CN108047623A - Using the raising odor-resistant result method of polyacrylic acid water-absorbent resin component - Google Patents

Abstract

The present invention relates to a kind of raising odor-resistant result methods using polyacrylic acid water-absorbent resin component, and the described method includes following：(a) a kind of deodorization combination is provided, one of which component is plant component and another component is chemical constituent, (b) plant component in the combination, the mode of deodorization can be that the smell of physics mode is neutralized or covered, or chemical reaction, (c) plant component in the combination, being used alone can be with the initial stink of substantially reduced body fluid, and plant component is bamboo powder in (d) combination；(e) bamboo powder in the combination, Particle size requirements can not only remove the initial niff of body fluid in below 800um, the combination, can also make this deodorization state continue 24 it is small when and more than.

Description

Using the raising odor-resistant result method of polyacrylic acid water-absorbent resin component

Technical field

The present invention relates to the raising odor-resistant result methods of application polyacrylic acid water-absorbent resin component.More particularly to applicable In absorbent commodity, such as：Paper nappy (disposable diaper), sanitary napkin, incontinence pad, mattress, pet pads, Wound care material, In the products such as construction material, soil water-retaining material, and with quick imbibition

The manufacturing method of the polyacrylic acid water-absorbent resin of performance, composition and other absorbent articles.

Background technology

High water absorbency polymer (Super absorbent polymer, SAP) is also known as high hydroscopic resin, is that one kind contains Strongly hydrophilic group, it is not soluble in water, but the cross-linked polymer of tens of, hundreds of or even thousands of times of water of dead weight can be absorbed.High water absorption Resin is now widely used in a variety of necks of the amenities and soil moisturizing agent etc. such as paper diaper, physiological hygiene cotton, adult-incontinence articles Domain.Stage now, water-absorbing resin neutralized it has been known that there is polyacrylic acid part after crosslinked, Starch and Acrylic Acid graft polymers Saponified, acrylonitrile copolymer crosslinked, the acrylamide copolymer of hydrolysate, vinyl acetate-acrylate copolymer Crosslinked and cationic monomer crosslinked etc..

Absorbent article such as disposable diaper, sanitary napkin, Pantiliner, incontinence pad, tampon etc. are commonly used in absorption Body fluid, such as urine, excrement, vaginal fluid and through liquid.After these fluids are absorbed, it is found that absorbent article is waved comprising many Hair property compound, the compound include with the aliphatic acid (such as isovaleric acid) of unpleasant smell, sulfur-containing compound (such as Mercaptan and sulfide), ammonia, amine (such as triethylamine), ketone (such as 4- heptanone), alcohol and alcohol (class alcohol), the smell is being worn It is released when period or processing from these products.The compound may be present in body fluid or be absorbed into suction in fluid It is generated at any time via chemical reaction and/or fluid degradation mechanism when receiving in product.In addition, oneself is absorbed into absorption in body fluid After in product, they usually equally can generate the microorganism of stench by-product and/or enzyme contacts, the drop with due to degradation mechanism Such as corrupt degradation of solution mechanism, acid degradation, protein degradation, fat acid decomposition.These smells can cause wearing for absorbent article The person of wearing and processor equally meet with unpleasant impression, and the concealed use of absorbent article and/or processing can be made to become tired It is difficult.

The technology of existing deodorization mainly includes three kinds：(1) by physical absorption adsorb malodor molecules (such as EP0295438B、WO1994022502A、EP0644207B、EP0538983B、US20050137546A、CN102225981A、 US20120258851A、CN103857714A、CN1668343A、CN1296981A、CN101050244A、CN101143913A、 CN101423588A、CN104448155A、CN102311557A、CN104448102A、CN103214616A、 CN103476811A、CN103857714A、CN105377921A、CN102317329A、CN102010560A)；(2) macromolecular bag Wrap up in malodor molecules (such as EP0591168A)；(3) chemically react, mainly there is acid-base neutralization, also have other inorganic polymer composite flocculants (such as WO2001089591A)；Wait strategies.

In deodorization technology, it is known that have using zeolite, bentonite other inorganic powders, gel, silica gel, aldehydes, quinones, Or addition aromatic.

But these current methods, all it is that deodorization ingredient is mixed in high water absorption system resin or the product is coated in height The surface of water-absorbing resins, but the state that super absorbent resin quickly absorbs water in itself so that the non-complete body fluid of deodorization is inhaled It receives inside high hydroscopic resin, can not be contacted with deodorization ingredient, so that deodorizing effect declines or is to use one merely Kind of substance uses a system, can not solve the initial stink of body fluid because body fluid have at the very start it is initial smelly Taste or using covering, physical absorption etc. again cannot remove stink from root, such as when absorbent is subject to external force to act on, Internal body fluid flow goes out, and stink again can be with the efficiency low consumption duration of its generation either reaction, it is impossible to stink is quickly removed, thorough Before removing stink, stink artistic conception allows people to feel under the weather.Aromatic is commonly used in absorbent article enhancing user to production The impression (such as release of pure and fresh fragrance) of product, these aromatic are usually added in low content, and in product entirely using following Faint odor control benefit is only provided in ring.In addition, general physical absorption system, such as activated carbon, usually not with fragrance Agent is compatible so that deodouring effect is had a greatly reduced quality.

The content of the invention

Present invention aims at provide a kind of inside just to have the water-absorbing resins of deodorization ingredient, the deodorizing effect of the resin Better than other deodorising products, and bulk density will not reduce, and not influence its imbibition characteristic, can efficiently produce at a high speed The method of the water-absorbing resins of rate of liquid aspiration, and one kind is obtained when body fluid touches absorbent, what stink was just substantially mitigated Water-absorbing resins.

