufacture method 1～4.

(manufacture method 1)

First kind of manufacture method (manufacture method 1) of the water absorbency resin composition that the present invention relates to is as follows: in the water-absorbent besin particles with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer, mix the powder of nitrogenous ketone compound (A) and the powder of water-soluble polyvalent metal salt.(being referred to as fusion in the following description).

Nitrogenous ketone compound (A) and the water-soluble polyvalent metal salt of fusion in water-absorbent besin particles, nitrogenous ketone compound (A) and water-soluble polyvalent metal salt can be fused simultaneously, also nitrogenous ketone compound (A) and water-soluble polyvalent metal salt separately can be fused.

The usage quantity of nitrogenous ketone compound (A) and water-soluble polyvalent metal salt, with respect to 100 mass parts water-absorbent besin particles, the total amount of nitrogenous ketone compound (A) and water-soluble polyvalent metal salt is preferably 0.01～100 mass parts, it more preferably is 0.05～50 mass parts, more preferably 0.1～10 mass parts is preferably 0.5～5 mass parts especially.If the total amount of nitrogenous ketone compound (A) and water-soluble polyvalent metal salt is less than 0.01 mass parts, then the circulation diffustivity of liquid and blocking rate to improve effect abundant inadequately, if more than 100 mass parts, then absorption characteristic such as CRC and AAP can significantly reduce.

The mass ratio of nitrogenous ketone compound (A) content and water-soluble polyvalent metal salts contg is preferably 1: 10～and 10: 1, more preferably 3: 7～7: 3.If the mass ratio of nitrogenous ketone compound (A) content and water-soluble polyvalent metal salts contg is outside 1: 10～10: 1 scope, then the circulation diffustivity of liquid and blocking rate to improve effect abundant inadequately, and absorption characteristics such as CRC and AAP can significantly reduce.

So-called fusion is meant among the present invention, contacts by at least a portion with nitrogenous ketone compound (A) and water-soluble polyvalent metal salt, makes its fusion or becomes more soft more than solid state, thereby adhere on the surface of water-absorbent besin particles.In addition, as mentioned above, when mixing, also can heat, can promote fusion by heating.

In other words, there is no particular limitation to aforesaid method, for example adopts the method for following (a)～(d).

(a) will be in water-absorbent besin particles on nitrogenous ketone compound (A) and the water-soluble polyvalent metal salt fusing point (the optional heating) and nitrogenous ketone compound (A) and water-soluble polyvalent metal salt blended method.

(b) the nitrogenous ketone compound (A) on nitrogenous ketone compound (A) fusing point (the optional heating) and water-soluble polyvalent metal salt on water-soluble polyvalent metal salt fusing point (the optional heating) and water-absorbent besin particles blended method.

(c) with water-absorbent besin particles with after nitrogenous ketone compound (A) and water-soluble polyvalent metal salt mix, with the method for this mixture heating up to the fusing point of nitrogenous ketone compound (A) and water-soluble polyvalent metal salt.

(d) will carry out the blended method at water-absorbent besin particles on nitrogenous ketone compound (A) and the water-soluble polyvalent metal salt fusing point (optional heat) and nitrogenous ketone compound (A) (the optional heating) and the water-soluble polyvalent metal salt on water-soluble polyvalent metal salt fusing point (the optional heating) on nitrogenous ketone compound (A) fusing point.

Preferred these methods also can be used other method.

As heater means, for example comprise heating, microwave, ultrasonic wave, far infrared rays etc.

When heating, preferably be heated on the fusing point of nitrogenous ketone compound (A) and water-soluble polyvalent metal salt.The temperature range of heating is preferably 100～200 ℃, more preferably 120～180 ℃, most preferably is 130～150 ℃.

Only just making it under the interfused situation, heat always not necessary by water-absorbent besin particles is mixed with nitrogenous ketone compound (A) and water-soluble polyvalent metal salt.

Interpolation and blended method are had no particular limits, can use known powder to add and the blended method.Preferably in water-absorbent besin particles in the lump or intermittently or add the nitrogenous ketone compound (A) of specified amount and the method for water-soluble polyvalent metal salt continuously.

Interpolation and mixing are preferably under agitation carried out.And preferred at least a portion that under agitation will nitrogenous ketone compound (A) and water-soluble polyvalent metal salt fuses on the surface of water-absorbent besin particles.

As whipping appts, can use paddle agitator, screw mixer, cylindrical blender, porcelain system cylinder, plough formula porcelain system mixing machine (プラウジャ-ミキサ-), mortar mixer.These whipping apptss can be the devices that can heat, and also can be can be with the mixture refrigerative device of heating.

There is no particular limitation to time of stirring, and is preferably 60 minutes or following, more preferably 30 minutes or following.

When heating and fusing (heat fusion), preferably water-absorbent besin particles and nitrogenous ketone compound (A) and the mixture of water-soluble polyvalent metal salt are pressurizeed.Can promote heat fusion by pressurization.

(manufacture method 2)

Second kind of manufacture method (manufacture method 2) of the water absorbency resin composition that the present invention relates to is as follows: in the water-absorbent besin particles with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer, add the fraction that contains nitrogenous ketone compound (A) and water-soluble polyvalent metal salt.

The consumption of nitrogenous ketone compound (A) is identical with the ratio of the consumption of water-soluble polyvalent metal salt and above-mentioned manufacture method 1.

As the fraction that contains nitrogenous ketone compound (A) and water-soluble polyvalent metal salt, for example can be the fraction that only contains nitrogenous ketone compound (A) and water-soluble polyvalent metal salt, can also be the fraction that wherein also contains water, polyvalent alcohol liquid such as (materials of enumerating preferably).Particularly, nitrogenous ketone compound (A) (preferred urea (being solid at normal temperatures)) and hydrazine aluminum sulfate (being solid at normal temperatures) are mixed, or nitrogenous ketone compound (A) (preferred urea (being solid at normal temperatures)) and 8 hydration basic zirconium chlorides (being solid at normal temperatures) mixed, thereby formation fraction, so far, the present inventor has finished the present invention.

In the fraction that contains nitrogenous ketone compound (A) (preferred urea) and water-soluble polyvalent metal salt, the content ratio of nitrogenous ketone compound (A) (preferred urea) is preferably 10～80 quality %, more preferably be 20～70 quality %, 30～60 quality % more preferably.

When fraction has high viscosity, also can use solvent etc.As solvent, preferably can be with an organic solvent, alcohols, water etc., water is particularly preferred.The ratio of the consumption of solvent in fraction is preferably 0～80 quality %, more preferably 10～60 quality %, more preferably 20～40 quality %.

With regard to the consumption of the fraction that contains nitrogenous ketone compound (A) (preferred urea) and water-soluble polyvalent metal salt, with respect to 100 mass parts water-absorbent besin particles, the amount that contains the fraction of nitrogenous ketone compound (A) (preferred urea) and water-soluble polyvalent metal salt is preferably 0.01～100 mass parts, more preferably 0.1～50 mass parts, more preferably 1.0～10 mass parts.

Interpolation and blending means are identical with method in the above-mentioned manufacture method 1.

(manufacture method 3)

The third manufacture method of the water absorbency resin composition that the present invention relates to (manufacture method 3) is as follows: the water-absorbent besin particles that will have an internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer and the aqueous solution that contains nitrogenous ketone compound (A) and the aqueous solution that contains water-soluble polyvalent metal salt mix.

In order to prevent to soak into and spread to water-absorbent besin particles inside, contain in the aqueous solution of nitrogenous ketone compound (A), the concentration of nitrogenous ketone compound (A) preferably saturation concentration 50% or more than, more preferably 60% or more than, more preferably 70% or more than, also be preferably 80% or more than, be preferably especially 90% or more than.Can certainly use saturation concentration.

In order to prevent to soak into and spread to water-absorbent besin particles inside, contain in the aqueous solution of water-soluble polyvalent metal salt, the concentration of water-soluble polyvalent metal salt preferably saturation concentration 50% or more than, more preferably 60% or more than, more preferably 70% or more than, also be preferably 80% or more than, be preferably especially 90% or more than.Can certainly use saturation concentration.

In the aqueous solution that contains nitrogenous ketone compound (A), for example can also contain the waterborne liquid of polyvalent alcohol (material of enumerating preferably) etc.

In containing the aqueous solution of water-soluble polyvalent metal salt, for example can also contain the waterborne liquid of polyvalent alcohol (material of enumerating preferably) etc.The waterborne liquid of above-mentioned polyvalent alcohol (material of enumerating preferably) etc. can not only play the effect of mixed aid, can also play the effect of surface crosslinking agent.

With regard to the consumption of the aqueous solution that contains nitrogenous ketone compound (A), with respect to 100 mass parts water-absorbent besin particles, the amount that contains the aqueous solution of nitrogenous ketone compound (A) is preferably 0.01～100 mass parts, more preferably 0.1～50 mass parts, more preferably 1.0～10 mass parts.

With regard to the consumption of the aqueous solution that contains water-soluble polyvalent metal salt, with respect to 100 mass parts water-absorbent besin particles, the amount that contains the aqueous solution of water-soluble polyvalent metal salt is preferably 0.01～100 mass parts, more preferably 0.1～50 mass parts, more preferably 1.0～10 mass parts.

