CN1261008A - Water absorbing agent and preparing method thereof - Google Patents
Water absorbing agent and preparing method thereof Download PDFInfo
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- CN1261008A CN1261008A CN 99127382 CN99127382A CN1261008A CN 1261008 A CN1261008 A CN 1261008A CN 99127382 CN99127382 CN 99127382 CN 99127382 A CN99127382 A CN 99127382A CN 1261008 A CN1261008 A CN 1261008A
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Abstract
To produce a water absorbent capable of improving the instantaneous water absorption rate and diffusion absorption rate into the interior of a resin in the intact state of a usual particle diameter by including a microfiller having specific physical properties in the water absorbing resin in a hydrous gel state. This water absorbent is produced by mixing (A) a hydrous gel of a water absorbing resin with (B) a microfiller having >0.1 and <=5 g/cm3 true density and drying the resultant mixture and has the component B included in the component A. The component A can be prepared by carrying out an aqueous solution polymerization of a water-soluble monomer and a crosslinking agent. The component B is preferably mixed in any stage from the polymerization of the component A to the time before drying. The component B preferably has 0.001-200 &mu m particle diameter thereof. The ratio of the components A to B is preferably 100:(0.05-10) based on mass. The absorbent preferably has 25-65 mL/g diffusion absorption rate for a 0.9% physiological saline solution and 18-40 g/g absorption amount of the initial pressurization.
Description
The invention relates to water absorbing agent, more particularly, the invention relates to specific pettiness filler, diffusion infiltration rate and improved water absorbing agent of initial stage pressurizing absorption amount and manufacture method thereof are housed in water-absorbing resins inside.
In order to improve the infiltration rate of water-absorbing resins, many kinds of methods were once proposed in the past, these methods comprise the surface area of expansion resin described below, increase and the contact area that is absorbed liquid, thus the method for the infiltration rate at the initial stage of raising.
A. in the manufacture process of water-absorbing resins, in polymerization stoste, add lower boiling volatile solvent, utilize heat of polymerization to make the volatile solvent gasification, make resin become the method (spy opens clear 59-18712) of porous matter;
B. at the water-absorbing resins that contains carboxyl with contain the blowing agent of mixed cross-linker and thermal decomposition type in the vistanex of glycidyl, make it foamable and form foamed method (spy opens clear 63-251437);
The blowing agent that is made of the azo-compound that contains amino is scattered in carries out polymerization in the monomer solution that contains unsaturated monomer and crosslinking agent, obtain the method (public again table special permission WO96-17884) of the water-absorbing resins of porous matter;
D. make water and hot-melt resin adhesive with the particulate process for granulating;
E. the mixture by water-absorbing resin particles and porous inorganic particle constitutes, and covers the method (spy opens flat 8-10616) of particle surface of tens % (weight) of water-absorbing resin particles total amount with this inorganic particulate.
But, when adopting these methods, may not necessarily meet the demands at aspects such as performance and manufacture methods.
The porous materialization method of above-mentioned a though can improve infiltration rate to a certain extent, must be used lower boiling volatile solvent, therefore needs special manufacturing equipments such as explosion-proof type.
The method of the use thermal decomposition type blowing agent of above-mentioned b, because the quality of raw material water-absorbing resins and vistanex is very hard, do not have pliability, acquire a certain degree than hyperbar the time, gas discharges quickly, thereby the foaming diameter is big, produces uneven bubble, causes the performance heterogeneity.
The method of above-mentioned c when producing nitrogen, generates free radical containing that amino azo-compound decomposes simultaneously, thereby the molecular weight of water-absorbing resins body reduces, and causes problems such as the low and water soluble ingredient amount increase of water absorbing properties.
The use adhesive of above-mentioned d is with the particulate process for granulating, if strengthen the cohesive force of adhesive, the effect of improving infiltration rate is undesirable, otherwise, if weaken the cohesive force of adhesive, then the mechanical strength of granulation thing is weakened, screw rod dispenser and empty sending in the operation because the effect of mechanical shear stress, granulation is destroyed, reverts to original particulate.
Above-mentioned e covers the method on the surface of a part of water-absorbing resin particles with the porous inorganic particle, though because the apparent surface area of resin particle enlarges, the transient absorption speed at absorption initial stage makes moderate progress to a certain extent, therefore but the infiltration to resin inside does not have any effect for liquid, spreads infiltration rate and initial stage pressurizing absorption amount does not improve.On the other hand, owing to must use a large amount of inorganic particulates, thereby the absorption multiplying power of resultant composition reduces.
The method of above-mentioned a～e, it is the surface area of taking to increase resin particle, improve the way of the transient absorption at absorption initial stage, in the occasion that a large amount of water-absorbing resin particles exists with the form of aggregation, the gel caking is the DeGrain that improves of so-called pimple phenomenon.In addition, be absorbed the infiltration of liquid and also significantly do not improve, thereby do not have positive effect for the improvement of diffusion infiltration rate and initial stage pressurizing absorption amount to the particle inside of water-absorbing resins.
The inventor has carried out deep research repeatedly to the problems referred to above, found that, mix small filler in the aqueous gel by the water-absorbing resins before the water-absorbing resins of aqueous gel state, particularly drying with specific rerum natura, with this mixture drying, make water-absorbing resin particles inside that the pettiness filler is housed, under the condition of common particle diameter, not only can improve transient absorption speed, and can improve diffusion infiltration rate, thereby finished the present invention to resin inside.
The 1st purpose of the present invention be, the water absorbing agent that transient absorption speed not only is provided but also all is improved to the diffusion infiltration rate of resin inside.
The 2nd purpose of the present invention be, provides the processing characteristics of particle good, seldom makes the water absorbing agent that particle destroys because of mechanical shear stress or friction.
The 3rd purpose of the present invention is to provide moisture-holding capacity and pressurizing absorption amount the good and less water absorbing agent of water soluble ingredient amount.
The 4th purpose of the present invention is to provide absorbent described below, promptly, when this water absorbing agent is used for absorbing products, resulting absorbing products can not produce resin particle because vibration waits to be separated with inorganic particulate, comes off from fibrous material, has stable performance.
The present invention is that apparent density with undried water-absorbing resins (A) and per 1 particle after the polymerization is greater than 0.1g/cm
3, less than 5g/cm
3Small filler (B) mix resulting aqueous gel drying, make the water absorbing agent of built-in in (A) (B).In addition, the present invention is the manufacture method of water absorbing agent, it is characterized in that, water-soluble monomer and crosslinking agent are carried out aqueous solution polymerization, dry then, make water-absorbing resins (A), wherein, the arbitrary stage before dry from being aggregated to of (A), with the apparent density of per 1 particle greater than 0.1g/cm
3Less than 5g/cm
3Small filler (B) mix with (A), be benchmark with the quality, be 100 (A): (0.05-10) with (B) ratio.