In order to solve described problem, the present invention added in wet gel shattering process deodorization component or deodorization component it One, after drying or after surface treatment or after post processing, add deodorization combination, the resistance to bulk density of the resin It will not reduce, conduct and be distributed the imbibitions excellents such as absorptive capacity under the ability of liquid, liquid-keeping property, pressure, have bright Aobvious fast deodorization performance.The product is suitable for adult diaper, pet urine pad, women physiological period nursing health product, Yi Jiqi He needs quickly to go to the place to eliminate the unusual smell.

The manufacturing method of polyacrylic acid water-absorbent resin of the present invention, comprises the following steps：

(a) obtain containing unsaturated acrylic monomer and cross-linking agent aqueous solution,

(b) blowing-agent particle and/or foaming agent solution are mixed with unsaturated acrylic monomer and cross-linking agent aqueous solution, Under the conditions of temperature is -10~120 DEG C, foaming agent monomer solution is prepared.

(c) in temperature under the conditions of 20~200 DEG C, addition initiator make the monomer solution carry out polymerization formed it is porous Gelatinous cross-linked polymer.

Aqueous gel shaped polymer is crushed in the course of the polymerization process or after polymerization,

Aqueous gel shaped polymer after crushing is thermally dried,

Grain refined is carried out to porous structure cross-linked polymer after drying and is sieved,

After surface crosslinking agent processing screening near the surface of water-absorbing resins, covalent bond is formed,

With cationic compound processing water-absorbing resins surface, ionic bond is formed.

Deodorant compositions are added into the water-absorbing resin after processing, make it have fast deodorization effect.

In order to achieve the above objectives, the present invention also provides a kind of polyacrylic acid water-absorbent resin, which is 200~600 microns, porous structure average pore size is 10~500 microns, and centrifuge retention capacity is 25~50g/g, and swirl method is tested Suction salt velocity is 10~50sec/g, and levels of residual monomers is in below 500ppm.

According to the present invention, a kind of polyacrylic water absorbency resin composition is obtained, said composition includes：Water imbibition tree Fat, the resin average grain diameter are 200~600 microns, and porous structure average pore size is 10~500 microns, and centrifuge retention capacity is 25~50g/g, it is 10~50sec/g that salt velocity is inhaled in swirl method test, and levels of residual monomers is in below 500ppm；And inorganic powder End.

The invention discloses a kind of water-absorbing resins with deodoriging properties, composition and other absorbents and its manufacturers Method, its advantage can quickly remove stink, and not generate the substance of other pollution environment, and buildup of resin density will not It excessively reduces, and it is special not influence the imbibitions such as the absorptive capacity under resin conduction and the distribution ability of liquid, liquid-keeping property, pressure Property.

Specific embodiment

The polyacrylic acid water-absorbent resin and its manufacturing method of the present invention are described in detail below, but the present invention Scope is not limited to these explanations.

The polyacrylic acid water-absorbent resin of the present invention is manufactured by following steps.

It obtains containing unsaturated acrylic monomer and cross-linking agent aqueous solution,

Blowing-agent particle and/or foaming agent solution are mixed with unsaturated acrylic monomer and cross-linking agent aqueous solution, Under stirring or static conditions, the foaming agent uniformly disperses in monomer solution, dissolves 0--10 in 100 mass parts monomer solutions Foaming agent described in mass parts；

Under the conditions of temperature is 20~200 DEG C, nitrogen, carbon dioxide, oxygen are released by chemistry and/or physical reactions One or more gases in gas, ammonia or water vapor gas cause the monomer solution carry out polymerization form porous gel shape Cross-linked polymer.

Aqueous gel shaped polymer is crushed in the course of the polymerization process or after polymerization,

In crushing process, one or more ingredients in addition deodorization combination

Aqueous gel shaped polymer after crushing is thermally dried,

Grain refined is carried out to porous structure cross-linked polymer after drying and is sieved,

After surface crosslinking agent processing screening near the surface of water-absorbing resins, covalent bond is formed,

With cationic compound processing water-absorbing resins surface, ionic bond is formed.

Deodorization combination is added in the water-absorbing resin handled with cationic compound, makes it have fast deodorization performance.

1.1 monomer solution

Obtain the step of containing unsaturated acrylic monomer and cross-linking agent aqueous solution.It is specifically described below.

Monomer (monomer) used in the present invention can be formed by free radical polymerization and inhaled to contain unsaturated double-bond Monomer of the Mono-olefinic unsaturation containing acid groups of water-base resin, is not particularly limited.It can be listed below：Acrylic acid, methyl Acrylic acid, ethylacrylic acid, α-chloroacrylic acid, alpha-cyanoacrylate, Beta-methyl acrylic acid (crotonic acid), atropic acid, β-acryloxy propionic, sorbic acid, α-chlorine sorbic acid, 2 '-methyl iso-crotonic acid, cinnamic acid, p- chloro-cinnamic acid, β-tristearin Acid, itaconic acid, citraconic acid, mesaconic acid, glutaconate, aconic acid, maleic acid, cinnamic acid, fumaric acid, tricarboxylic ethylene and maleic acid Acid anhydride, particularly preferred acrylic acid and methacrylic acid, most preferably acrylic acid.

It can be copolymerized using other class monomers with the monomer containing carboxyl.It can be listed below：Vinyl sulfonic acid, alkene Propyltoluene sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, 2- (methyl) acrylamide-2-methyl propane sulfonic, 2- (methyl) The anionic properties such as acryloyl group ethanesulfonic acid, 2- (methyl) acryloyl groups propane sulfonic acid, (methyl) acryloyl group phosphoric acid 2- hydroxy methacrylates Unsaturated monomer and its salt；Unsaturated monomer containing sulfydryl；The unsaturated monomer of phenolic hydroxy group；(methyl) acrylamide, N- second The unsaturated monomer of the amide-containings such as base (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide；(methyl) acrylic acid N, N- dimethyl amido ethyl ester, (methyl) acrylic acid N, N- dimethyl amido propyl ester, N, N- Dimethylaminopropyls (methyl) third Amino-containing unsaturated monomer such as acrylamide etc..