To the aqueous solution that contains nitrogenous ketone compound (A) with contain the interpolation order of the aqueous solution of water-soluble polyvalent metal salt there is no particular limitation, can add simultaneously, also can begin to add any earlier.The preferred aqueous solution that contains water-soluble polyvalent metal salt that adds adds the aqueous solution that contains nitrogenous ketone compound (A) afterwards again.Wherein, more preferably contain the aqueous solution of water-soluble polyvalent metal salt and water-absorbent besin particles is carried out surface treatment (preferably surface-crosslinked processing) by interpolation.And surface treatment (preferably surface-crosslinked processing) is preferably carried out under 150～250 ℃ temperature.

Interpolation and blending means are identical with above-mentioned manufacture method 1.

(manufacture method 4)

The 4th kind of manufacture method (manufacture method 4) of the water absorbency resin composition that the present invention relates to is as follows: in nitrogenous ketone compound (A) and the water-soluble polyvalent metal salt any is blended in the water-absorbent besin particles with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer with aqueous solution form, and another kind of doing mixed to this water-absorbent besin particles.

In order to prevent to soak into and spread to water-absorbent besin particles inside, the concentration that contains ketone compound nitrogenous in the aqueous solution of nitrogenous ketone compound (A) (A) preferably saturation concentration 50% or more than, more preferably 60% or more than, more preferably 70% or more than, also be preferably 80% or more than, be preferably especially 90% or more than.Can certainly use saturation concentration.

In order to prevent to soak into and spread to water-absorbent besin particles inside, the concentration that contains water-soluble polyvalent metal salt in the aqueous solution of water-soluble polyvalent metal salt preferably saturation concentration 50% or more than, more preferably 60% or more than, more preferably 70% or more than, also be preferably 80% or more than, be preferably especially 90% or more than.Can certainly use saturation concentration.

When use contains the aqueous solution of nitrogenous ketone compound (A), contain the waterborne liquid that for example can also contain polyvalent alcohol (material of enumerating preferably) etc. in the aqueous solution of nitrogenous ketone compound (A).

When use contains the aqueous solution of water-soluble polyvalent metal salt, contain the waterborne liquid that for example can also contain polyvalent alcohol (material of enumerating preferably) etc. in the aqueous solution of water-soluble polyvalent metal salt.

In water-absorbent besin particles, in nitrogenous ketone compound (A) and the water-soluble polyvalent metal salt any sneaked into aqueous solution form, and another kind is done and mixed, in the case, aqueous solution and dried mixing can be carried out simultaneously, also can begin to add any earlier.

[water-absorbing body]

Water absorbency resin composition among the present invention for example can form the water-absorbing body that is applicable to the sanitary material absorption layer by making up with suitable material.Below water-absorbing body is illustrated.

The so-called absorption body is meant, be used for absorbing blood and body fluid, urine etc. sanitary materials such as paper nappy, sanitary towel, incontinence pad, medical liner water absorbency resin composition with and the composition that forms with other materials, the example of material therefor for example can be a cellulosic fibre.The example of cellulosic fibre for example can be wood pulp fibers such as the mechanical pulp made by timber, dissolving pulp, semi-chemical pulp, solvability paper pulp, artificial fiber cellulose fibers such as regenerated fiber, acetic ester etc.Preferred cellulosic fibre is the wood pulp fiber.This cellulosic fibre can also contain synthon such as part nylon, polyester.When water absorbency resin composition of the present invention uses as the part of water-absorbing body, in the water-absorbing body quality optimization of contained water absorbency resin composition of the present invention be 20 quality % or more than, more preferably 30 quality % or more than, more preferably 40 quality % or more than.If the quality of contained water absorbency resin composition of the present invention is lower than 20 quality % in the water-absorbing body, then can't reach effect of sufficient.

In order to obtain water-absorbing body from water-absorbent resin composition of the present invention and cellulosic fibre, can suitably select the following known method for preparing water-absorbing body, for example, on the paper nappy that cellulosic fibre is made, scatter water absorbency resin composition, in case of necessity it is seized on both sides by the arms the method for set, with mixed uniformly method of cellulose fiber peacekeeping water absorbency resin composition etc.Preferably with the method for compressing after water absorbency resin composition and the mixing of cellulosic fibre dry type.By this method, can obviously suppress water absorbency resin composition and come off from cellulosic fibre.Compression is preferably carried out under heating, and its temperature range is for example between 50～200 ℃.In addition, for obtaining water-absorbing body, the also preferred method of putting down in writing in special flat 9-509591 communique of table and the flat 9-290000 communique of Te Kai that adopts.

When water absorbency resin composition of the present invention is used for water-absorbing body, because every physicals is all excellent, so can in time absorb liquid, and also the liquid residue on water-absorbing body top layer is few, thus obtain very excellent water-absorbing body.

Because water absorbency resin composition of the present invention has excellent water absorption character, so can be used as the water-absorbing water-retaining agent that serves many purposes.For example, can be used as the water-absorbing water-retaining agent of using in the absorbing articles such as paper nappy, sanitary towel, incontinence pad, medical liner; The anti-caking distillate medicinal water of using as the water-holding agent of agricultural or horticultural uses such as sphagna substitute, soil quality modifying agent, water-holding agent, pesticide effectiveness sustained release dosage, as decoration wall material, as water-holding agents for building such as cement additires; Also adjust material etc. as dewatering agent, siccative, the humidity of release control agent, cold-retaining agent, disposable body warmer, mud peptizer, food preservative, ion-exchange column material, mud or oil.In addition, water absorbency resin composition of the present invention is particularly suitable for using in paper nappy, sanitary towel etc. is used for absorbing the sanitary material of excrement, urine or blood.

When being used for sanitary materials such as paper nappy, sanitary towel, incontinence pad, medical liner when water-absorbing body, preferably can make following structure uses: this structure comprises that (a) presses close to the top layer with liquid perviousness of wearer's body, (b) away from wearer's body, near the bottom that liquid is had non-perviousness of wearer's clothing, and (c) water-absorbing body between top layer and bottom.Water-absorbing body can be two layers or more than, also can use with pulp layer etc.

[embodiment]

The present invention will be described in more detail by the following examples, yet the present invention is not limited to these embodiment.For convenience's sake, below " mass parts " only is designated as " part ", " liter " only is designated as " L ".In addition, " quality % " is designated as " wt% ".

The various performances of water-absorbent besin particles or water absorbency resin composition are measured by following method.If do not have specified otherwise to limit, then carry out under the Yi Xia condition that is determined at room temperature (20～25 ℃) and humidity 50RH%.

In addition, using as finished product forms such as sanitary materials under the situation of water absorbency resin composition, because water absorbency resin composition meeting moisture absorption, therefore aptly water absorbency resin composition is separated from finished product, (for example, under 1mmHg or following and 60 ℃ temperature drying 12 hours) measured in dry back under the decompression low temperature.In addition, the water ratio of the water absorbency resin composition that uses in embodiments of the invention and the comparative example all is 6 quality % or following.

＜separating centrifuge keeps capacity (CRC) 〉

Separating centrifuge keeps capacity (CRC) to be illustrated in not adding depressing in 30 minutes the specific absorption to 0.90 quality % salt solution.In addition, also CRC is called and does not add the specific absorption of depressing.

With 0.200g water-absorbent besin particles or water absorbency resin composition evenly put into non-woven fabric (southern part of the country パ Le プ industry (strain) is produced, trade(brand)name: ヒ-トロ Application ペ-パ-, model: GSP-22) bag of system (flood in 0.90 quality % salt solution (sodium chloride solution) excessive (being generally about 500ml) under the room temperature in then by 85mm * 60mm) and heat-sealing.After 30 minutes, bag is taken out, use separating centrifuge (コ of Co., Ltd. Network サ Application society produces, the whizzer of model H-122), the centrifugal force of putting down in writing in edanaABSORBENCYII441.1-99 (250G) dehydration was down measured the quality W1 (g) of bag after 3 minutes.In addition, carry out same operation not using under water absorbing resin particle or the water absorbency resin composition situation, measure the quality W0 (g) of this moment.According to following formula, calculate separating centrifuge by W1, W0 and keep capacity (CRC) (g/g) then.

Separating centrifuge keeps capacity (CRC) (g/g)

=(W1 (g)-W0 (g))/(quality of water-absorbent besin particles or water absorbency resin composition (g))-1

＜absorptive capacity (AAP) under pressure 〉

Absorptive capacity under pressure (AAP) is illustrated under the 4.83kPa in 60 minutes the specific absorption to 0.90 quality % salt solution.In addition, also AAP is called specific absorption under 4.83k Pa pressure.

Use device shown in Figure 1; internal diameter is bottom and stainless steel 400 purpose wire nettings 101 (purpose the is of a size of 38 μ m) fusion that the plastics of 60mm are supported cylinder 100; in room temperature (20～25 ℃) and humidity is under the condition of 50RH%; 0.900g water-absorbent besin particles or water absorbency resin composition uniformly dispersing is online at this; place external diameter in the above successively and be slightly less than 60mm; and support very close to each other and move up and down unimpeded piston 103 and load 104 between the cylinder; make the load that can evenly apply 4.83kPa (0.7psi) to water-absorbent besin particles or water absorbency resin composition; and adjust, thereby measure the whole weight W a (g) of this device.