The preferred implementation of invention is described below:
[object lesson of water-absorbing resins (A)]
In the present invention, water-absorbing resins (A) for example can be enumerated: starch-acrylates crosslinking copolymers body, starch-acrylonitrile copolymer saponified, the crosslinked body of polyacrylate, the polyacrylate of self-crosslinking, the crosslinked body of (methyl) acrylate-acetate ethylene copolymer saponified, the crosslinked body of isobutene/copolymer-maleic anhydride, the crosslinked body of polysulfonate, polyacrylate/polysulfonate crosslinking copolymers body, the crosslinked body of poly propenoic acid acrylamide copolymer, cross-linked polyacrylamide and hydrolysate thereof, PVPP, the crosslinked body of cellulose derivative etc.Preferably, utilize ionic osmotic pressure can absorb, keep big quantity of fluid, even the water that imposed load or external force break away from also seldom the polymerizable monomer to contain carboxylate and/or carboxylic acid is the water-absorbing resins of main composition composition, more preferably starch-acrylates crosslinking copolymers body and the crosslinked body of polyacrylate.
When (A) being the resin of neutralized salt form, the kind and the degree of neutralization of salt have no particular limits, and the kind of salt is alkali metal salt normally, and preferably sodium salt and sylvite generally are 50-90% (moles) for the degree of neutralization of acid group, preferably 60-80% (mole).
The water-soluble monomer that uses when making (A) for example can be enumerated free-radical polymerised water-soluble monomer and the salt thereof with carboxyl, sulfonic group, phosphate.
Free-radical polymerised water-soluble monomer with carboxyl for example can be enumerated undersaturated monobasic or polybasic carboxylic acid [(methyl) acrylic acid (referring to acrylic acid and/or methacrylic acid, hereinafter identical), crotonic acid, sorbic acid, maleic acid, itaconic acid, cinnamic acid and their salt etc.] and acid anhydrides [maleic anhydride etc.] thereof.
Have sulfonic free-radical polymerised water-soluble monomer and for example can enumerate aliphatic acid or aromatic ethenyl sulfonic acid (vinyl sulfonic acid, allyl sulphonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid etc.), (methyl) acrylic alkyl sulfonic acid [(methyl) sulfoethyl acrylate, (methyl) acrylic acid sulfopropyl ester etc.], (methyl) acrylamide alkyl sulfonic acid [2-acrylamide-2-methyl propane sulfonic acid etc.] and their salt etc.
Free-radical polymerised water-soluble monomer with phosphate for example can be enumerated (methyl) acrylic acid hydroxy alkyl phosphate monoester [2-ethoxy (methyl) acryloyl group phosphate, phenyl-2-acryloxy ethyl phosphonic acid ester etc.] etc.
Above-mentioned monomer can more than 2 kinds and be used.Wherein, preferably water-soluble monomer is free-radical polymerised water-soluble monomer and the salt thereof with carboxyl, more preferably unsaturated monobasic or polybasic carboxylic acid and salt thereof, preferably (methyl) acrylic acid and salt thereof.
The crosslinking agent that uses when making (A) for example can be enumerated crosslinking agent, the crosslinking agent with ethene unsaturated group and reactive functional group with 2 above ethene unsaturated groups, have the crosslinking agent of 2 above reactive functional group etc.
Object lesson with compound of 2 above ethene unsaturated groups can be enumerated: N, N '-methylene two (methyl) acrylamide, ethylene glycol bisthioglycolate (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, glycerine (two or three) acrylate, trimethylolpropane triacrylate, triallylamine, triallyl cyanurate, triallyl isocyanurate, tetraene propoxyl group ethane and pentaerythrite three allyl ethers etc.
Object lesson with compound of ethene unsaturated group and reactive functional group can be enumerated (methyl) glycidyl acrylate, N-methylol (methyl) acrylamide etc.
Object lesson with compound of 2 above reactive functional group can be enumerated ethylene glycol, diethylene glycol, glycerine, propane diols, diethanol amine, trimethylolpropane and polymine etc.
These crosslinking agents can more than 2 kinds and be used.Wherein, the crosslinking agent that preferably has the combined polymerization of 2 above ethene unsaturated groups, N more preferably, N '-methylene diacrylamine, glycol diacrylate, trimethylolpropane triacrylate, tetraene propoxyl group ethane, pentaerythrite three allyl ethers, triallylamine.
With the total Mass Calculation of water-soluble monomer and crosslinking agent, the consumption of crosslinking agent generally is 0.001-5%, preferably 0.05-2%, preferably 0.1-1%.
The consumption of crosslinking agent is higher than at 0.001% o'clock, and the important performance of suction, these water-absorbing resins of water holding capacity increases, and the gel after the suction can not become the colloidal sol shape.In addition, the drying property of the aqueous gel shaped polymer after the polymerization is good, and productivity ratio is higher.On the other hand, its consumption is 5% when following, crosslinked can be too not strong, can give full play to suction, water holding capacity.
The polymerization of water-absorbing resins (A) has no particular limits, and for example can adopt water solution polymerization process, inverse suspension polymerization method, spray polymerization method, light initiation polymerization method, radiation-initiated polymerization method etc.
Preferred polymerization is to use radical polymerization initiator to carry out the method for aqueous solution polymerization.At this moment, the kind of radical polymerization initiator and radical polymerization condition all have no particular limits, and can carry out routinely.
In addition, in these polymerizations system, can add various additives, chain-transferring agent (for example mercaptide etc.), surfactant etc. as required.
As for the water absorbing properties of resulting water-absorbing resins (A), be 10-23ml/g for the diffusion infiltration rate of 0.9% (quality) normal saline solution, be 5-18g/g for the initial stage pressurizing absorption amount of 0.9% normal saline solution.
[object lesson of pettiness filler (B)]
In the present invention, the apparent density of per 1 particle of small filler (B) is normally greater than 0.1g/cm
3, less than 5g/cm
3, 0.15-4g/cm preferably
30.3-4g/cm preferably
3
The apparent density of per 1 particle (B) surpasses 5g/cm
3The time, do not find that water absorbing agent has big volume to increase, thereby the raising effect deficiency of the diffusion infiltration rate of resulting water absorbing agent.Otherwise the apparent density of per 1 particle (B) is lower than 0.1g/cm
3The time, the volume of water absorbing agent increases excessive, and the diffusion infiltration rate reduces on the contrary, and particle intensity is low, and particle is subjected to the time spent of doing of mechanical shear stress or impact, friction and destroys, generation particulate etc., processability has problems sometimes.
The apparent density of said here per 1 particle (hereinafter to be referred as apparent density) is meant the quality of the per unit volume of the particle that comprises bubble, for example the value that adopts " ACCUPYC 1330 PYCNOMETER " to measure.The example of concrete measurement operation is as follows.
2 chambers that useful valve connects in " PYCNOMETER ", i.e. cell and expanding chamber, their volume is represented with Vc and Ve respectively.In cell, establishing volume is V, measures the quality (W) of sample, closes the valve that is connected with expanding chamber, is P1 with the pressure fixing in the cell.The pressure of the expanding chamber of this moment is Pa.Open the valve that is connected with expanding chamber then, measure the pressure P 2 that reaches homogeneous in two chambers.Obtain volume of sample by volume and the pressure of opening each chamber, valve front and back, calculate apparent density by following formula.