These unsaturated monomers can be used alone, and can also be mixed with two or more, comprehensive absorbent resin powder It is preferable to use contain acrylic acid and/or its salt (such as sodium salt, lithium salts, sylvite, ammonium salt, amine etc. for performance and cost Salt), wherein in terms of cost, the polyacrylic acid water-absorbent resin of the acrylic monomer of more preferable sodium salt.

There is no particular restriction for the neutralization ratio of these undersaturated monomers containing acid groups, can be in part and/or complete It neutralizes, preferably part neutralizes, and can also optionally neutralize polymeric gel after polymerisation.The unsaturation contains acid groups The preferred degree of neutralization of monomer is 25~100mol%, particularly preferably reaches at least 40~95mol%, more preferably up to 50~ 90mol%.The neutralization of monomer of the unsaturation containing acid groups can carry out before or after the polymerization.Alkali metal hydrogen can be used Oxide, alkaline earth metal hydroxide, ammonia and carbonate and bicarbonate are neutralized.It is in addition it is possible to use any other Can with it is described acid formed water soluble salt alkali.It can also be neutralized using a variety of alkali.It is preferable to use ammonia or alkali metal hydrogen-oxygens Compound neutralizes, and is particularly preferably neutralized using sodium hydroxide.

As polyacrylic absorbent resin powder, the usage amount of acrylic acid and/or its salt compared with whole monomers into Divide (except crosslinking agent), be usually more than 60mol%, be preferably more than 75mol%, be preferably more than 90mol%, it is further excellent Elect more than 95mol% as.

Monomer concentration is also not particularly limited, the unsaturated monomer containing acid groups and cross-linking agent aqueous solution concentration for 25~ 60wt%, preferably 30~55wt%, further preferred 35~50wt%.In the case of monomer concentration is less than 25wt%, energy is produced Power can reduce, therefore not good enough.When monomer concentration is higher than in the case of 60wt%, crushing load increases, and production stability is caused to be deteriorated. The solvent of monomer is water, can also and with a small amount of organic solvent.

As internal crosslinker, the compound for containing multiple vinyl selected from intramolecular, intramolecular contain at least one ethylene Based compound and it is at least one can have with the compound of the functional group of carboxyl reaction on the unsaturated monomer, intramolecular it is multiple It can be with the one or more in the compound of the functional group of carboxyl reaction on the unsaturated monomer.Previously many institute's weeks can be used The internal crosslinking agent known.Specifically, such as can enumerate：N, N '-methylene-bisacrylamide, trimethylolpropane tris (first Base) acrylate, ethylene glycol two (methyl) acrylate, polyethyleneglycol diacrylate, polyethylene glycol two (methyl) acrylic acid Ester, polyethylene glycol diallyl ether, pentaerythritol tetraacrylate, triarylamine, ethylene glycol diglycidylether, ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,4- butanediols, glycerine, pentaerythrite, polyethylene glycol and one kind in ethylene carbonate or It is a variety of, these internal crosslinking agents, it is contemplated that reactivity can use one or more.Wherein, preferred trimethylolpropane tris In (methyl) acrylate, polyethyleneglycol diacrylate, ethylene glycol diglycidylether, polyethylene glycol, 1,4- butanediols One or more, further preferred trimethylolpropane tris (methyl) acrylate, polyethyleneglycol diacrylate, ethylene glycol two One or more in glycidol ether.

The usage amount of internal crosslinker is determined according to the physical property of required water-absorbing resins, compared with content of monomer, is preferably 0.001~5mol%, more preferably 0.005~2mol%, further preferably 0.01~1mol%.If the use of internal crosslinker Amount is less than 0.001mol%, and the water soluble apparent extract of gained water-absorbing resins increases, and can not substantially ensure the suction under pressurization Water.If the usage amount of internal crosslinking agent is more than 5mol%, chemical crosslinking density is too high, the absorbent resin powder of gained Water absorption deficiency.In addition, internal crosslinking agent can be once added in reaction system, can also be added batch-wise to reaction system In.

1.2 prepare foaming agent monomer solution

As foaming agent, occur physically and/or chemically to react in the manufacturing process of water-absorbing resins, decompose to give off gas Body (such as carbon dioxide, oxygen, nitrogen, ammonia etc.), to increase the hole of resin surface.The foaming agent be selected from ammonium carbonate, Ammonium hydrogen carbonate, sodium carbonate, sodium acid carbonate, calcium carbonate, potassium carbonate, saleratus, magnesium carbonate, two melon acid esters, azodiisobutyronitrile, Azobisisoheptonitrile, azobisisovaleronitrile, azodicarbonamide, azo-bis-isobutyrate hydrochloride, diisopropyl azodiformate, Two azoaminobenzenes, nitrourea, dinitrosopentamethylene tetramine, unifor, ketone hydrazone in tolysulfonyl, 4,4 '- One or more in oxobenzenesulfonyl hydrazide, 2,4 methyl benzyl disulphonyl hydrazide, SODIUM PERCARBONATE, hydrogen peroxide, benzoyl peroxide.

Blowing-agent particle and/or foaming agent solution with acrylic monomer and cross-linking agent aqueous solution are mixed, prepare foaming Agent monomer solution, foaming agent need Monodispersed in monomer solution under stirring or static condition.Dispersing mode can be that will send out It is added to after infusion dissolving in monomer solution, re-forms blowing-agent particle process, it can also be by blowing-agent particle directly by stirring Mix or static conditions under be dispersed in monomer solution, can also previously prepared foaming agent emulsion, then by emulsion and monomer Solution mixes.