Be that the inboard of the culture dish 105 of 150mm is placed diameter (Sogo Corporation's physics and chemistry is learned nitre making and produced by the glass filter 106 of 90mm at diameter, pore diameter: 100～120 μ m), add the salt solution 108 (20～25 ℃) of 0.90 quality %, make it and flush above the glass filter.The filter paper 107 that to place a diameter in the above then be 90mm (ADVANTEC Toyo Co., Ltd., trade(brand)name: (JIS P3801, No. 2), and thickness 0.26mm keeps particle diameter 5 μ m), the paper surface is removed the liquid of surplus by complete wetting.

Determinator described above is placed on the above-mentioned wetting filter paper, under load, absorbs liquid.After 1 hour, take off whole determinator, measure its quality Wb (g).Then by following formula, by Wa, Wb calculate under pressure absorptive capacity (AAP) (g/g).

Absorptive capacity under pressure (AAP)

=(Wb (g)-Wa (g))/(quality of water-absorbent besin particles or water absorbency resin composition (0.900g))

＜salt solution water conservancy diversion (SFC) 〉

The numerical value of the liquid perviousness when salt solution water conservancy diversion (SFC) is expression water-absorbent besin particles or water absorbency resin composition expansion.The value of SFC is big more, shows that the liquid perviousness is high more.

Carry out according to salt solution water conservancy diversion (SFC) test that the spy shows to put down in writing in the flat 9-509591 communique.

Use device shown in Figure 2; the water-absorbent besin particles or the water absorbency resin composition (0.900g) that evenly are put in the container 40 were expanded 60 minutes in artificial urine (1) under 0.3psi (2.07kPa) pressure; note the gel coat height of gel 44; then; under 0.3psi (2.07kPa) pressure, make the salt solution of 0.69 quality % pass through the expanded gel layer from the storage tank 31 under the constant static-pressure.This SFC test is carried out under room temperature (20～25 ℃).Use computer and balance, the amount of liquid that passes through gel coat that in 10 minutes, write down as the function of time every 20 seconds.Divided by the time (s) that increases, determine the flow rate F s (T) by expanded gel 44 (mainly being between particle) with the quality (g) that increases, unit is g/s.The required time of certain static pressure and stable flow velocity that will reach is as Ts, calculate and only Ts and the data that obtain in the time between 10 minutes are used for flow velocity, use is calculated the initial flow-rate by final gel coat in the value of Ts and the flow rate F s (T=0) that obtains in the time between 10 minutes.Fs (T=0) is extrapolated to T=0 by the result that Fs (T) is carried out method of least squares to the time to calculate.

Salt solution water conservancy diversion (SFC)

＝(Fs(t＝0)×L0)/(ρ×A×ΔP)

＝(Fs(t＝0)×L0)/139506

Wherein,

Fs (t=0): the flow velocity of representing with g/s

L0: the height of the gel coat of representing with cm

ρ: the density (1.003g/cm of NaCl solution ³)

A: the area (28.27cm of gel coat upside in the bin 41 ²)

Δ P: (4920 dyne/cm of the static pressure in the gel coat ²)

In device shown in Figure 2, in storage tank 31, insert Glass tubing 32, adjust the lower end of Glass tubing 32, the bottom that makes the salt solution 33 of 0.69 quality % maintain than expansion gel 44 in the bin 41 exceeds 5cm.The salt solution 33 of 0.69 quality % in the storage tank 31 is supplied in the bin 41 by the L pipe 34 of band valve.Be equipped with the container of collecting by liquid 48 below bin 41, collection container 48 is placed on the table balance 49.The internal diameter of bin 41 is 6cm, and bottom surface is provided with the wire netting (order directly is 38 μ m) 42 of No. 400 stainless steels.For liquid is passed through, in the bottom of piston 46 enough big hole 47 is arranged, do not enter in the hole 47 in order to make water-absorbent besin particles or water absorbency resin composition or its expansion gel, be provided with the good glass filtration unit 45 of perviousness in the bottom.Bin 41 is positioned on the platform of placing bin, and the table top that contacts with bin is installed on the wire netting 43 that does not hinder the stainless steel that liquid passes through.

Used artificial urine (1) for example is the material that has added 0.25g two hydration calcium chloride, 2.0g Repone K, 0.50g Magnesium dichloride hexahydrate, 2.0g sodium sulfate, 0.85g primary ammonium phosphate, 0.15g Secondary ammonium phosphate and 994.25g pure water.

The logstandard deviation of＜mass median diameter (D50) and size-grade distribution (σ ξ) 〉

By the aperture is the JIS standard sieve of 850 μ m, 710 μ m, 600 μ m, 500 μ m, 425 μ m, 300 μ m, 212 μ m, 150 μ m, 45 μ m etc., absorbent resin or water absorbency resin composition are sieved, and R maps on logarithmic probability paper with retained percentage.Therefrom read particle diameter corresponding to R=50 quality %, with it as mass median diameter (D50).Calculate the logstandard deviation (σ ξ) of size-grade distribution then by following formula, the value of σ ξ is more little, means that size-grade distribution is narrow more.

σξ＝0.5×ln(X2/X1)

(particle diameter when X1 is R=84.1%, the particle diameter when X2 is R=15.9%)

Used stage division is during the logstandard deviation of quality measurement median size (D50) and size-grade distribution (σ ξ); in room temperature (20～25 ℃) and humidity is under the condition of 50RH%; it is 850 μ m that 10.0g water-absorbent besin particles or water absorbency resin composition are put into the aperture; 710 μ m; 600 μ m; 500 μ m; 425 μ m; 300 μ m; 212 μ m; 150 μ m; the JIS standard sieve of 45 μ m (THE IIDA TESTING SIEVE: footpath 8cm); by vibration separation device (IIDA SIEVE SHAKER; type: ES-65 type, sequence number 0501) carries out 5 minutes classification.

＜blocking rate (BR) 〉

Be illustrated in 20 ℃ and relative humidity 70% time through 1 hour blocking rate (Blocking ratio).

Is 50mm with 2.00g water-absorbent besin particles or water absorbency resin composition uniformly dispersing at the bottom surface internal diameter; height be 10mm polypropylene system the cup end on; put into rapidly and be adjusted into 25 ℃ in advance; relative humidity is in 70% the controlled thermohygrostat (the PALTIOOUS LUCIFER PL-2G that バイエスペ Star Network is produced), places 60 minutes.Then the water-absorbent besin particles of moisture absorption or water absorbency resin composition being moved to diameter is that 7.5cm, order directly are in the JIS standard sieve of 2000 μ m; by vibration separation device (IIDA SIEVESHAKER; type: ES-65 type; sequence number 0501) carries out 5 minutes classification, be determined at that sieve is gone up the quality W4 (g) of remaining water-absorbent besin particles or water absorbency resin composition and by the water-absorbent besin particles of sieve or the quality W5 (g) of water absorbency resin composition.

Blocking rate (BR) (%)=quality W4 (g)/(W4 (g)+W5 (g)) * 100

Calculate blocking rate (%) thus.The moisture absorption blocking rate is low more, and the flowability during moisture absorption is excellent more.

＜water soluble branch (water soluble composition) amount 〉

The 0.90 quality % salt solution of measuring 184.3g is put in the 250ml plastic containers with cover; in this aqueous solution, add 1.00g water-absorbent besin particles or water absorbency resin composition; by the agitator that circles round circle round stir 16 hours after, extract the solvable composition in the resin.Filter extraction liquid with 1 filter paper (ADVANTEC Toyo Co., Ltd., trade(brand)name: (JIS P3801, No. 2), thickness 0.26mm, reservation particle diameter 5 μ m), obtain filtrate, measure this filtrate of 50.0g as measuring solution.

At first, only at 0.90 quality % salt solution, earlier with the NaOH aqueous solution titration of 0.1N to pH be 10, then with the HCl aqueous solution titration of 0.1N to pH be 2.7, obtain blank titration amount ([bNaOH] ml, [bHCl] ml).

Carry out same titration operation to measuring solution, thereby obtain titer ([NaOH] ml, [HCl] ml).

For example; constitute under the situation of water-absorbent besin particles or water absorbency resin composition at vinylformic acid and its sodium salt by known quantity; according to this monomeric molecular-weight average and the titer that obtains by aforesaid operations, can calculate solvable one-tenth component in water-absorbent besin particles or the water absorbency resin composition by following calculating formula.Under the situation of unknown quantity, the neutralization ratio of trying to achieve by titration calculates monomeric molecular-weight average.

Solvable composition (quality %)=0.1 * (molecular-weight average) * 184.3 * 100 * ([HCl]-[bHCl])/1000/1.0/50.0

Neutralization ratio (mole %)=(1-([NaOH]-[bNaOH])/([HCl]-[bHCl])) * 100

＜Dust Capacity 〉

Applied in advance the PE bag of static inhibitor (No. 13, in 0.03 * 260 * 380mm), put into absorbent resin or water absorbency resin composition.After vibrating this bag 30 times, bag is opened, measured 1 minute by DIGITALDUST INDICATOR P-5L (SHIBATA production).Measure 10 times, ask its mean value.The unit of Dust Capacity is mg/m ³

＜coating vibrator test 〉

Coating vibrator test (PS) is meant; in the Glass Containers of diameter 6cm, high 11cm; it is 6mm and the coating vibrator of having put into 10g granulated glass sphere, 30g water-absorbent besin particles or water absorbency resin composition (Japan system machinery production institute that diameter is installed; system Article Number 488); carry out shake with 800 rev/mins (CPM), detailed device is disclosed in the spy and opens in the flat 9-235378 communique.