Apparent density=W ÷ V=W ÷ [Vc+Ve * Pa-P2} ÷ P1-P2}]
Apparent density can be by not containing bubble the density and the bubble quantity and bubble of object itself adjusted.
(B) particle diameter is 0.001-200 μ m normally, preferably 0.005-150 μ m, preferably 0.01-100 μ m.Here said particle diameter not necessarily is meant the particle diameter of primary particle, also comprises the particle diameter of agglutinator or granulation thing.(B) particle diameter is greater than the occasion of 200 μ m, and the homogeneity when mixing (B) in the aqueous gel of (A) reduces, and the raising effect of the diffusion infiltration rate of resulting water absorbing agent is less sometimes, thereby inadvisable.Otherwise, less than the occasion of 0.001 μ m, when in the aqueous gel of (A), mixing (B), (B) produce aggegation to each other, take place to mix inhomogeneous, also inadvisable easily.
(B) specific area that employing BET method is measured has no particular limits, normally 50m
2More than/the g, 100m preferably
2More than/the g, 150-1000m preferably
2/ g.The specific area of pettiness filler is big more, and the raising effect of diffusion infiltration rate is often also big more.
(B) kind has no particular limits, so long as water insoluble and do not get final product with water-absorbing resins reaction, can be in organic system or the inorganic system any.
The example of organic system pettiness filler can be enumerated
(1) the organic system filler that only constitutes: polyethylene, polypropylene, polystyrene, Parylene, polybutadiene etc. by carbon atom;
(2) the organic system filler that constitutes by carbon and oxygen atom: polyacrylate, polymethacrylates, polyvinyl acetate, polyvinylether, thermoplastic polyester, Merlon, polyphenylene oxide, polyepoxide, polyacetals, cellulose derivative etc.;
(3) contain the organic system filler of nitrogen-atoms: polyacrylonitrile, polyamide, thermoplastic polyurethane etc.;
(4) other organic system filler: polyvinyl chloride, polyvinylidene chloride, fluorine resin, polysulfones etc. and the monomer filler that combined polymerization obtains more than 2 kinds that will constitute these resins.Wherein, preferentially select (1) for use.In addition, the organic system filler can not melt when making aqueous gel dry, and its fusion temperature must be more than baking temperature.Balance each other with baking temperature, the fusion temperature of organic system filler is normally more than 130 ℃, preferably more than 150 ℃.
Inorganic is that the pettiness filler can be any in natural inorganic thing and the synthesizing inorganic thing, for example can enumerate oxides such as silica, aluminium oxide, iron oxide, titanium oxide, magnesia, zirconia.They can be more than 2 kinds and usefulness, perhaps also can form composite oxides more than 2 kinds.
Wherein, the pettiness filler of inorganic system preferably.
(B) shape has no particular limits, and can be hollow form, cellular, petal-shaped, aggegation shape, granulation shape etc.Preferred shape is hollow form and cellular.
The object lesson of the small filler (B) among the present invention for example can be enumerated: three machine chemical industry are built キ ョ-ワ-De that サ Application キ ラ イ ト that society makes, テ ラ Off ア イ Application that the マ テ リ ア of space portion Le ズ society makes, worker ア ロ ジ Le 200 that Japanese ア worker ロ ジ Le society makes, Off ロ-ラ イ ト, Off ア イ Application シ-Le, consonance chemical industry society that ト Network ヤ マ society makes make etc.
With respect to water-absorbing resins (A), the amount of small filler (B) is 0.05-10% (quality) normally, preferably 0.1-7% (quality), preferably 0.2-5% (quality).Addition is 0.05% when above, can bring into play the effect that improves the diffusion infiltration rate, on the other hand, 10% when following, the diffusion infiltration rate improves, and the increase of the mechanical strength of resulting water absorbing agent particle, in addition, the absorption multiplying power of resulting water absorbing agent, moisture-holding capacity and pressurizing absorption amount can not reduce.
[manufacture method of water absorbing agent]
(B) is mixed in the dry preceding aqueous gel of (A), can cooperates in the dry arbitrary stage before that is aggregated to from manufacturing (A) time.That is, can add making it polymerization in the polymer fluid to, be formed on the mixture that cooperates (B) in the aqueous gel shaped polymer of (A), add (B) in also can the aqueous gel shaped polymer after polymerization to form mixture.Preferably mixing method is carried out in interpolation (B) the aqueous gel shaped polymer in the stage before dry after the polymerization of (A).If cooperate after drying (B), the pettiness filler covers the particle surface of (A), and perhaps (A) separates with small filler, as the two mixture and exist, thereby run counter to original intention of the present invention.Under such state, though transient absorption is improved to some extent, the pettiness filler is not to be present in resin particle inside, thereby the diffusion infiltration rate of liquid to resin inside do not improve.Under the aqueous gel state, cooperate the pettiness filler, then the water evaporates in the aqueous gel is fallen, make resin inside contain (built-in) pettiness filler, can improve the diffusion infiltration rate of liquid to resin inside.
(B) can add with any form of powder, slurry or dispersion liquid.In addition, the moisture content in aqueous gel (A) and the mixture (B) has no particular limits, and preferably, with respect to the solid shape branch of (A), the amount of water is its 2-10 times.The water yield is more than 2 times the time, and the homogeneity when mixing increases, and the diffusion infiltration rate of resulting water absorbing agent is improved; In addition, the water yield is below 10 times the time, and the dry needed time does not prolong, and is both economical.
Cooperate in (A) of aqueous gel state (B), the mixing arrangement that its homogeneous is mixed can use known in the past device.The object lesson of this device can be enumerated double arm kneading mixer, banbury (Banbury), self-cleaning mixing roll, gear mixer, screw extruder, screw mixer, pulverizer etc.These devices also can several be used in combination.
Added normally 60-230 ℃ of the baking temperature of the aqueous gel shape mixture of (B), preferably 100-200 ℃, preferably 105-180 ℃.When baking temperature is lower than 60 ℃, the dry needs, very uneconomical than the long time; Otherwise, when being higher than 230 ℃, producing side reaction sometimes or cause resin decomposition etc., cause absorbent properties and diffusion infiltration rate to reduce.
The device that is used for (A) of dry aqueous gel state and mixture (B) can be conventional device, for example drum dryer and flow belt dryer (tunnel dryer), ventilation belt dryer, discharging jet (nozzle formula) drier, box hot-air drier, infared dryer etc.Thermal source has no particular limits, and these driers can several uses that combine.Pulverize after the drying, adjust granularity in case of necessity, use acidic groups such as having 2 carboxyls at least and/or can be the near surface of resulting water absorbing agent particle is surface-crosslinked, obtain water absorbing agent of the present invention with the functional group's of this alkali reaction crosslinking agent.The water absorbing agent of surface-crosslinked type so not only depress its absorbent properties and infiltration rate is all very good under normal pressure but also adding, and gel strength is also very big, thereby is suitable for the present invention.