Foaming agent is -10~120 DEG C in temperature, the time is in 1~60 minute, in 100 mass parts lists in monomer solution 0~10 mass parts can be dissolved in liquid solution, 0~1 mass parts of dissolving is preferably able to, can further preferably dissolve 0~0.5 matter Measure part.Number average bead diameter of the blowing-agent particle in monomer solution is 0.1~900 micron, is preferably 0.5~100 micron, further Preferably 1~25 micron.

In order to effectively control dispersiveness, solubility and grain size of the foaming agent in monomer solution, dissolving in foaming agent, point Organic solvent can be used in scattered or emulsion mixed process, such as can be enumerated：Methanol, ethyl alcohol, glycerine, acetone, acetic acid second Ester, dimethyl sulfoxide, (poly-) ethylene glycol, (poly-) propylene glycol, ethylene carbonate, ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1, 4- butanediols etc..These organic solvents can use one or more.When using organic solvent, consumption of organic solvent is with water quality Gauge is controlled in below 20wt%, preferably below 10wt%, further preferred below 5wt%.Alternatively, it is also possible to by adding Add foaming agent protection materials (such as non-in starch, starch derivatives, cellulose, cellulose derivative, inorganic salts, monomer solution Dissolving polymer material etc.), precipitating reagent, the methods of cooling control dispersiveness, solubility of the foaming agent in monomer solution And grain size.

Above-mentioned foaming agent can discharge gas by chemistry and/or physical reactions, and the generation and release of gas are in resin system Standby temperature-rise period realizes that gas release temperature is 20~200 DEG C, preferably 40~180 DEG C, further preferably 70~160 DEG C, When gas release temperature is less than 20 DEG C, gas can not be rested on effectively in polymerization system, it is impossible to reach preferable pore Effect, when gas release temperature is less than 200 DEG C, gas yield in entire resin manufacturing processes is seldom.

Foaming agent consumption is in terms of 100 parts by weight unsaturated monomers, in the range of 0.005~20 parts by weight, preferably 0.01~ 10 parts by weight, further preferred 0.02~5 parts by weight, when foaming agent consumption is less than the situation of 0.005 parts by weight, it is impossible to obtain Preferably high rate of liquid aspiration is obtained, when foaming agent consumption is higher than 20 parts by weight, resin property deterioration is produced, transports and used Dust is serious in journey, and impact resistance declines, and production cost is higher.

Foaming agent disperses before prepared by unsaturated acrylic monomer and cross-linking agent aqueous solution, in preparation process or after preparing To monomer solution.In addition, foaming agent initiator add in monomer solution before, in adition process or add in after be added to solution In.

1.3 polymerization procedure

Polymerization procedure is the step of monomer solution is polymerize.Polymerization process can normal pressure, decompression or pressurization under into Row, preferably carries out under normal pressure.

As the polymerization initiator used in this step, there is no particular restriction, can use and under polymerization conditions can It forms free radical and is commonly used for preparing any initiator of water-absorbing resins.It can also be by acting on and can gather electron beam The water-containing monomer solution of conjunction and trigger polymerization.It can also act on triggering by high-energy radiation in the presence of photoinitiators poly- It closes.According to monomeric species, polymerizing condition being polymerize etc., from the polymerization initiator utilized when usually manufacturing water-absorbing resins Selection is one or more to be used.

Polymerization initiator is preferably peroxide, hydroperoxides, hydrogen peroxide, persulfate and azo-compound.It is excellent Choosing uses water soluble starter.Specifically enumerate：Heat decomposition type initiator, such as sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate over cure Hydrochlorate；The peroxide such as hydrogen peroxide, tert-butyl peroxide, methyl ethyl ketone peroxide, azonitrile compound, azo amidine chemical combination Object, annular azo amidine compound, azo amide compound, alkyl azo-compound, double (2- amidine propanes) disalts of 2,2 '-azo The azo-compounds such as double [2- (2- imidazoline -2- bases) propane] dihydrochlorides of hydrochlorate, 2,2 '-azo；Or photodegradation type initiator, Such as Benzoin derivative, benzil derivatives, acetophenone derivs, benzophenone derivates, azo-compound.These trigger In agent, it is preferably heat decomposition type initiator for cost and the ability of reduction residual monomer, is more preferably persulfuric acid Salt.

In addition, the decomposition of these polymerization initiators can be promoted by and with reducing agent.Therefore, it is possible to use redox System initiator.It as the reducing agent, is not particularly limited, can be selected from：Sodium pyrosulfite, sodium sulfite, bisulfite The sulfurous acid such as sodium (hydrogen) (salt), L-AA (salt), metal salt (such as iron (II) ion or silver ion), amine etc..In oxygen In the case that change reduction series initiators so use oxidative polymerization initiator and reducing agent, it can be closed respectively with monomer solution Reducing agent, can also be mixed in monomer solution by stream in advance.

When carrying out the polymerization, poly- second two can also be added in the reaction system before polymerization or in polymerization as needed Alcohol, starch, starch derivatives, cellulose, cellulose derivative, polyvinyl alcohol, polyacrylic acid (salt), polyacrylic acid (salt) crosslinking The hydrophilic polymers such as body；Or chain-transferring agents, the chelating agent such as ortho phosphorous acid (salt) etc..It, can be preferable as hydrophilic macromolecule Ground uses water-soluble resin or water-absorbing resins, can improve the viscosity of reaction system.Compared with monomer, hydrophilic polymer Usage amount is preferably 0~30wt%, more preferably 0.001~20wt%, further preferably 0.01~10wt%.

As the polymerization employed in this step, it is not particularly limited.Free radical polymerization in preferably homogeneous (such as free radical polymerization in aqueous solution), the precipitation polymerization from organic solvent, suspension polymerisation, emulsion polymerization or mini-emulsion polymerization Deng.It is preferred that the free radical polyalcohol in homogeneous system, the free radical polymerization in further preferred aqueous solution.Water solution polymerization process has Make the standing polymerization that monomer solution is polymerize under static condition and the stirring polymerization being polymerize in agitating device Method etc..In addition, polymerization is divided into batch method according to continuous production and continuity method polymerize.It is particularly suitable for the polymerization solved the problems, such as It is aqueous solution polymerization, especially continuous conveyor polymerization or continuous kneader polymerization.