With the shake time be 30 minutes as coating vibrator test 1, with the shake time be 10 minutes as coating vibrator test 2.

After soaking into, directly remove granulated glass sphere, obtain impaired water-absorbent besin particles or water absorbency resin composition for the JIS standard sieve of 2mm by order.

＜liquid velocity of diffusion (LDV) 〉

Liquid velocity of diffusion (LDV) is measured by the absorptive index measuring apparatus that the spy opens record in flat 5-200068 number (EP532002).In addition, groove and thin slice carry out precision work with the 2B grade stainless steel of SUS304 and make.

Become with thin slice in the groove of 20 ° of angles at groove, scatter 1.00g ± 0.005g water absorbency resin composition equably by the graduation range of 0～20cm.In addition, with scraper water absorbency resin composition is disperseed more equably.

The liquid that uses in liquid-absorbent is in 0.9 weight % salt solution (sodium chloride aqueous solution) with respect to 1L, uses edible blue No. 1 (Tokyo HuaCheng Industry Co., Ltd) painted liquid by 0.01g.

Liquid absorption time (WT) is after the liquid level with stationary tank is adjusted to more than the lowest part 0.5cm of groove, when stainless steel mesh (400 order) begins when contacting with liquid to measure.Liquid absorption time (WT) express liquid absorbs the time (second) to the 10cm position.In addition, the liquid of stationary tank and the screen cloth of stainless steel are that the speed with 1.35～1.40mm/s on the vertical direction of liquid level is flooded from the speed that begins to flood more than the minimum position 0.5cm of groove.

Calculate liquid velocity of diffusion (LDV) according to following formula.

LDV(mm/s)＝100(mm)/WT(s)

(Production Example 1)

Having 2 E type paddles, being provided with internal capacity is to add a cover in the reactor of formation on 10 liters the stainless steel ridge system double-screw type kneader of chuck, and the 37 quality % sodium acrylate aqueous solution of 505.6g vinylformic acid, 4430.8g, 497.0g pure water, 12.79g polyethyleneglycol diacrylate (molecular weight 523) dissolving are formed reaction solution.Then, under nitrogen atmosphere, this reaction solution carried out 20 minutes the degassing.Then, under agitation, in reaction solution, add the 10 quality % sodium persulfate aqueous solutions of 29.34g and the 0.1 quality %L aqueous ascorbic acid of 24.45g, begin polymerization after about 1 minute.In addition, on one side the gel of generation is pulverized,, after polymerization begins 30 minutes, take out the cross-linked polymer of aqueous gel shape Yi Bian under 20～95 ℃, carry out polymerization.The aqueous gel shape cross-linked polymer that obtains is carried out sectionalization, and making its diameter is about 5mm or following.

The aqueous gel shape cross-linked polymer of sectionalization is spread out on 50 purpose wire nettings, use warm air drying 50 minutes down at 180 ℃, pulverize dry thing with three-stage roll mill, be of a size of the JIS standard sieve that 600 μ m and order be of a size of 150 μ m by order again and carry out classification, thereby obtain the water-absorbent besin particles that mass median diameter is the unsetting broken shape of 350 μ m (1).It is 33.0g/g that the separating centrifuge of water-absorbent besin particles (1) keeps capacity (CRC), and the water soluble composition is 9.0 quality %.

For the water-absorbent besin particles (1) that 100 mass parts obtain, make by 0.4 mass parts 1, the surface treatment agent that the mixed solution of 4-butyleneglycol, 0.6g propylene glycol, 3.0 mass parts pure water is formed mixes with it, then 200 ℃ of following heated mixt 30 minutes.And this particle is pulverized, and can directly be the JIS standard sieve of 600 μ m by order until it.Next, this particle is carried out above-mentioned coating vibrator test 1.Obtain the water-absorbent besin particles (A) that the surface is crosslinked thus.

(Production Example 2)

Be coated with the thermal insulation material foamed styrene, internal diameter is 80mm, capacity is in 1 liter the container of polypropylene system, mixing 185.4g vinylformic acid by magnetic stirrer, 0.942g (0.07 mole of %, with respect to vinylformic acid) diacrylate macrogol ester (molecular weight 523) and the 1.0 quality % diethylene triamine pentaacetic acids of 1.13g and the solution (A) that five sodium acetate aqueous solutions obtain, and the 159.71g ion exchanged water that mixes the 48.5 quality % aqueous sodium hydroxide solutions of 148.53g and temperature adjustment to 50 ℃ obtain solution (B) time, under open system, in (A), add (B) and mixing rapidly.Neutralization heat and solution heat make fluid temperature rise to about 100 ℃, obtain monomer solution.

In the monomer solution that obtains, the 3 quality % sodium persulfate aqueous solutions that add 4.29g, after stirring the several seconds, by electric furnace (NEO HOTPLATE H1-1000, containing flourish hall in (strain) well produces) surface temperature is heated to 100 ℃, under open system, being injected into inner face, to have pasted テ Off ロ Application (registered trade mark) and bottom surface be that the Stainless Steel Kettle of 250 * 250mm describes in the device.Stainless Steel Kettle describes that device is of a size of, and the bottom surface is 250 * 250mm, is 640 * 640mm above, and height is 50mm, and center section is trapezoidal, is open above.

Polymerization did not also begin when monomer solution was injected pot.Carry out polymerization when the water vapour generation is also expanded foamed towards periphery, be contracted to the size more slightly bigger then than the bottom surface.This expands to shrink in 1 minute and finishes, and keeps taking out aqueous polymers after 4 minutes in aggregation container.

The pulverizer (ROYAL MEAT CHOPPER VR400K, meal grave mound Industrial Co., Ltd produces) that is of a size of 9.5mm by mould will obtain the aqueous polymers pulverizing, obtain aqueous polymers after the sectionalization.

The aqueous gel shape cross-linked polymer of sectionalization is spread out on 50 purpose wire nettings, use warm air drying 50 minutes down at 180 ℃, pulverize dry thing with three-stage roll mill, be of a size of the JIS standard sieve that 850 μ m and order be of a size of 150 μ m by order again and carry out classification, thereby obtain the water-absorbent besin particles that mass median diameter is the unsetting broken shape of 450 μ m (2).It is 36.0g/g that the separating centrifuge of water-absorbent besin particles (2) keeps capacity (CRC), and the water soluble composition is 12.0 quality %.

For the water-absorbent besin particles (2) that 100 mass parts obtain, make by 0.4 mass parts 1, the surface treatment agent that the mixed solution of 4-butyleneglycol, 0.6g propylene glycol, 3.0 mass parts pure water is formed mixes with it, then 200 ℃ of following heated mixt 40 minutes.And this particle is pulverized, and can directly be the JIS standard sieve of 850 μ m by order until it.Next, this particle is carried out above-mentioned coating vibrator test 1.Obtain the water-absorbent besin particles (B) that the surface is crosslinked thus.

In addition, for the water-absorbent besin particles (2) that 100 mass parts obtain, make by 0.4 mass parts 1, the surface treatment agent that the mixed solution of 4-butyleneglycol, 0.6g propylene glycol, 3.0 mass parts pure water is formed mixes with it, then 200 ℃ of following heated mixt 30 minutes.And this particle is pulverized, and can directly be the JIS standard sieve of 850 μ m by order until it.Next, this particle is carried out above-mentioned coating vibrator test 1.Obtain the water-absorbent besin particles (C) that the surface is crosslinked thus.

Embodiment 1

In the water-absorbent besin particles (A) that obtains in 100 mass parts Production Examples 1, evenly add the aqueous solution (A) that is formed by 1 mass parts 14-18 hydrazine aluminum sulfate, 1.5 mass parts urea, 1 mass parts pure water, drying is 1 hour under 60 ℃.The dry thing that obtains is pulverized, and can directly be the JIS standard sieve of 600 μ m by order until it.Then, said composition is carried out above-mentioned coating vibrator test 2.Obtain water absorbency resin composition (1d) thus.

Embodiment 2

Except that the urea amount with the aqueous solution (A) in the foregoing description 1 becomes 1.0 mass parts, carry out operation similarly to Example 1, obtain water absorbency resin composition (2d).

Embodiment 3

Except that the quantitative change with the urea of the aqueous solution (A) in the foregoing description 1 is 2.0 mass parts, carry out operation similarly to Example 1, obtain water absorbency resin composition (3d).

Embodiment 4

Except that the composition with the aqueous solution (A) in the foregoing description 1 becomes the aqueous solution of 1 mass parts 14-18 hydrazine aluminum sulfate, 1 mass parts urea, the formation of 0.22 mass parts pure water, carry out operation similarly to Example 1, obtain water absorbency resin composition (4d).