Surface-crosslinked employed crosslinking agent can use employed in the past known crosslinking agent.Concrete example can be enumerated: poly epihydric alcohol ether compound (ethylene glycol diglycidylether, glycerine-1,3-diglycidyl ether, glycerine triglycidyl ether, polyethyleneglycol diglycidylether, polyglycereol polyglycidyl ether etc.); Polyol compound (glycerine, ethylene glycol, polyethylene glycol etc.); Polyamine compounds (ethylenediamine, Diethylenetriamine etc.); Polyamine is resin (polyamide polymeric amine epichlorohydrin resin, polymeric amine epichlorohydrin resin etc.), ethylene carbonate, nitrogen heterocycle propane compound, polyimide compound etc.Wherein, consider that from carrying out surface-crosslinked angle at a lower temperature preferentially selecting poly epihydric alcohol ether compound, polyamine for use is resin and nitrogen heterocycle propane compound.
Dosage of crosslinking agent when surface-crosslinked can change according to the kind of crosslinking agent, crosslinked condition and desired performance etc., have no particular limits, with respect to water-absorbing resins (A), 0.001-3% (weight) normally, preferably 0.01-2% (weight), preferably 0.05-1% (weight).The amount of crosslinking agent is when 0.001% (weight) is above, and above-mentioned performance is better than not carrying out surface-crosslinked water-absorbing resins.On the other hand, when 3% (weight) was following, absorbent properties can not reduce yet.
In (A) and mixture (B) of aqueous gel state, can add additive and extender as required, for example residual monomer reduces agent (as sodium sulfite, hydrogen peroxide etc.), antiseptic (as quarternary ammonium salt compound, washing must safe compound, slaine series antibacterial agent etc.), anticorrisive agent, aromatic, deodorant, colouring agent, antioxidant etc.These additives can add in the dry run of aqueous gel shape mixture or after dry.Do not comprise in extender and the colouring agent (B).
The size distribution of water absorbing agent of the present invention does not change in surface-crosslinked front and back.The size distribution of water absorbing agent normally, the particle amount of 1000 μ m-150 μ m is more than 90% (quality), preferably more than 95% (quality).
The oversize grain amount that surpasses 1000 μ m is when 10% (quality) is following, and the diffusion infiltration rate does not reduce.When 10% (quality) was following, the generation of dust can not increase less than the particulate amount of 150 μ m, was not easy caking under high humidity, can not produce problems such as the low and operating environment deterioration of powder processability.
Average grain diameter generally is 300-700 μ m, preferably 350-600 μ m.
Under the moisture of particle was drying regime below 1.5%, the breaking stress of particle is 10N/m normally
2More than, 20N/m preferably
2More than, 25N/m preferably
2More than.
Because water absorbing agent of the present invention is 25-65ml/g for the diffusion infiltration rate of 0.9% (quality) normal saline solution, 28-60ml/g preferably, thereby when being used for amenities such as nappy, have the effect that improves dry feeling and reduce seepage.In addition, the initial stage pressurizing absorption amount of the surface-crosslinked water absorbing agent of the present invention that obtains has improved, diffusion infiltration rate for 0.9% normal saline solution is 25-65ml/g, 28-60ml/g preferably, and the initial stage pressurizing absorption amount for 0.9% normal saline solution is 18-40g/g, 25-40g/g preferably, thereby when being used for amenities such as nappy, dry feeling further improves, and can further reduce seepage.
[absorbent commodity]
The absorbed layer that absorbent commodity of the present invention is made of water absorbing agent of the present invention and fibrous material is wrapped in the sealer with water penetration part and constitutes.For example; the adult with or the occasion of the nappy used of children or physiological articles etc.; the use form of sealer is by usually constituting at the impermeable stratum of outer surface with at the pervious bed of inner surface; the above-mentioned absorbed layer of between this is two-layer, packing into; this two-layer marginal portion couples together, and forms absorbent article.As required, the absorbed layer between two-layer can and be used with blotting paper and fluid diffusion layer.
The fibrous material that uses in this absorbed layer has no particular limits, and for example can enumerate known in the past fibrous materials such as paper pulp, synthetic fibers, semisynthetic fibre, natural fiber.The length of the thickness of fibrous material etc. also has no particular limits.
When making absorbent commodity of the present invention, can on the surface of this water absorbing agent, further apply surfactant.
The kind of surfactant has no particular limits, and can use in non-ionic surface active agent, anion surfactant, cationic surfactant and the amphoteric surfactant any.
The example of non-ionic surface active agent can be enumerated and be selected from following more than one: induced by alkyl hydroxybenzene, aliphatic alcohols, carboxylic acids, aliphatic amine, fatty acid acyl amine, contain the compound of addition of ethylene oxide in the compound bearing active hydrogen and/or expoxy propane (in the random addition of occasion or the block addition of oxirane and expoxy propane and usefulness) at hydroxyl modification or amine modified polyorganosiloxane etc., with the polyalcohols of fatty acid partial esterification etc.
The object lesson of non-ionic surface active agent can be enumerated as follows.
The induced by alkyl hydroxybenzene of, C8-C24 oxyalkylated with oxirane and/or expoxy propane;
The aliphatic alcohols of oxyalkylated equally, C10-C24;
The fatty acid of oxyalkylated equally, C10-C24;
The aliphatic amine of oxyalkylated equally, C10-C24;
The fatty acid acyl amine of oxyalkylated equally, C10-C24;
The silicone oil of PEO modification;
With the polyalcohols fatty acid partial esterification, C3-C6 of C10-C24, perhaps, the oxirane of further addition 2-20 mole and/or the compound of expoxy propane on this partial esterification thing.
Examples of anionic surfactants can be enumerated: (C8-C24) alkali metal salt of the alkali metal salt of alkyl sulfonic acid, (C8-C24) alkyl sulfate or three alkanol ammonium salts, sulfosuccinic acid diesters class, sulfosuccinic acid monoesters class, (C8-C24) alkarylsulphonic acid, on alkyl phenol or aliphatic alcohol the sulfate hemiester class etc. of the product of addition of ethylene oxide.These anion surfactants can be more than 2 kinds and usefulness, also can and use with above-mentioned non-ionic surface active agent.
The example of cationic surfactant can be enumerated: aliphatic higher amines (lauryl amine, octadecylamine etc.) inorganic acid (hydrochloric acid) salt or organic acid (acetate, formic acid etc.) salt, higher fatty acids (the stearic acid of rudimentary amine, oleic acid etc.), salol bright (ソ ロ ミ Application) A type cationic surfactant, Sa Paming (サ パ ミ Application) A type cationic surfactant, quaternary ammonium salt (chain alkyl benzyl dimethyl ammonium chloride etc.) with long-chain (C10-C22) alkyl, the inorganic acid of the epoxides of aliphatic amine (oxirane etc.) addition product or acylate etc.