The manufacture device of water-absorbing resins as the present invention, is not particularly limited, and is preferably continuous conveyor polymerization dress Put or continuously stir polyplant.

Continuous conveyor polyplant is preferably that the continuous of annular conveyer belt type stands polyplant, and conveyer belt is fluororesin System or the conveyer belt to be formed with fluororesin-coated surface.Furthermore it is preferred that possess heating unit or attemperator, and have By the device of the steam of generated water and/or monomer solution when polymerizeing is recycled and is recycled system.

It continuously stirs polyplant and uniaxial agitating device may be employed, can also use continuous kneader etc. that there is multiple stir The agitating device of axis is mixed, for productive viewpoint, it is preferable to use multi-shaft stirring devices.

When polymerization start temperature refers to that initiator adds to monomer solution, the real time temperature of polymerization system.The monomer is water-soluble In the step of liquid is polymerize, in order to solve the problems, such as in the invention and promote the progress of foaming process, polymerization start temperature is 20~120 DEG C, be preferably 40~110 DEG C, preferably further preferably 60~100 DEG C.If polymerizeing start temperature is less than 20 DEG C, polymerization time is long, and production capacity is greatly reduced, and the physical property of water-absorbing resins may also reduce.If it polymerize start temperature Higher than 120 DEG C, then there is the worry that the physical property of water-absorbing resins reduces.It is not particularly limited for polymerization time, according to monomer and gathers Close initiator species, polymerization temperature etc. it is appropriate determine, but in terms of the production capacity for, polymerization time is more short better.

In addition, in order to promote to foam, preferably make peak temperature during polymerization higher, peak temperature is excellent in polymerization procedure Elect 100 DEG C or more as, more preferably 100~170 DEG C, further preferably 100~150 DEG C.

1.4 pulverising step

The step of aqueous gel shape cross-linked polymer of above-mentioned gained is crushed, pulverising step can polymerization when or It is carried out after polymerization.Crushing process during polymerization can use kneader, and the crushing after polymerization can use cutting machine, meat grinder Deng.Preferably 0.5~10 millimeter of gel particle size after crushing, if gel particle is too small, wind that level of residual monomers can be brought higher Danger if water-setting gum polymers are not crushed or gel particle is too big, cannot obtain final granular product, especially In subsequent heat drying steps, it is difficult to evaporate the moisture in hydrogel.

1.5 heat-drying step

Heat-drying step is that the aqueous gel shape cross-linked polymer is subject to drying, forms porous structure drying polymerization Object.Drying is usually in 60~300 DEG C as heating medium temperature, preferably 100~250 DEG C, more preferable 120~220 DEG C of temperature Degree is lower to carry out.Drying time depends on surface area and the water content of polymer and drier type, is selected to obtain target Water content (water content passes through the weightless measurement when 105 DEG C of dryings 3 are small).

Water content for water-absorbing resin of the present invention is not particularly limited, the more preferable 0.2~30wt% of water content, further It is preferred that 0.3~15wt%, particularly preferred 0.5~10wt%.Too high-moisture not only damages mobility, and therefore influences production, And make being crushed into for water-absorbing resin can not possibly and may be out of hand to specific size distribution.

It is not particularly limited as used drying means, a variety of methods can be used to obtain target water content, specifically It enumerates：Heat drying, hot-air are dry, be dried under reduced pressure, infrared drying, microwave drying, by with hydrophobic organic solvent Azeotropic mixture is dehydrated and using the drying of high-temperature steam high humility.

In addition, foaming agent can pass through further thermal decomposition under the drying temperature, further foaming process is realized.

1.6 grain refineds and screening step

In order to obtain the water-absorbing resins (adjusting grain size jointly with following micro mist granulation process) with specified particle size, it is necessary to The step of grain refined is carried out to porous structure cross-linked polymer after drying and is sieved.

For obtaining having irregular pulverized shape, and the absorbent resin that grain size can be controlled effectively, grain refined uses Machine include shearing crude pulverizer, impact powder pulverizer and high-speed rotation type powder pulverizer.It is and right after grain refined Resin particle is further sieved.

The Mass median diameter (D50) of water-absorbing resins, is preferably regulated as 200~650 microns, is more preferably adjusted to 200 ~550 microns, further preferably it is adjusted to 300~500 microns.Particle fraction control of the diameter less than 150 microns for 0~ 8wt%, preferably 0~5wt%, more preferable 0~2wt%.In addition, diameter is more few better higher than 850 microns of particle fraction, control For 0~8wt%, preferably 0~5wt%, more preferable 0~2wt%.In the present invention, it is preferred in 150~850 microns of particle Ratio carries out surface-crosslinked under conditions of being more than 95wt%, more preferably more than 98wt%.The logarithmic scale of size distribution is inclined Poor (σ ζ) is preferably controlled to 0.20~0.40, more preferable 0.20~0.38, further preferred 0.20~0.36.

The recycling of 1.7 fine grained water-absorbing resins

In the present invention, by being recycled to control small particle fine grained (less than 150 by fine grained water-absorbing resins The particle of micron) yield.

The small particle water absorbing resin particle (particle for being less than 106 microns) obtained by grain refined and screening can pass through return Polymerize again to monomer solution or mixed with a large amount of hot water carry out agglomeration (weight ratio of little particle water-absorbing resin and hot water be 2: 1~1:2), to revert to water-setting gum-like product again.Then by be granulated, dry and grain refined and etc. readjust as mesh Mark grain size water absorbing resin particle.Amount of waste can be reduced by the particle for recycling and regenerating beyond target zone.