Embodiment 5

1 mass parts 14-18 hydrazine aluminum sulfate and 1 mass parts urea are mixed.After 24 hours, this mixture becomes liquid.Except that the aqueous solution (A) in the foregoing description 1 being become this liquid of 2 mass parts, carry out operation similarly to Example 1, obtain water absorbency resin composition (5d).

Embodiment 6

Except that the composition with the aqueous solution (A) in the foregoing description 1 becomes the aqueous solution of 11 mass parts 14-18 hydrazine aluminum sulfates, 11 mass parts urea, the formation of 11 mass parts pure water, carry out operation similarly to Example 1, obtain water absorbency resin composition (6d).

Embodiment 7

Except that the composition with the aqueous solution (A) in the foregoing description 1 becomes the aqueous solution of 1 mass parts 14-18 hydrazine aluminum sulfate, 1 mass parts urea, 1 mass parts pure water, the formation of 0.05 mass parts propylene glycol, carry out operation similarly to Example 1, obtain water absorbency resin composition (7d).

Embodiment 8

Except that the composition with the aqueous solution (A) in the foregoing description 1 becomes the aqueous solution of 1 mass parts 14-18 hydrazine aluminum sulfate, 1 mass parts urea, 0.25 mass parts pure water, the formation of 0.25 mass parts propylene glycol, carry out operation similarly to Example 1, obtain water absorbency resin composition (8d).

Embodiment 9

In the water-absorbent besin particles (1) that obtains in 100 mass parts Production Examples 1, evenly add the aqueous solution (A) that is formed by 1 mass parts 14-18 hydrazine aluminum sulfate, 1.5 mass parts urea, 1 mass parts pure water, drying is 1 hour under 60 ℃.The dry thing that obtains is pulverized, and can directly be the JIS standard sieve of 600 μ m by order until it.Then, said composition is carried out above-mentioned coating vibrator test 2.Thereby obtain water absorbency resin composition (9d).

Embodiment 10

The water-absorbent besin particles (A) that obtains in the 100 mass parts Production Examples 1 is heated to 150 ℃, to wherein evenly adding 1 mass parts 14-18 hydrazine aluminum sulfate (particle diameter is 600 μ m or following), 0.5 mass parts urea (particle diameter is 600 μ m or following) and fusion.And then under 100 ℃, heated 30 minutes, the composition that obtains is pulverized, can directly the JIS standard sieve of 600 μ m by order until it.Thereby obtain water absorbency resin composition (10).Then, water absorbency resin composition (10) is carried out above-mentioned coating vibrator test 2.Thereby obtain water absorbency resin composition (10d).

Embodiment 11

Except that the quantitative change with urea in the foregoing description 10 is 1.0 mass parts, carry out operation similarly to Example 10, obtain water absorbency resin composition (11) and water absorbency resin composition (11d).

Embodiment 12

Except that the quantitative change with urea in the foregoing description 10 is 1.5 mass parts, carry out operation similarly to Example 10, obtain water absorbency resin composition (12) and water absorbency resin composition (12d).

Embodiment 13

Water-absorbent besin particles (A), 1 mass parts 14-18 hydrazine aluminum sulfate (particle diameter is 600 μ m or following), 1 mass parts urea (particle diameter is 600 μ m or following) that 100 mass parts Production Examples 1 are obtained mix.Heat this mixture to 140 ℃, stir and made its fusion in 5 minutes.In addition, the composition that obtains being pulverized, can directly be the JIS standard sieve of 600 μ m by order until it.Thereby obtain water absorbency resin composition (13).

Embodiment 14

The quantitative change that removes 14-18 hydrazine aluminum sulfate in the foregoing description 13 is 11 mass parts, and the quantitative change of urea is beyond 11 mass parts, to carry out operation similarly to Example 13.Thereby obtain water absorbency resin composition (14).

Embodiment 15

Except that the quantitative change with urea in the foregoing description 13 is 11 mass parts, carry out operation similarly to Example 13, obtain water absorbency resin composition (15).

Embodiment 16

Except that the quantitative change with 14-18 hydrazine aluminum sulfate in the foregoing description 13 is 11 mass parts, carry out operation similarly to Example 13.Thereby obtain water absorbency resin composition (16).

Embodiment 17

Except that the water-absorbent besin particles in the foregoing description 13 (A) being become water-absorbent besin particles (1), carry out operation similarly to Example 13, obtain water absorbency resin composition (17).

Embodiment 18

Except that the 14-18 hydrazine aluminum sulfate in the foregoing description 1 aqueous solution (A) being become 6 Ferric Chloride Hydrateds (III), carry out operation similarly to Example 1, thereby obtain water absorbency resin composition (18d).

Embodiment 19

In the water-absorbent besin particles (1) that 100 mass parts Production Examples 1 obtain, uniform mixing 0.3 mass parts 1, behind the surface treatment agent that the mixed solution of 4-butyleneglycol, 0.5 mass parts propylene glycol, 2.7 mass parts pure water, 1.0 mass parts 14-18 hydrazine aluminum sulfates forms, under 200 ℃, mixture heating up was handled 30 minutes.After the heat treated, said composition is cooled to 60 ℃, with the aqueous solution of urea uniform mixing of 2 mass parts, 50 quality %.It is following dry 1 hour at 60 ℃.Pulverizing this drying thing, can directly be the JIS standard sieve of 600 μ m by order until it.Thereby obtain water absorbency resin composition (19).

Embodiment 20

In the absorbent resin purport particle (1) that 100 mass parts Production Examples 1 obtain, dry type is mixed 1 mass parts 14-18 hydrazine aluminum sulfate (particle diameter is 600 μ m or following), then the aqueous solution of urea of uniform mixing 2 mass parts 50 quality % in said composition.It is following dry 1 hour at 60 ℃.Pulverizing this drying thing, can directly be the JIS standard sieve of 600 μ m by order until it.Thereby obtain water absorbency resin composition (20).

Embodiment 21

In the water-absorbent besin particles (1) that 100 mass parts Production Examples 1 obtain, dry type is mixed 1 mass parts urea (particle diameter is 600 μ m or following), then the aqueous solution that uniform mixing 1 mass parts 14-18 hydrazine aluminum sulfate and 1 mass parts pure water form in said composition.It is following dry 1 hour at 60 ℃.Pulverizing this drying thing, can directly be the JIS standard sieve of 600 μ m by order until it.Thereby obtain water absorbency resin composition (21).

Embodiment 22

In the water-absorbent besin particles (1) that 100 mass parts Production Examples 1 obtain, the aqueous solution that uniform mixing 1 mass parts 14-18 hydrazine aluminum sulfate and 1 mass parts pure water form and the aqueous solution of urea of 2 mass parts, 50 quality %.It is following dry 1 hour at 60 ℃.Pulverizing this drying thing, can directly be the JIS standard sieve of 600 μ by order until it.Thereby obtain water absorbency resin composition (22).

Embodiment 23

In the water-absorbent besin particles (B) that obtains in 100 mass parts Production Examples 2, evenly add the aqueous solution (A) that is formed by 1 mass parts 14-18 hydrazine aluminum sulfate, 1.5 mass parts urea, 1 mass parts pure water, drying is 1 hour under 60 ℃.Pulverizing this drying thing, can directly be the JIS standard sieve of 600 μ m by order until it.Then said composition is carried out above-mentioned coating vibrator test 2.Thereby obtain water absorbency resin composition (23d).

Embodiment 24

In the water-absorbent besin particles (C) that obtains in 100 mass parts Production Examples 2, evenly add the aqueous solution (A) that is formed by 1 mass parts 14-18 hydrazine aluminum sulfate, 1.5 mass parts urea, 1 mass parts pure water, drying is 1 hour under 60 ℃.The dry thing that obtains is pulverized, and can directly be the JIS standard sieve of 600 μ m by order until it.Then said composition is carried out above-mentioned coating vibrator test 2.Thereby obtain water absorbency resin composition (24d).

Embodiment 25

In the water-absorbent besin particles (A) that in 100 mass parts Production Examples 1, obtains, evenly add by 1 mass parts 14-18 hydrazine aluminum sulfate, 0.2 mass parts N, the aqueous solution that dinethylformamide, 1 mass parts pure water form is (through after a few hours, precipitate appears, produce white opacity), drying is 1 hour under 60 ℃.The dry thing that obtains is pulverized, and can directly be the JIS standard sieve of 600 μ m by order until it.Then said composition is carried out above-mentioned coating vibrator test 2.Thereby obtain water absorbency resin composition (25d).

Embodiment 26

In the water-absorbent besin particles (A) that obtains in 100 mass parts Production Examples 1, evenly add the aqueous solution that is formed by 1 mass parts 14-18 hydrazine aluminum sulfate, 0.2 mass parts ethylidene urea, 1 mass parts pure water, drying is 1 hour under 60 ℃.The dry thing that obtains is pulverized, and can directly be the JIS standard sieve of 600 μ m by order until it.Then said composition is carried out above-mentioned coating vibrator test 2.Thereby obtain water absorbency resin composition (26d).

Embodiment 27

In the water-absorbent besin particles (A) that obtains in 100 mass parts Production Examples 1, evenly add the fraction that is formed by 1 mass parts, 8 hydration basic zirconium chlorides, 1 mass parts urea, drying is 1 hour under 60 ℃.The dry thing that obtains is pulverized, and can directly be the JIS standard sieve of 600 μ m by order until it.Then said composition is carried out above-mentioned coating vibrator test 2.Thereby obtain water absorbency resin composition (27d).