The example of amphoteric surfactant can be enumerated the compound that has 1 cationic base (for example quaternary ammonium group) and anionic property base (for example carboxylic acid ester groups, sulphate groups) in a part at least, specifically can enumerate salt, 3-(3-fatty acid amide-propyl group) Dimethyl Ammonium-2-hydroxypropanesulfonic acid ester class etc. in dimethyl carboxyl methyl-aliphatic acid-alkylamide ammonium carboxylic acid.
Wherein preferably HLB (Griffin value [ゲ リ Off イ Application]) more than 3, the particularly non-ionic surface active agent of 8-14.Here said HLB is the hydrophily of presentation surface activating agent and the index of oil loving balance, kind that can be by the functional group and quantity or control by the addition molal quantity and the molecular weight of epoxides.
With the quality is benchmark, and with respect to above-mentioned water absorbing agent, the amount of surfactant is 0.1-5% normally, preferably 0.1-3%, preferably 0.2-2%.The amount of surfactant can embody with the resulting treatment effect of surfactant 0.1% when above, and the compatibility raising of resulting water absorbing agent and blood can obtain for the good water absorbing agent of the infiltration rate of blood.On the other hand, the amount of surfactant is 5% when following, and except infiltration rate improved, the powder flowbility of resulting water absorbing agent was also fine.
By on the surface of above-mentioned water absorbing agent, applying surfactant, make its surface go up the attaching surface activating agent, if surfactant has permeability, will be penetrated into the inside of water absorbing agent.
The method that applies surfactant on above-mentioned water absorbing agent has no particular limits, and for example can use conventional mixing arrangement mixed surfactant in water absorbing agent.Surfactant can be a surfactant itself, also can be the product of water or water-based liquid dilution.
Concrete device can use the device identical with above-mentioned mixing arrangement.
The water absorbing agent of handling with surfactant generally is below 30 seconds for the infiltration rate of sheep blood, and preferably below 25 seconds, and the moisture-holding capacity of swelling after 30 minutes is normally more than the 20g/g, preferably more than the 23g/g in sheep blood.
The balance that has this absorption characteristic (infiltration rate and moisture-holding capacity) owing to the water absorbing agent of handling with surfactant for blood; therefore be used for various absorbent commodities (for example sanltary towel, women with briefs, tampon, operation with liner, obstetric table with mat, wound protection with dress materials etc.), during especially for sanltary towel; compare with water-absorbing resins in the past, have the effect that improves surperficial dry feeling, reduces seepage and increase moisture-holding capacity.
Embodiment
Further specify the present invention below by embodiment and comparative example, but the present invention is not subjected to the restriction of these embodiment.The breaking stress (rupture strength) of the diffusion infiltration rate of resulting water absorbing agent, initial stage pressurizing absorption amount, pressurizing absorption amount, moisture-holding capacity and particle is measured as follows.Hereinafter, if the special instruction that does not have, % is expression quality %.
[assay method of diffusion infiltration rate]
Preparation is adjusted into granularity 30-60 purpose water absorbing agent 0.10g as sample with the JIS standard screen.
Device shown in Figure 1 is placed on the estrade of level.In addition, confirm that the tubule position 5. of air inflow aperture and dull and stereotyped upper face 6. are levels.
The cock of closing the buret foot 1. with the cock of cross-drilled hole 2., by the top of buret with the normal saline solution of 0.9% (quality) pack into buret 4. in.The cock of closing the buret topmost then 3., the cock of opening foot 1. with the cock 2. of cross-drilled hole before, the scale of the normal saline solution capacity in the reading displayed buret.On the flat board hole 6. in hole, place the plain weave nylon screen (5cm * 5cm) 7., place 8. 0.10g of sample in the above of 63 μ m width of mesh with 3mm.In case put sample, just begin suction, begin constantly to measure from this, read the scale on the buret, measure the uptake after 2 minutes.With the suction decrement buret in normal saline solution capacity 10 times of values as the diffusion infiltration rate.
[assay method of initial stage pressurizing absorption amount and pressurizing absorption amount]
Posting on the bottom surface packs in the cylinder type plastic tube (internal diameter 30mm, height 60mm) of 250 purpose nylon wires is adjusted into granularity 30-60 purpose water absorbing agent sample 0.10g with the JIS standard screen, and it is flattened.On this water absorbing agent, place the counterweight of external diameter 30mm, make it to reach 20g/cm
2Load.Leave standstill the plastic tube of the water absorbing agent of packing in the central authorities of the culture dish of putting into the 60ml0.9% saline solution (diameter 12cm), make under nylon wire one side direction.Measure water absorbing agent after 10 minutes and after 60 minutes and absorb the quality that increases behind 0.9% saline solution.With 10 times of values of gaining in weight after 5 minutes as initial stage pressurizing absorption amount for 0.9% normal saline solution, with 10 times of values of the weight that increases after 60 minutes as pressurizing absorption amount for 0.9% normal saline solution.
[assay method of moisture-holding capacity]
In the tea-bag made from 250 purpose nylon wires (long 20cm, wide 10cm), pack into and be adjusted into granularity 30-60 purpose water absorbing agent sample 1.00g with the JIS standard screen, it is flooded in 0.9% (quality) normal saline solution of 500ml, absorbs 60 minutes, hang then and removed moisture in 15 minutes, use centrifugal dehydrator with the centrifugal force centrifugal dehydration of 150G 90 seconds again, the quality that measure to increase, as for 0.9% normal saline solution moisture-holding capacity.
[assay method of particle breaking stress]
Use creepmeter (Network リ-プ メ--) (electricity Co., Ltd. in mountain makes) that the sample of 425-500 μ m particle diameter is carried out compression test, obtain the stress value of particle when disrumpent feelings, as the breaking stress (N/m of unit
2).
[the infiltration rate assay method of sanitary napkin]
With weight per unit area is 100g/m
2Pulp layer be cut into 6cm * 15cm size, uniformly dispersing 0.4g absorbent composition sample in the above.Stack same weight per unit area and onesize pulp layer again, on woven wire with 10kg/cm
2Suppressed 30 seconds, and made absorber layers.Dispose the leakproof film bigger than absorber layers in its lower section, prepare the nonwoven that artificial silk is made in the above, heat sealing around inciting somebody to action along absorber layers is made the sanitary napkin model.In the hole that the central authorities with the acrylic panel of the same area of absorber layers of sanitary napkin model open a diameter 12mm, the cylinder of fixed inner diameter 12mm (length 10cm) is made injection plate on the hole.With this injection plate be configured in the sanitary napkin model above, the load of placing 20g is equably injected 5g sheep blood from cylinder, measure 5g sheep whole absorbed times of blood.Measure three times, average as infiltration rate.
[assay method of sanitary napkin moisture-holding capacity]
The sanitary napkin model is flooded in excessive sheep blood, absorbs 5 minutes, then, make surperficial nonwoven one side outwardly, with 250G gravity centrifugal dehydration 2 minutes, obtain the weight of increase, first behind the decimal point rounds up, and institute's value is as moisture-holding capacity.