1.8 surface cross-linking step

In the manufacturing method of the present invention, further include using surface crosslinking agent to the water-absorbing resins surface after Sieving and casing Nearby carry out the step of surface treatment forms covalent bond.By carrying out surface-crosslinked step to the water-absorbing resins after Sieving and casing Suddenly, the water absorbent rate and permeability for liquids under resin pressurization can effectively be promoted.But for the present invention water-absorbing resin from Heart water holding capacity (CRC), compared to having and reducing to a certain degree before crosslinking, is original centrifuge retention capacity after surface-crosslinked 50~95%, it is further reduced to 60~90%.The reduction degree of centrifuge retention capacity can by the type and dosage of crosslinking agent, Reaction temperature and time adjustment.

The surface-crosslinked processing of the present invention means to increase the operation of crosslink density near particle surface.More specifically It says, it is that have at least two can be formed with the compound of the functional group of carboxyl reaction by being added in particle surface in molecule New crosslinked operation, the compound can be by forming key with the acidic group included in particulate water-absorbing resin or its reactant salt It closes.The surface crosslinking agent that this step uses is preferably able to form covalent bond or ionic bond with water-absorbing resins surface functional group Surface crosslinking agent.

As the surface crosslinking agent that can be used in this step, preferably for example：It is polyol compound, epoxide, more Amine compounds or with the condensation product, oxazoline compounds of its halogenated epoxy compound, (mono-, di- or poly-) oxazoles pyridine ketone compound, Carbonic acid alkane diester compound.It specifically includes：Polyalcohol such as polyethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, a contracting dipropyl two Alcohol, 2,3,4- trimethyl -1,3- pentanediols, polypropylene glycol, glycerine, polyglycereol, 2- butylene-1,4-diols, 1,4- butanediols, 1, 3- butanediols, 1,5- pentanediols, 1,6-HD, 1,2- cyclohexanedimethanols etc.；Epoxide such as ethylene glycol two shrinks sweet Oily ether, Polyethylene Glycol Bisglycidyl Ether, glycidol etc.；Multivalence amine compounds such as ethylenediamine, diethylenetriamines, triethylene Tetramine, tetren, penten, polyethyleneimine etc.；Halogenated epoxide such as epoxychloropropane, epoxy bromine Propane, Alpha-Methyl epoxychloropropane etc.；The condensation product of multivalence amine compounds and halogenated epoxide；Oxazolidinone compounds example Such as 2- oxazolidones；Ring urea；Alkylene carbonate compound is such as ethylene carbonate.They can be used alone or a variety of It is used in combination.To give full play to the effect of the present invention, it is preferable to use polyol compounds and epoxide to be combined.As polynary Alcohol preferably has the polyalcohol of 2~10 carbon atoms, the further preferably polyalcohol with 3~8 carbon atoms.

The dosage of surface crosslinking agent depends on using type of crosslinking agent and its combination, is preferably based on water-absorbing resin 0.01 ~10wt%, more preferable 0.05~5wt%.

In the present invention is surface-crosslinked, it is preferable to use water for the solvent of surface crosslinking agent.The dosage of water depends on surface-crosslinked The water content of agent effective ingredient consumption and water-absorbing resin, is preferably based on water-absorbing resin 0.2~20wt%, more preferable 0.3~ 15wt%, further preferred 0.5~10wt%.In addition, hydrophilic organic solvent can be used to be used in mixed way with water, it is hydrophilic when using Property organic solvent when, preferable organic solvent dosage be based on 0~10wt% of water-absorbing resin, more preferable 0~8wt%, further preferred 0 ~5wt%.

It is preferred that surface crosslinking agent is pre-mixed in water and/or hydrophilic organic solvent, then to by treatment fluid spraying or It is added dropwise to water-absorbing resin, more preferable spray method.The mean droplet size of the spraying is preferably 0.1~500 micron, more preferably 0.1~200 micron.

After surface crosslinking agent is added to water-absorbing resin, preferably it is heat-treated.It is 100~220 to be surface-treated temperature DEG C, preferably 130~210 DEG C, further preferred 160~200 DEG C, when heating time is preferably 1 minute~2 small.

1.9 chelating agent

By adding in chelating agent, the time course point derived from component in urine with the water absorbing agent of Fe ionic reactions can inhibit Solution, equally can inhibit the dissolving of water absorbing agent, reduces the absorptivity of water absorbing agent, reduce the permeability for liquids of water absorbing agent.Chelating agent exists It is added in selected from following one or more times：(1) during polymerization；(2) after polymerisation with it is surface-crosslinked before；(3) exist Surface-crosslinked period；(4) during agglomeration.

Chelating agent for water absorbing agent of the present invention is preferably to have high sealing ability or sequestering power to Fe or Cu ions Chelating agent, preferably amino polyvalent carboxylic acid and its salt particularly preferably have the amino carboxylic acid and its salt of no less than 3 carboxyls.

It is 0.00001~10wt%, preferably 0.0001~1wt% that the dosage of amino polyvalent carboxylic acid, which is based on water-absorbing resin,.

1.10 inorganic powder

By adding in inorganic powder, the permeability for liquids of water-absorbing resin can be effectively promoted, preferably inorganic powder is average grain SiO 2 powder of the footpath below 100 nanometers.The inorganic powder additive amount in terms of water-absorbing resins, be 0.001~ 10wt%, preferably 0.005~1wt%, further preferred 0.01~0.5wt%.