Embodiment 28

In the water-absorbent besin particles (A) that obtains in 100 mass parts Production Examples 1, the state with powder adds 1 quality, 8 hydration part basic zirconium chlorides and 1 mass parts urea respectively, stirs by scraper.In case stir, 8 hydration basic zirconium chlorides and urea are promptly had an effect, and water-absorbent besin particles is wetted, continue to stir a little while again.The composition that obtains is like this pulverized, and can directly be the JIS standard sieve of 600 μ m by order until it.Thereby obtain water absorbency resin composition (28).

Embodiment 29

In the water-absorbent besin particles (A) that obtains in 100 mass parts Production Examples 1, the state with powder adds 1 mass parts hydrazine aluminum sulfate and 2 mass parts urea respectively, stirs by scraper.In case stir, hydrazine aluminum sulfate and urea are promptly had an effect, and water-absorbent besin particles is wetted, continue to stir a little while again.The composition that obtains is like this pulverized, and can directly be the JIS standard sieve of 600 μ m by order until it.Thereby obtain water absorbency resin composition (29).

Embodiment 30

In the water-absorbent besin particles (1) that obtains in 100 mass parts Production Examples 1, evenly add the fraction that is formed by 1 mass parts, 8 hydration basic zirconium chlorides and 1 mass parts urea, drying is 1 hour under 100 ℃.The dry thing that obtains is pulverized, and can directly be the JIS standard sieve of 600 μ m by order until it.Thereby obtain water absorbency resin composition (30).

Embodiment 31

In the water-absorbent besin particles (B) that obtains in 100 mass parts Production Examples 2, evenly add the fraction that is formed by 1 mass parts, 8 hydration basic zirconium chlorides and 1 mass parts urea, drying is 1 hour under 60 ℃.The dry thing that obtains is pulverized, and can directly be the JIS standard sieve of 850 μ m by order until it.Then said composition is carried out above-mentioned coating vibrator test 2.Thereby obtain water absorbency resin composition (31d).

Embodiment 32

In the water-absorbent besin particles (C) that obtains in 100 mass parts Production Examples 2, the state with powder adds 1 mass parts, 8 hydration basic zirconium chlorides and 1 mass parts urea respectively, stirs by scraper.In case stir, 8 hydration basic zirconium chlorides and urea are promptly had an effect, and water-absorbent besin particles is wetted, continue to stir a little while again.The composition that obtains is like this pulverized, and can directly be the JIS standard sieve of 850 μ m by order until it.Then said composition is carried out above-mentioned coating vibrator test 2.Thereby obtain water absorbency resin composition (32d).

Comparative example 1

With the water-absorbent besin particles (A) that obtains in the Production Example 1 water-absorbent besin particles (1) as a comparison.

Comparative example 2

With the water-absorbent besin particles (B) that obtains in the Production Example 2 water-absorbent besin particles (2) as a comparison.

Comparative example 3

With the water-absorbent besin particles (C) that obtains in the Production Example 2 water-absorbent besin particles (3) as a comparison.

Comparative example 4

In the water-absorbent besin particles (A) that obtains in 100 mass parts Production Examples 1, evenly add the aqueous solution that is formed by 1 mass parts 14-18 hydrazine aluminum sulfate and 1 mass parts pure water, drying is 1 hour under 60 ℃.The dry thing that obtains is pulverized, and can directly be the JIS standard sieve of 600 μ m by order until it.Thereby obtain comparison water absorbency resin composition (4).Then this comparison water absorbency resin composition (4) is carried out above-mentioned coating vibrator test 2.Thereby obtain comparison water absorbency resin composition (4d).

Comparative example 5

In the water-absorbent besin particles (A) that obtains in 100 mass parts Production Examples 1, evenly dry type is mixed 1 mass parts 14-18 hydrazine aluminum sulfate (particle diameter is 600 μ m or following).Thereby obtain comparison water absorbency resin composition (5).Then this comparison water absorbency resin composition (5) is carried out above-mentioned coating vibrator test 2.Thereby obtain comparison water absorbency resin composition (5d).

Comparative example 6

The water-absorbent besin particles (A) that obtains in the 100 mass parts Production Examples 1 is heated to 150 ℃,, fuses to wherein evenly adding 1.6 mass parts, 12 hydrazine aluminum sulfate potassium (particle diameter is 600 μ m or following).In addition, heating 30 minutes down at 100 ℃, the composition that obtains is pulverized, can directly be the JIS standard sieve of 600 μ m by order until it.Thereby obtain comparison water absorbency resin composition (6).Then this comparison water absorbency resin composition (6) is carried out above-mentioned coating vibrator test 2.Thereby obtain comparison water absorbency resin composition (6d).

Comparative example 7

With respect to the hot solution (the aluminium component content that is converted into aluminum oxide is 10.75 quality %) of 30g potassium aluminium sulfate (potassium alum), behind the powder of the adding dry potassium aluminium sulfate of 7.5g (exsiccated alum), stir and carry out homodisperse, obtain the slurries of white.In above-mentioned slurries, add 26.2g urea then, after the dissolving, add the water-absorbent tree resin particle (1) that obtains in the 34.2g Production Example 1, homodisperse obtains slurries, is injected in the drying basin, open drying basin behind the certain hour, and under the temperature about 60 ℃, carry out warm air drying.After the drying, obtain the solid matter of the white odorless of 93g pulverizing.Thereby obtain comparison water absorbency resin composition (7).

Comparative example 8

Except that the water-absorbent besin particles (1) with above-mentioned comparative example 7 becomes the absorbent resin (A) that obtains in the Production Example 1, carry out the operation same with comparative example 7.Thereby obtain comparison water absorbency resin composition (8).

Comparative example 9

In the water-absorbent besin particles (1) that in 100 mass parts Production Examples 1, obtains, uniform mixing is by 0.3 mass parts 1, the surface treatment agent that the mixed solution of 4-butyleneglycol, 0.5 mass parts propylene glycol, 2.7 mass parts pure water, 1.0 mass parts 14-18 hydrazine aluminum sulfates forms carries out 30 minutes heat treated to mixture under 200 ℃.After the heat treated said composition being pulverized, can directly be the JIS standard sieve of 600 μ m by order until it.Thereby obtain comparison water absorbency resin composition (9).

Comparative example 10

In the water-absorbent besin particles (1) that obtains in 100 mass parts Production Examples 1, evenly add the aqueous solution that is formed by 1 mass parts, 8 hydration basic zirconium chlorides and 1 mass parts pure water, drying is 1 hour under 100 ℃.The dry thing that obtains is pulverized, and can directly be the JIS standard sieve of 600 μ m by order until it.Thereby obtain comparison water absorbency resin composition (10).

Comparative example 11

In the water-absorbent besin particles (1) that obtains in 100 mass parts Production Examples 1, evenly add the aqueous solution that is formed by 1 mass parts, 8 hydration basic zirconium chlorides and 1 mass parts pure water, drying is 1 hour under 60 ℃.The dry thing that obtains is pulverized, and can directly be the JIS standard sieve of 600 μ m by order until it.Then said composition is carried out above-mentioned coating vibrator test 2.Thereby obtain comparison water absorbency resin composition (11d).

The separating centrifuge of the water absorbency resin composition that obtains in the foregoing description and the comparative example, comparison water-absorbent besin particles, comparison water absorbency resin composition keeps the measurement result of capacity (CRC), the absorptive capacity under pressure (AAP), salt solution water conservancy diversion (SFC) to provide in table 1 and 2.

The measurement result of the Dust Capacity of water absorbency resin composition (1d), (11d), comparison water-absorbent besin particles (1), comparison water absorbency resin composition (4d), (5d), (6d) provides in table 3.In addition, the measurement result of the Dust Capacity of water absorbency resin composition (27d), (28), (29), comparison water-absorbent besin particles (1), comparison water absorbency resin composition (11d) provides in table 4.

In addition, the measurement result of the Dust Capacity of water absorbency resin composition (19), comparison water absorbency resin composition (9) provides in table 5.

The measurement result of the blocking rate (BR) of water absorbency resin composition (1d), (8d), (11d), (27d), (28), comparison water-absorbent besin particles (1), (2), (3) provides in table 6.

The logstandard deviation (σ ξ) of the mass median diameter (D50) of water-absorbent besin particles (A), (C), water absorbency resin composition (1d), (24d), (27d), (32d) and size-grade distribution provides in table 7.

The measurement result of the liquid velocity of diffusion (LDV) of water absorbency resin composition (1d), comparison water-absorbent besin particles (1), comparison water absorbency resin composition (4d) provides in table 8.