[assay method of the diffusion area of sanitary napkin]
After measuring infiltration rate, obtain absorber layers and absorb the area that spreads behind the sheep blood, with the mean value measured for three times as diffusion area.
[assay method of the surperficial dry feeling of sanitary napkin]
After measuring diffusion area, judge the dry feeling of sanitary napkin model surface by finger touch by 5 experts.This operation is averaged after carrying out three times repeatedly, estimates by following standard.
◎: dry feeling is good.
Zero: a little a bit wet, do not have problems in the practicality.
Δ: small amount of liquid oozes out, and is a bit sticking.
*: liquid oozes out more, and is slimy.
In capacity is 1 liter the reaction vessel of glass system, pack into PAA 77g, acrylic acid 22.8g, N, N '-methylene diacrylamine 0.2g and deionized water 295g, one side stirs, mixes, and one side remains on 3 ℃ with the temperature of content.
In content, flow into nitrogen, soluble oxygen content is reduced to below the 1ppm, add 1% aqueous solution 1g of hydrogen peroxide, 0.2% aqueous solution 1.2g and 2 of ascorbic acid then, 2% aqueous solution 2.8g of 2 '-azo diamidino propane dihydrochloride, mix, initiated polymerization, polymerization obtain aqueous gel shaped polymer (A1) after about 5 hours.With banbury (A1) carefully is broken into the 2-5mm size, adds DGEEG 0.1g and サ Application キ ラ イ ト YO2 (apparent density=0.66g/cm then
3, particle diameter 20-70 μ m) and (B1) 3g, after further mixing with banbury, carry out drying with ventilation type belt dryer (aboveground metal industry manufacturing) under 150 ℃, the condition of wind speed 2.0m/ second.
Pulverize resulting dry thing, granularity is adjusted into the 20-100 order, obtain water absorbing agent (1).The performance evaluation of this water absorbing agent (1) the results are shown in the table 1.
With banbury the aqueous gel shaped polymer (A1) that obtains among the embodiment 1 carefully is broken into the 2-5mm size, adds and mix, operate similarly to Example 1 subsequently, obtain the water absorbing agent of 20-100 order granularity with (B1) of embodiment 1 equivalent amount.With this water absorbing agent high-speed stirred of 100g, meanwhile, 10% water/methyl alcohol mixed solution (water/methyl alcohol=30/70) 2g that adds ethylene glycol diglycidylether also mixes, and subsequently 140 ℃ of heat cross-linkings 30 minutes, obtains the water absorbing agent (2) of surface-crosslinked type.The performance evaluation of this water absorbing agent (2) the results are shown in the table 1.
In embodiment 2, change the addition of (B1) into 1g and 6g respectively, in addition operation similarly to Example 2 obtains the water absorbing agent (3) and the water absorbing agent (4) of surface-crosslinked type.Their performance evaluation the results are shown in the table 1.
In embodiment 2, replace (B1) to use (B2) of same quantity and (B3) respectively, in addition operate similarly to Example 2, obtain pettiness filler water absorbing agent (5) and water absorbing agent (6).The performance evaluation of these water absorbing agents the results are shown in the table 1.
(B2): テ ラ Off ア イ Application (apparent density=0.71g/cm
3, particle diameter 10-30 μ m)
(B3): ア エ ロ ジ Le 200 (apparent density=2.2g/cm
3, particle diameter 0.01 μ m)
Embodiment 7
PAA 77g, acrylic acid 22.75g, N pack in capacity is 1 liter the reaction vessel of glass system, N '-methylene diacrylamine 0.25g and deionized water 293g, one side stirs, mixes, and one side is added " サ Application キ ラ イ ト YO2 " (B1) 3g, and the temperature of content is remained on 3 ℃.
In content, flow into nitrogen, soluble oxygen content is reduced to below the 1ppm, add 1% aqueous solution 1g of hydrogen peroxide, 0.2% aqueous solution 1.2g and 2 of ascorbic acid then, 2% aqueous solution 2.8g of 2 '-azo diamidino propane dihydrochloride, mix, initiated polymerization, polymerization are contained the aqueous gel shaped polymer complex (AB1) of (B1) after about 5 hours.
With banbury (AB1) carefully is broken into the 2-5mm size, under 150 ℃, the condition of wind speed 2.0m/ second, carries out drying with the ventilation type belt dryer.Pulverize resulting dry thing, granularity is adjusted into the 20-100 order, obtain water absorbing agent.With this water absorbing agent high-speed stirred of 100g, meanwhile, 10% water/methyl alcohol mixed solution (water/methyl alcohol=30/70) 2g that adds ethylene glycol diglycidylether also mixes, and 140 ℃ of heat cross-linkings 30 minutes, obtains water absorbing agent (7).The performance evaluation of this water absorbing agent (7) the results are shown in the table 1.
In capacity is 1 liter the reaction vessel of glass system, pack into acrylic acid 81.75g, N, N '-methylene diacrylamine 0.25g and deionized water 241g, one side stirs, mixes, and one side remains on 3 ℃ with the temperature of content.
In content, flow into nitrogen, soluble oxygen content is reduced to below the 1ppm, add 1% aqueous solution 1g of hydrogen peroxide, 0.2% aqueous solution 1.2g and 2 of ascorbic acid then, 2% aqueous solution 2.8g of 2 '-azo diamidino propane dihydrochloride, mix, initiated polymerization, polymerization obtain the aqueous gel shaped polymer of acid type after about 5 hours.
With banbury this aqueous gel shaped polymer carefully is broken into the 2-5mm size, meanwhile adds 30% sodium hydrate aqueous solution 109.1g and carry out mixingly, obtain the aqueous gel shaped polymer (A2) that carboxylic acid group's 72% (mole) is neutralized.
In aqueous gel shaped polymer (A2), add (B1) of quantity similarly to Example 1, mix, under 150 ℃, the condition of wind speed 2.0m/ second, carry out drying then with the ventilation type belt dryer.
Pulverize resulting dry thing, granularity is adjusted into the 20-100 order, obtain water absorbing agent.With this water absorbing agent high-speed stirred of 100g, meanwhile, 10% water/methyl alcohol mixed solution (water/methyl alcohol=30/70) 2g that adds ethylene glycol diglycidylether also mixes, and 140 ℃ of heat cross-linkings 30 minutes, obtains water absorbing agent (8).The performance evaluation of this water absorbing agent (8) the results are shown in the table 1.
Comparative example 1
With banbury the aqueous gel shaped polymer (A1) that obtains among the embodiment 1 carefully is broken into the 2-5mm size, add ethylene glycol diglycidylether 0.1g then, mix with banbury again, under 150 ℃, the condition of wind speed 2.0m/ second, carry out drying with the aeration type belt dryer.
Pulverize resulting dry thing, granularity is adjusted into the 20-100 order, obtain comparison water absorbing agent (a).The evaluation result of this comparison water absorbing agent (a) is shown in Table 1.