1.11 deodorization is combined

Original of the plant component preferably on the plant component that can add deodorization functions in the deodorization combination of the present invention Tannin plant can enumerate Theaceae, Rubiaceae, grass family, mountain galley proof section plant etc., preferably lift Theaceae, grass.This Outside, on plant of theaceae, camellia, tea plum can be enumerated, tea tree, carry wood, Ternstroemia gymnanthera etc., preferably tea tree.On madder wort, Madder, coffee tree, Morinda officinalis etc., preferably coffee tree can be enumerated.On grass, rice, thin bamboo, bamboo, corn, small can be enumerated Wheat etc., preferably thin bamboo, bamboo.On the plant of mountain galley proof section, mountain galley proof, robe, bastard, Oak Tree etc., preferably Oak Tree can be enumerated. In addition, green tea, black tea, oolong tea, Pu'er tea that the leaf or stem to the tea tree are processed and obtain etc. can also be used as energy attached Add the plant component of deodorization functions.On the ingredient from plant described in deodorization functions can be added, can enumerate contained in plant Polyphenol and caffeine etc., contained polyphenol or caffeine preferably in the plants such as Theaceae, Rubiaceae, grass family, mountain galley proof section Deng.Particularly preferably containing the polyphenol in plant.In plant contained polyphenol preferably containing flavonoids, phenolic acid, boots spend acid, lignan, Curcumin, cumarin more preferably spend acid, lignan containing flavonoids, boots, and then preferably contain flavonoids.The flavonoids preferably contains Catechin, cyanine are general, boots matter, rutin, isoflavones, more preferably containing catechin, boots matter.On the catechin, such as there is teas The derivative of catechin, teas catechin.On the boots matter, such as there are water-disintegrable boots matter and condensed type boots matter, be preferably condensed Type boots matter.Natural fine bamboo powder is selected in the present invention.

Chemical constituent, preferably aldehydes can be used for the exemplary aldehyde of malodor control compositions to include but not limited to the clean red aldehyde of ripple (4- 2-methyl-2-phenylpropanes propionic aldehyde), lilial 33 (2- methyl -4- tert-butyl-phenyls propionic aldehyde), cinnamic acid, citral, geranial, neral (dimethyl octadiene aldehyde, 3,7- dimethyl -2,6- octadiene -1- aldehyde), ligustral (Cyclal C) (2,4- dimethyl -3- rings Hexene -1- formaldehyde), cyanine aldehyde (3- (3- isopropyl phenyls), butyraldehyde perfume, cyclamen aldehyde (Cymal), cyclamen aldehyde (cyclamen Aldehyde), cyclosal (Cyclosal), bitter orange aldehyde (a- methyl-p-isopropyl phenyl propyl aldehyde), first Base nonyl acetaldehyde, hydration citronellal (the light base -3,7- dimethyl-octas -1- aldehyde of 7-), helional (a- methyl -3,4- (methylene Dioxy) hydrocinnamaldehyde), hydrocinnamaldehyde (3- hydrocinnamicaldehydes, 3- hydrocinnamicaldehydes), the different hendecanal (ten -- 10- alkene -1- aldehyde), Ligustral, melonal (2,6- dimethyl -5- heptenals), methoxyl group melonal (6- methoxyl groups -2,6 dimethyl heptanal), methoxy The blue or green aldehyde of base cinnamic acid (trans -4- methoxycinnamic aldehydes), Myracaldehyde (Myrac aldehyde) (isohexenyl cyclohexenyl carbaldehyde), grass (trifernal) (3- methyl 4-phenyl propionic aldehyde, 3- phenyl butyraldehyde) etc..

Further preferably there is the substance of oxidized form, further preferably perborate, such as sodium perborate (any hydrate, including-water Close object or tetrahydrate), most preferably sodium carbonate peroxyhydrate or equivalent percarbonate, peroxide hydration sodium pyrophosphate, peroxide water, Or sodium peroxide.Available oxygen source, such as persulfate (such as the OXONE produced by DuPont) also can be used.Oxide can wrap Containing dry particle, the particle has the particle mean size in about 100 microns to about 1,000 micron range, no more than about 10 weights The particle for measuring % is less than about 200 microns, and the particle of no more than about 10 weight % is greater than about 500 microns.

More than deodorization component can be comprising dry particle, powder, the particle or with about 100 microns to about 1,000 micron In the range of particle mean size, the no more than about particle of 10 weight % is less than about 200 microns, and no more than about 10 weight % Particle be greater than about 500 microns.The percarbonate is optionally coated with silicate, borate or water soluble surfactant active.With Trade name oronain T, which derives from lark prestige Science and Technology Ltd., to be uncoated or coated form, and can be used in the present invention.

[2] physical property of polyacrylic acid water-absorbent resin

The polyacrylic acid water-absorbent resin of the present invention has the particulate water-absorbing agent of irregular pulverized shape, specific physical property It is as follows.

2.1 surface apertures

Water-absorbing resins surface porosity is observed by scanning electron microscope, in order to effectively promote the suction of resin Liquid speed rate controls the apparent density of resin and improves the impact resistance crushing performance of resin, and the porous structure average pore size is preferred For 10~500 microns, more preferably 10~300 microns, more preferably 10~200 microns, especially preferably 10~150 microns.

2.2 centrifuge retention multiplying powers (CRC)

Centrifuge retention multiplying power (CRC) to the sodium-chloride water solution of 0.9wt% is preferably 10~60g/g, and more preferably 20 ~55g/g, into-step preferably 25~50g/g, especially preferably 25~45g/g.For absorbability.CRC is the higher the better, But it needs to be balanced with other physical property as the case may be in actual use.

2.3 pressurization water absorbent rates (AUP)

Water-absorbing resins are carried out surface-crosslinked to promote its water suction to the sodium-chloride water solution of 0.9wt% under stress Multiplying power (pressurization water absorbent rate, AUP).Under 1.9kPa pressure, AUP is preferably 15~55g/g, more preferably 15~50g/g, Into-step preferably 15~45g/g, especially preferably 15~40g/g.Under 4.8kPa pressure, AUP is preferably 10~50g/g, more Preferably 10~45g/g, into-step preferably 10~40g/g, especially preferably 10~35g/g.AUP is the higher the better, but actually makes Used time needs are balanced as the case may be with other physical property.