[table 1]

	C?R?C (g/g)	A?A?P (g/g)	S?F?C (×10 ^-7·cm ³·s·g ^-1)
	C?R?C (g/g)	A?A?P (g/g)	S?F?C (×10 ^-7·cm ³·s·g ^-1)	Water absorbency resin composition (1d)	25.2	22.5	171
Water absorbency resin composition (2d)	25.4	22.1	127	Water absorbency resin composition (1d)	25.2	22.5	171
Water absorbency resin composition (2d)	25.4	22.1	127	Water absorbency resin composition (3d)	25.0	22.0	138
Water absorbency resin composition (4d)	25.5	23.2	127	Water absorbency resin composition (3d)	25.0	22.0	138
Water absorbency resin composition (4d)	25.5	23.2	127	Water absorbency resin composition (5d)	25.6	23.3	128
Water absorbency resin composition (6d)	18.3	15.3	248	Water absorbency resin composition (5d)	25.6	23.3	128
Water absorbency resin composition (6d)	18.3	15.3	248	Water absorbency resin composition (7d)	25.3	22.5	143
Water absorbency resin composition (8d)	25.5	22.6	145	Water absorbency resin composition (7d)	25.3	22.5	143
Water absorbency resin composition (8d)	25.5	22.6	145	Water absorbency resin composition (9d)	30.3	9.7	3
Water absorbency resin composition (10)	25.6	22.8	145	Water absorbency resin composition (9d)	30.3	9.7	3
Water absorbency resin composition (10)	25.6	22.8	145	Water absorbency resin composition (10d)	25.7	22.8	147
Water absorbency resin composition (11)	25.5	22.5	147	Water absorbency resin composition (10d)	25.7	22.8	147
Water absorbency resin composition (11)	25.5	22.5	147	Water absorbency resin composition (11d)	25.5	22.6	155
Water absorbency resin composition (12)	25.5	22.4	146	Water absorbency resin composition (11d)	25.5	22.6	155
Water absorbency resin composition (12)	25.5	22.4	146	Water absorbency resin composition (12d)	25.6	22.7	148
Water absorbency resin composition (13)	25.4	22.7	138	Water absorbency resin composition (12d)	25.6	22.7	148
Water absorbency resin composition (13)	25.4	22.7	138	Water absorbency resin composition (14)	21.6	16.1	109
Water absorbency resin composition (15)	25.3	19.9	129	Water absorbency resin composition (14)	21.6	16.1	109
Water absorbency resin composition (15)	25.3	19.9	129	Water absorbency resin composition (16)	23.4	17.1	122
Water absorbency resin composition (17)	32.9	9.4	0	Water absorbency resin composition (16)	23.4	17.1	122

[table 2]

	C?R?C (g/g)	A?A?P (g/g)	S?F?C (×10 ^-7·cm ³·s·g ^-1)
	C?R?C (g/g)	A?A?P (g/g)	S?F?C (×10 ^-7·cm ³·s·g ^-1)	Water absorbency resin composition (18d)	25.1	21.3	118
Water absorbency resin composition (19)	25.9	22.7	135	Water absorbency resin composition (18d)	25.1	21.3	118
Water absorbency resin composition (19)	25.9	22.7	135	Water absorbency resin composition (20)	25.1	22.3	155
Water absorbency resin composition (21)	25.2	22.0	132	Water absorbency resin composition (20)	25.1	22.3	155
Water absorbency resin composition (21)	25.2	22.0	132	Water absorbency resin composition (22)	25.1	21.8	128
Water absorbency resin composition (23d)	28.0	22.8	140	Water absorbency resin composition (22)	25.1	21.8	128
Water absorbency resin composition (23d)	28.0	22.8	140	Water absorbency resin composition (24d)	30.2	23.2	57
Water absorbency resin composition (25d)	23.5	21.5	131	Water absorbency resin composition (24d)	30.2	23.2	57
Water absorbency resin composition (25d)	23.5	21.5	131	Water absorbency resin composition (26d)	23.5	21.5	136
Water absorbency resin composition (27d)	25.4	21.4	130	Water absorbency resin composition (26d)	23.5	21.5	136
Water absorbency resin composition (27d)	25.4	21.4	130	Water absorbency resin composition (28)	25.3	20.5	136
Water absorbency resin composition (29)	25.3	20.8	110	Water absorbency resin composition (28)	25.3	20.5	136
Water absorbency resin composition (29)	25.3	20.8	110	Water absorbency resin composition (30)	30.1	13.3	3
Water absorbency resin composition (31d)	27.7	22.3	86	Water absorbency resin composition (30)	30.1	13.3	3
Water absorbency resin composition (31d)	27.7	22.3	86	Water absorbency resin composition (32d)	30.2	22.8	44
Compare water-absorbent besin particles (1)	25.8	23.6	64	Water absorbency resin composition (32d)	30.2	22.8	44
Compare water-absorbent besin particles (1)	25.8	23.6	64	Compare water-absorbent besin particles (2)	28.5	24.9	51
Compare water-absorbent besin particles (3)	30.7	25.4	26	Compare water-absorbent besin particles (2)	28.5	24.9	51
Compare water-absorbent besin particles (3)	30.7	25.4	26	Compare water absorbency resin composition (4)	25.2	21.7	121
Compare water absorbency resin composition (4d)	25.3	21.6	109	Compare water absorbency resin composition (4)	25.2	21.7	121
Compare water absorbency resin composition (4d)	25.3	21.6	109	Compare water absorbency resin composition (5)	25.5	23.2	158
Compare water absorbency resin composition (5d)	25.5	22.8	144	Compare water absorbency resin composition (5)	25.5	23.2	158
Compare water absorbency resin composition (5d)	25.5	22.8	144	Compare water absorbency resin composition (6)	25.4	22.8	95
Compare water absorbency resin composition (6d)	25.5	22.7	68	Compare water absorbency resin composition (6)	25.4	22.8	95
Compare water absorbency resin composition (6d)	25.5	22.7	68	Compare water absorbency resin composition (7)	6.7	4.1	135
Compare water absorbency resin composition (8)	5.6	4.4	154	Compare water absorbency resin composition (7)	6.7	4.1	135
Compare water absorbency resin composition (8)	5.6	4.4	154	Compare water absorbency resin composition (9)	25.8	22.1	121
Compare water absorbency resin composition (10)	30.7	8.7	0	Compare water absorbency resin composition (9)	25.8	22.1	121
Compare water absorbency resin composition (10)	30.7	8.7	0	Compare water absorbency resin composition (11d)	25.6	23.3	100

[table 3]

	Dust Capacity (mg/m ³)
	Dust Capacity (mg/m ³)	Water absorbency resin composition (1d)	0.23
Water absorbency resin composition (11d)	0.24	Water absorbency resin composition (1d)	0.23
Water absorbency resin composition (11d)	0.24	Compare water-absorbent besin particles (1)	0.35
Compare water absorbency resin composition (4d)	0.68	Compare water-absorbent besin particles (1)	0.35
Compare water absorbency resin composition (4d)	0.68	Compare water absorbency resin composition (5d)	1.24
Compare water absorbency resin composition (6d)	1.94	Compare water absorbency resin composition (5d)	1.24

[table 4]

	Dust Capacity (mg/m ³)
	Dust Capacity (mg/m ³)	Water absorbency resin composition (27d)	0.19
Water absorbency resin composition (28)	0.18	Water absorbency resin composition (27d)	0.19
Water absorbency resin composition (28)	0.18	Water absorbency resin composition (29)	0.22
Compare water-absorbent besin particles (1)	0.35	Water absorbency resin composition (29)	0.22
Compare water-absorbent besin particles (1)	0.35	Water absorbency resin composition (11d)	0.41

[table 5]

	Dust Capacity (mg/m ³)
	Dust Capacity (mg/m ³)	Water absorbency resin composition (19)	0.98
Compare water absorbency resin composition (9)	13.4	Water absorbency resin composition (19)	0.98

[table 6]

	Blocking rate (BR) (%)
	Blocking rate (BR) (%)	Water absorbency resin composition (1d)	0
Water absorbency resin composition (8d)	0	Water absorbency resin composition (1d)	0
Water absorbency resin composition (8d)	0	Water absorbency resin composition (11d)	4
Water absorbency resin composition (27d)	0	Water absorbency resin composition (11d)	4
Water absorbency resin composition (27d)	0	Water absorbency resin composition (28)	8
Compare water-absorbent besin particles (1)	84	Water absorbency resin composition (28)	8
Compare water-absorbent besin particles (1)	84	Compare water-absorbent besin particles (2)	38
Compare water-absorbent besin particles (3)	45	Compare water-absorbent besin particles (2)	38

[table 7]