Comparative example 2
In the aqueous gel shaped polymer (A1) that embodiment 1 obtains, add (B1) 3g, mix, under 150 ℃, the condition of wind speed 2.0m/ second, carry out drying then with the aeration type belt dryer with banbury.Pulverize resulting dry thing, granularity is adjusted into the 20-100 order, obtain comparison water absorbing agent (b).The evaluation result of this comparison water absorbing agent (b) is shown in Table 1.
Comparative example 3
With banbury the aqueous gel shaped polymer (A1) that obtains among the embodiment 1 carefully is broken into the 2-5mm size, under 150 ℃, the condition of wind speed 2.0m/ second, carries out drying with the aeration type belt dryer.Pulverize resulting dry thing, granularity is adjusted into the 20-100 order, obtain water absorbing agent.With this water absorbing agent high-speed stirred of 100g, meanwhile, 10% water/methyl alcohol mixed solution (water/methyl alcohol=30/70) 2g that adds ethylene glycol diglycidylether also mixes, and 140 ℃ of heat cross-linkings 30 minutes, obtains the comparison water absorbing agent (c) of surface-crosslinked type.The performance evaluation of this comparison water absorbing agent (c) the results are shown in the table 1.
Comparative example 4 and 5
In embodiment 2, change the addition of (B1) into 0.01g and 15g respectively, in addition operation is similarly to Example 2 carried out the dry thing 100g of resulting granularity 30-60 purpose surface-crosslinkedly similarly to Example 2, obtains comparison water absorbing agent (d) and (e).Their evaluation result is shown in Table 1.
Comparative example 6
In embodiment 2, replace (B1), use the エ Network ス パ Application セ Le 461DE (apparent density=0.06g/cm of same quantity
3, particle diameter 20-40 μ m, Japanese Off エ ラ イ ト society makes) (B4), in addition operation similarly to Example 2 obtains comparison water absorbing agent (f).The performance evaluation of this comparison water absorbing agent the results are shown in the table 1.
(B4): エ Network ス パ Application セ Le 461DE (apparent density=0.06g/cm
3, particle diameter 20-40 μ m, Japanese Off エ ラ イ ト society makes)
Comparative example 7
The aqueous gel (A1) that embodiment 1 is obtained with banbury carefully is broken into the 2-5mm size, then, solid shape with respect to (A1) is divided interpolation 3% thermal decomposition type blowing agent " PVC ニ ホ-Le AZ-S " (100 ℃ of decomposition temperatures, main component: azodiisobutyronitrile, Yonghe County changes into Industrial Co., Ltd and makes), mix with banbury, under 150 ℃, the condition of wind speed 2.0m/ second, carry out drying then with the aeration type belt dryer.Pulverize resulting dry thing, granularity is adjusted into the 20-100 order, obtain the comparison water absorbing agent.With this water absorbing agent high-speed stirred of 100g, meanwhile, 10% water/methyl alcohol mixed solution (water/methyl alcohol=30/70) 2g that adds ethylene glycol diglycidylether also mixes, and 140 ℃ of heat cross-linkings 30 minutes, obtains the comparison water absorbing agent (g) of surface-crosslinked type.The performance evaluation of this comparison water absorbing agent (g) the results are shown in the table 1.
Comparative example 8
At 100 parts of foaming シ ラ ス (" シ ラ ッ Network ス PB10 ", the シ ラ ッ of Co., Ltd. Network ス makes, average grain diameter 470 μ m) 10% aqueous solution of middle interpolation, mixing pva (jelly grade 88% (mole)) is 15 parts, in resulting mixture, add the comparison water absorbing agent (a) that obtains in 100 parts of comparative examples 1, left standstill 1 hour after fully mixing, drying is 3 hours under 120 ℃, obtains comparison water absorbing agent (h).The performance comparison result of this comparison water absorbing agent (h) is shown in Table 1.
[table 1]
| Water absorbing agent | Diffusion absorbs ml/g | Initial stage g/g | Pressurizing absorption amount g/g | Moisture-holding capacity g/g | Breaking stress N/m 2 | |
| Embodiment 1 | ??(1) | ????35 | ????22 | ????29 | ????35 | ????30 |
| Embodiment 2 | ??(2) | ????33 | ????25 | ????32 | ????38 | ????26 |
| Embodiment 3 | ??(3) | ????28 | ????27 | ????33 | ????38 | ????30 |
| Embodiment 4 | ??(4) | ????34 | ????26 | ????31 | ????37 | ????26 |
| Embodiment 5 | ??(5) | ????32 | ????25 | ????30 | ????38 | ????30 |
| Embodiment 6 | ??(6) | ????33 | ????25 | ????31 | ????39 | ????31 |
| Embodiment 7 | ??(7) | ????31 | ????26 | ????32 | ????38 | ????28 |
| Embodiment 8 | ??(8) | ????32 | ????27 | ????33 | ????41 | ????30 |
| Comparative example 1 | ??(a) | ????24 | ????17 | ????27 | ????35 | ????27 |
| Comparative example 2 | ??(b) | ????24 | ????8 | ????14 | ????46 | ????29 |
| Comparative example 3 | ??(c) | ????22 | ????17 | ????29 | ????38 | ????30 |
| Comparative example 4 | ??(d) | ????22 | ????19 | ????31 | ????39 | ????31 |
| Comparative example 5 | ??(e) | ????18 | ????18 | ????28 | ????37 | ????20 |
| Comparative example 6 | ??(f) | ????21 | ????23 | ????33 | ????38 | ????5 |
| Comparative example 7 | ??(g) | ????20 | ????16 | ????24 | ????34 | ????1 |
| Comparative example 8 | ??(h) | ????15 | ????5 | ????10 | ????17 | ????29 |
Use water absorbing agent (a) that embodiment 4 and 8 resulting water absorbing agents (4) and (8) and comparative example 1 and 3 obtain and (c) make the sanitary napkin model, estimate its performance, the results are shown in the table 2.[table 2]
| Water absorbing agent | Infiltration rate (second) | Moisture-holding capacity g | Diffusion area cm 2 | The surface dry feeling | |
| Embodiment 9 | ???(4) | ????20 | ????15 | ??????45 | ????◎ |
| | ???(8) | ????23 | ????15 | ??????44 | ????○-◎ |
| Comparative example 9 | ???(a) | ????66 | ????8 | ??????26 | ????× |
| Comparative example 10 | ???(c) | ????60 | ????9 | ??????29 | ????× |
Application on industry water absorbing agent of the present invention and manufacture method thereof have following feature and effect.
1. diffusion absorption speed is fast, and initial stage pressurizing absorption amount (expression adds the infiltration rate of depressing) is good, thereby, for example when being used as the absorbent of amenities, have the effect of raising initial stage dry feeling and minimizing seepage.
2. moisture-holding capacity and pressurizing absorption amount are all very good.
3. the processability of powder is good, and, atomic granules basically can be owing to the effect of mechanical shear stress or friction failure, produce particulate.
When 4. being mixed and made into absorber with fibrous materials such as paper pulp, even apply the external force such as vibration, basically can not break away from from fibrous material yet.