	Water-absorbent besin particles (A)	Water-absorbent besin particles (C)	Water absorbency resin composition (1d)	Water absorbency resin composition (24d)	Water absorbency resin composition (27d)	Water absorbency resin composition (32d)
	Water-absorbent besin particles (A)	Water-absorbent besin particles (C)	Water absorbency resin composition (1d)	Water absorbency resin composition (24d)	Water absorbency resin composition (27d)	Water absorbency resin composition (32d)	850 μ m above (quality %)	0.0	0.0	0.0	0.0	0.0	0.0
850 ~ 710 μ m (quality %)	0.0	2.5	0.0	2.7	0.0	3.0	850 μ m above (quality %)	0.0	0.0	0.0	0.0	0.0	0.0
850 ~ 710 μ m (quality %)	0.0	2.5	0.0	2.7	0.0	3.0	710 ~ 600 μ m (quality %)	0.0	25.7	0.1	26.1	0.0	27.0
600 ~ 500 μ m (quality %)	3.2	17.1	3.2	17.3	3.8	18.0	710 ~ 600 μ m (quality %)	0.0	25.7	0.1	26.1	0.0	27.0
600 ~ 500 μ m (quality %)	3.2	17.1	3.2	17.3	3.8	18.0	500 ~ 425 μ m (quality %)	18.1	13.8	18.4	13.9	18.8	13.4
425 ~ 300 μ m (quality %)	38.4	23.1	38.7	23.0	38.9	22.4	500 ~ 425 μ m (quality %)	18.1	13.8	18.4	13.9	18.8	13.4
425 ~ 300 μ m (quality %)	38.4	23.1	38.7	23.0	38.9	22.4	300 ~ 212 μ m (quality %)	25.4	11.2	25.5	10.8	24.6	10.2
212 ~ 150 μ m (quality %)	13.0	4.2	12.5	4.1	12.1	3.9	300 ~ 212 μ m (quality %)	25.4	11.2	25.5	10.8	24.6	10.2
212 ~ 150 μ m (quality %)	13.0	4.2	12.5	4.1	12.1	3.9	150 ~ 45 μ m (quality %)	1.8	2.3	1.6	2.1	1.7	2.0
45 μ m following (quality %)	0.1	0.1	0.0	0.0	0.1	0.1	150 ~ 45 μ m (quality %)	1.8	2.3	1.6	2.1	1.7	2.0
45 μ m following (quality %)	0.1	0.1	0.0	0.0	0.1	0.1	Amount to (quality %)	100.0	100.0	100.0	100.0	100.0	100.0
D50(μm)	326	473	328	478	331	488	Amount to (quality %)	100.0	100.0	100.0	100.0	100.0	100.0
D50(μm)	326	473	328	478	331	488	σζ	0.35	0.40	0.35	0.39	0.35	0.38

[more than the X μ m] expression after the progressive operation, is of a size of water-absorbent besin particles residual on the sieve of X or water absorbency resin composition at order.

[Y μ m is following] expression after the progressive operation, is of a size of the water-absorbent besin particles or the water absorbency resin composition of the sieve of Y by order.

[X～Y μ m] expression after the progressive operation, is of a size of the sieve of X and is of a size of water-absorbent besin particles residual on the sieve of Y or water absorbency resin composition at order by order.

[table 8]

	Liquid velocity of diffusion (LDV) (mm/s)
	Liquid velocity of diffusion (LDV) (mm/s)	Water absorbency resin composition (1d)	2.7?5
Compare water-absorbent besin particles (1)	0.7	Water absorbency resin composition (1d)	2.7?5
Compare water-absorbent besin particles (1)	0.7	Compare water absorbency resin composition (4d)	1.8

In addition, the concrete embodiment or the embodiment that in the preferred forms of invention, list, make technology contents of the present invention clear fully, but can not be interpreted as to narrow sense the present invention and only limit to these specific exampless, as long as, just can carry out implementing after the various conversion to the present invention in spirit of the present invention with in the scope of the claim of putting down in writing subsequently.

Industrial applicibility

Because the water absorbency resin composition among the present invention has excellent water absorption character etc., so can be used as the water-absorbing water-retaining agent that serves many purposes. For example, can be used as the water-absorbing water-retaining agent of using in the absorbing articles such as paper nappy, sanitary napkin, incontinence pad, medical liner; Water-loss reducer as agricultural or horticultural uses such as sphagna substitute, soil quality modifying agent, water-loss reducer, pesticide effectiveness sustained release agents; The anti-caking distillate medicinal water of using as decoration wall material, as water-loss reducers for building such as cement additires; Also adjust material etc. as dehydrating agent, drier, the humidity of release control agent, cold-retaining agent, disposable body warmer, mud coagulating agent, food preservative, ion-exchange column material, mud or oil. In addition, the water absorbency resin composition among the present invention is particularly suitable for using in paper nappy, sanitary napkin etc. is used for absorbing the hygienic material of excrement, urine or blood.

Claims

1. water absorbency resin composition, this water absorbency resin composition comprises water-absorbent besin particles with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer, have the nitrogenous of structure shown in the general formula (1) but do not contain the ketone compound (A) of carboxyl and the water-soluble polyvalent metal salt of divalent and/or 3 valencys and/or 4 valencys, it is characterized in that, with respect to 100 mass parts water-absorbent besin particles, nitrogenous ketone compound (A) is 0.05～50 mass parts with the total amount of the water-soluble polyvalent metal salt of divalent and/or 3 valencys and/or 4 valencys.

2. water absorbency resin composition according to claim 1, wherein, above-mentioned nitrogenous ketone compound (A) is urea and/or its derivative with structure shown in the general formula (2).

3. water absorbency resin composition according to claim 1 and 2, wherein, at least a portion on above-mentioned water-absorbent besin particles surface by nitrogenous ketone compound (A) and 2/ or or the water-soluble polyvalent metal salt of 3 valencys and/or 4 valencys apply.

4. water absorbency resin composition according to claim 1 and 2 wherein, has carried out surface-crosslinked processing or thermal treatment to above-mentioned water-absorbent besin particles.

5. water absorbency resin composition according to claim 1 and 2, wherein, above-mentioned water absorbency resin composition the absorptive capacity under the 4.83kPa pressure (AAP) be 15 (g/g) or more than.

6. water absorbency resin composition according to claim 1 and 2, wherein, the salt solution water conservancy diversion (SFC) of above-mentioned water absorbency resin composition is 30 (* 10 ^-7Cm ³Sg ^-1) or more than.

7. the manufacture method of the attached oil/fat composition of water-absorbent, this method comprises: in the water-absorbent besin particles with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer, mixing has the nitrogenous of structure shown in the general formula (1) but does not contain the ketone compound (A) of carboxyl and the water-soluble polyvalent metal salt of divalent and/or 3 valencys and/or 4 valencys, it is characterized in that, with respect to the water-absorbent besin particles of 100 mass parts, mixing total amount is the nitrogenous ketone compound (A) of 0.05～50 mass parts and the water-soluble polyvalent metal salt of divalent and/or 3 valencys and/or 4 valencys.

8. the manufacture method of water absorbency resin composition according to claim 7 is characterized in that, above-mentioned water-absorbent besin particles is mixed with the powder of above-mentioned nitrogenous ketone compound (A) and the powder of above-mentioned water-soluble polyvalent metal salt.

9. the manufacture method of water absorbency resin composition according to claim 7, it is characterized in that, above-mentioned water-absorbent besin particles is mixed with a kind of fraction, and this fraction contains above-mentioned nitrogenous ketone compound (A) and the normal dissolubility polyvalent metal salt of above-mentioned water.

10. the manufacture method of water absorbency resin composition according to claim 7, it is characterized in that, above-mentioned water-absorbent besin particles and the aqueous solution that contains above-mentioned nitrogenous ketone compound (A) and the aqueous solution that contains above-mentioned water-soluble polyvalent metal salt are mixed.

11. the manufacture method of water absorbency resin composition according to claim 7, it is characterized in that, with above-mentioned water-absorbent besin particles with contain above-mentioned nitrogenous ketone compound (A) and above-mentioned water-soluble polyvalent metal salt in any mix with aqueous solution form, another kind of do mixed with this water-absorbent besin particles.

12. according to the manufacture method of each described water absorbency resin composition among the claim 7-11, wherein, above-mentioned nitrogenous ketone compound (A) is urea and/or its derivative with structure shown in the general formula (2).

13. granular water absorbency resin composition, wherein, this water absorbency resin composition comprises water-absorbent besin particles, wetting ability organic compound and the water-soluble polyvalent metal salt with the internal crosslinking structure that obtains by the polymerization water-soluble unsaturated monomer, with respect to 100 weight parts suction shape resin particle, the total amount of wetting ability organic compound and water-soluble polyvalent metal salt is 0.05～50 weight part, it is characterized in that the liquid velocity of diffusion (LDV) of said composition is 2.1～10.0mm/s.

14. water absorbency resin composition according to claim 13 is characterized in that, above-mentioned water-soluble polyvalent metal salt is divalent and/or 3 valencys.

15. according to claim 13 or 14 described water absorbency resin compositions, it is characterized in that, in the above-mentioned water absorbency resin composition, particle diameter be the particle of 150～850 μ m account for 90 quality % or more than, and the logstandard deviation of size-grade distribution (σ ξ) is 0.25～0.45.

16. water absorbency resin composition according to claim 13 is characterized in that, water-absorbent besin particles contained in the above-mentioned water absorbency resin composition has passed through surface treatment.

17. water absorbency resin composition according to claim 13 is characterized in that, the water ratio of above-mentioned water absorbency resin composition is 0.1～10 quality %.

18. water absorbency resin composition according to claim 13 is characterized in that, it is 25～40g/g that the separating centrifuge of above-mentioned water absorbency resin composition keeps capacity (CRC).

19. water absorbency resin composition according to claim 13, wherein, above-mentioned wetting ability organic compound comprises the nitrogenous of the structure shown in (1) that has general formula but does not contain the ketone compound (A) of carboxyl.

20. water absorbency resin composition according to claim 13 is characterized in that, above-mentioned wetting ability organic compound comprises polyvalent alcohol.

21. water absorbency resin composition according to claim 13 is characterized in that, above-mentioned water-soluble polyvalent metal salt is a Tai-Ace S 150.