5. different from the improvement of adopting thermal decomposition type blowing agent to obtain, do not produce free radical etc. during heat drying, thereby the manufacture process performance can be not deteriorated, and not only diffusion absorption speed and absorbent properties are good, and can obtain the less water absorbing agent of water soluble ingredient amount.
6. because the interior built-in pettiness filler of water-absorbing resin particles, compare with the water-absorbing resins that covers with the porous inorganic particle, the separation of the inorganic particulate that can not occur in the transportation or cause owing to vibration, inhomogeneous and come off can obtain stable and good performance.
7. adopt in the water-absorbing resins polymerization process or mix small filler from the arbitrary stage before dry after the polymerization after carry out dry straightforward procedure, just can realize the improvement of diffusion absorption speed.
Owing to have an above-mentioned effect, the water absorbing agent that obtains with manufacture method of the present invention is particularly suitable for diaper that disposable paper diaper (child with and the nappy of adult's usefulness), sanltary towel, aconuresis person use, breast milk pad, operation with amenities and medical supplies such as pad, obstetric table pad, wound protection dress materials, pet pads. In addition, can also be applicable to various absorbent sheet classes (such as flashing of pet urine absorbing sheet, antistaling tablet, the absorbing sheet that drips, raising rice seedlings sheet, cement conservation sheet, cable class etc.). In addition, can also be applicable to use the purposes of water absorbing agent powder, such as the electrolyte gelating agent of the solid agent of water-loss reducer of soil, sludge solidifying agent, useless blood and water-based waste liquid etc., urine gelating agent, battery etc.
Fig. 1 is the stereogram of diffusion infiltration rate determining instrument of the present invention.
Each symbol among the figure:
1. cock, 3. plate plug, 5. tubule, 7. nylon screen, 9. normal saline solution,
2. cock, 4. buret, 6. porose flat board, 8. sample, 10. atmospheric pressure
Claims (14)
1. water absorbing agent, it is that apparent density with undried water-absorbing resins (A) after the polymerization and per 1 particle is greater than 0.1g/cm
3, less than 5g/cm
3Small filler (B) mix resulting aqueous gel dry and constitute and (A) in built-in (B).
2. the described water absorbing agent of claim 1 is characterized in that, (A) is water-soluble monomer and crosslinking agent to be carried out aqueous solution polymerization and the water-absorbing resins that obtains, and is to mix (B) and form in above-mentioned (A) of the state of polymerisation to the drying process.
3. the described water absorbing agent of claim 1 is characterized in that, is benchmark with the quality, is 100 with (B) ratio (A): (0.05-10).
4. the described water absorbing agent of claim 1 is characterized in that, (B) has the particle diameter in the 0.001-200 mu m range.
5. the described water absorbing agent of claim 1 is characterized in that, (B) be inorganic be filler.
6. the described water absorbing agent of claim 1 is characterized in that, (B) be selected from silica, aluminium oxide, iron oxide, titanium oxide, magnesia, zirconia and their compound more than a kind or 2 kinds.
7. the described water absorbing agent of claim 1 is characterized in that, in the aqueous gel of (A) and mixture (B), the amount of water is (A) 2-10 a times.
8. water absorbing agent, it is further pulverized resulting particle shape thing with the described water absorbing agent of claim 1 and carries out surface-crosslinked and form.
9. claim 1 or 8 described water absorbing agents is characterized in that, the size distribution of this water absorbing agent is, the particle amount of 1000-150 mu m range is more than 90% (quality), and average grain diameter is 300-700 μ m.
10. the described water absorbing agent of claim 8 is characterized in that, this water absorbing agent is 25-65ml/g for the diffusion infiltration rate of 0.9% normal saline solution, and, be 18-40g/g for the initial stage pressurizing absorption amount of 0.9% normal saline solution.
11. the manufacture method of the water absorbing agent of built-in (A) (B) is characterized in that, water-soluble monomer and crosslinking agent are carried out aqueous solution polymerization, dry then, make water-absorbing resins (A), wherein, from the arbitrary stage before the drying of being aggregated to, with the apparent density of per 1 particle greater than 0.1g/cm
3, less than 5g/cm
3Small filler (B) mix with (A), be benchmark with the quality, be 100 (A): (0.05-10) with (B) ratio.
12. the described water absorbing agent manufacture method of claim 11 is characterized in that, making the water yield is to contain (B) in the aqueous gel of 2-10 (A) doubly of (A).
13. the manufacture method of water absorbing agent is characterized in that, the water absorbing agent that will obtain with the manufacture method of claim 11 is further pulverized the particle shape thing that obtains and is carried out surface-crosslinked.
14. absorbent commodity is characterized in that, parcel is by described water absorbing agent of claim 1-8 or the absorbed layer that is made of water absorbing agent and fibrous material that obtains with the manufacture method of claim 11-13 in having the sealer of water penetration part.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP327254/1998 | 1998-11-17 | ||
| JP32725498A JP3202703B2 (en) | 1998-08-07 | 1998-11-17 | Water absorbing agent and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1261008A true CN1261008A (en) | 2000-07-26 |
| CN1134282C CN1134282C (en) | 2004-01-14 |
Family
ID=18197065
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991273826A Expired - Fee Related CN1134282C (en) | 1998-11-17 | 1999-11-17 | Water absorbing agent and preparing method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101466280A (en) * | 2006-06-09 | 2009-06-24 | 美津浓株式会社 | Swimsuit and process for manufacturing the same |
| CN104174373A (en) * | 2014-08-30 | 2014-12-03 | 周峰 | Silica-gel drying agent |
| CN108464430A (en) * | 2018-04-09 | 2018-08-31 | 袁国森 | A kind of food desiccant and preparation method thereof |
| CN111068629A (en) * | 2019-12-25 | 2020-04-28 | 太仓运通新材料科技有限公司 | Water absorbent |
| CN111094441A (en) * | 2017-09-22 | 2020-05-01 | 三大雅株式会社 | Water-absorbent resin composition and method for producing same |
-
1999
- 1999-11-17 CN CNB991273826A patent/CN1134282C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101466280A (en) * | 2006-06-09 | 2009-06-24 | 美津浓株式会社 | Swimsuit and process for manufacturing the same |
| CN101466280B (en) * | 2006-06-09 | 2011-07-13 | 美津浓株式会社 | Swimsuit and process for manufacturing the same |
| CN104174373A (en) * | 2014-08-30 | 2014-12-03 | 周峰 | Silica-gel drying agent |
| CN111094441A (en) * | 2017-09-22 | 2020-05-01 | 三大雅株式会社 | Water-absorbent resin composition and method for producing same |
| CN108464430A (en) * | 2018-04-09 | 2018-08-31 | 袁国森 | A kind of food desiccant and preparation method thereof |
| CN111068629A (en) * | 2019-12-25 | 2020-04-28 | 太仓运通新材料科技有限公司 | Water absorbent |
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| Publication number | Publication date |
|---|---|
| CN1134282C (en) | 2004-01-14 |
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