2.4 leachable objects (Extr)

The solvable apparent extract (Extr) of water-absorbing resins of the present invention is preferably 0~40wt%, more preferably 1~ 30wt%, into-step preferably 3~25wt%.

2.5 swirl method infiltration rates

The swirl method infiltration rate of water-absorbing resins of the present invention is shorter than 60sec/g, preferably 1~55sec/g, more preferable 2~ 45sec/g.Water absorbing agent of the infiltration rate more than 60sec/g may not achieve the effect that enough.

2.6 apparent density

Apparent density represents the quality accumulated after the powder freely falling body of unit volume.Water-absorbing resins of the present invention it is apparent Density is 0.50~0.80g/cm³, it is preferably 0.51~0.75g/cm³, into-step preferably 0.52~0.70g/cm³。

2.7 particle sizes and distribution

The median granularity of quality (D50) of water-absorbing resins of the present invention, is preferably regulated as 200~650 microns, more preferably adjusts For 200~550 microns, into-step be preferably regulated as 300~500 microns.Particle fraction control of the diameter less than 150 microns for 0~ 8wt%, preferably 0~5wt%, more preferable 0~2wt%.In addition, diameter is more few better higher than 850 microns of particle fraction, control For 0~8wt%, preferably 0~5wt%, more preferable 0~2wt%.In the present invention, it is preferred in 150~850 microns of particle Ratio carries out surface-crosslinked under conditions of being more than 95wt%, more preferably more than 98wt%.The logarithmic scale of size distribution is inclined Poor (σ ζ) is preferably controlled to 0.20~0.40, more preferable 0.20~0.38, into-step preferably 0.20~0.36.

2.8 water content

Water content is to determine the parameter of the volatile materials such as water included in water-absorbing resins.Water imbibition tree of the present invention The water content of fat is preferably 1~10wt%, more preferable 2~10wt%.

2.9 levels of residual monomers

The levels of residual monomers of water-absorbing resins of the present invention is preferably 0~600ppm, more preferably 0~500ppm.

[3] purposes of polyacrylic acid water-absorbent resin

The application of particle-shape water-absorbing resin of the present invention is not particularly limited, and be can be used for paper diaper, physiological hygiene cotton, is lost Prohibit the absorbent commodities such as protection pad, be preferred for for example thin absorbing articles of thin absorption base and absorbing articles.

In absorbent commodity ,-as contain other absorbent materials (paper pulp fiber etc.), the wherein content of water-absorbing resins It is preferably 40~100wt% for 30~100wt%, more preferably 50~100wt%, into-step preferably 60~100wt%.

[4] embodiment

The present invention will be illustrated with following embodiment and comparing embodiment, but the invention is not restricted to following embodiments.

The various performances of water-absorbing resins are measured through following methods.It is outer unless specified otherwise, water-absorbing resin, water absorbing agent and absorption Article uses under conditions of 25 ± 2 DEG C and 50%RH (relative humidity).Used normal saline solution is the chlorine of 0.90wt% Change sodium water solution.

4.1 surface apertures

Water-absorbing resins surface porosity and aperture are observed by scanning electron microscope, by particle-shape water-absorbing Resin sample is adhered on sample stage, is tested after metal spraying.

4.2 centrifuge retention multiplying powers (CRC)

Centrifuge retention multiplying power (CRC) is represented under no pressurization to 0.90wt% sodium-chloride water solutions (also referred to as physiological saline Water) water absorbent rate that is centrifuged after water suction 30 minutes.

0.20g water-absorbing resins are weighed, record weight is W₀(g), it is uniformly put into the cloth made of supatex fabric In bag, sealing is immersed in normal saline solution of the control at 25 ± 2 DEG C.After 30 minutes by the bag containing water-absorbing resins from It is taken out in saline solution.It is dehydrated 3 minutes under 250G using centrifuge, then weighs to obtain weight W₂(g).Without using any The weight W of bag is measured after the similar operations of water absorbing agent₁(g).Centrifuge retention multiplying power (g/g) is calculated according to the following formula.

Centrifuge retention multiplying power (g/g)=((W₂(g)-W₁(g))/W₀(g))-1

4.3 pressurization water absorbent rates (AUP)

Load weighted sample is laid on filter screen ,-the bottom of a special cylinder is covered, begins to use uniform pressure (1.9kPa/0.3psi) is applied in test sample, then cylinder is placed in-a culture dish filled with sodium chloride solution in.Sample After when product absorption 1 is small, cylinder is taken out, test absorbs amount of liquid, specific as follows：

0.900g water-absorbing resins are weighed, record weight is W₃(g), it is laid in dry plexiglass cylinder strainer On, it is uniformly distributed it.Piston is placed on cylinder, and weighs the weight of a whole set of cylinder, is recorded as W₄(g).Filter plate is put It puts in culture dish, 120 ml NaCls is added in, so that liquid surface floods surface of aluminum plate.Circular filter paper is put into filter On plate, with sodium chloride solution complete wetting, surface is avoided to have bubble generation.A whole set of drum equipment is placed on to the filter soaked On paper, place 1 it is small when after, sample is allowed to fully absorb sodium chloride solution.Lift complete equipment and remove its piston, weigh circle again Cylinder device is recorded as W₅(g).Pressurization water absorbent rate (AUP) is calculated according to the following formula.

Pressurize water absorbent rate (g/g)=(W₅(g)-W₄(g))/W₃(g)

4.4 solvable apparent extracts (Extr)

Preparation-part is used for the sample to be tested of test.Accurately added in graduated cylinder 200 ml NaCls be transferred to-only 250 In the conical flask or beaker of milliliter, added with magnetic stir bar.1.000 grams of water-absorbing resins accurately are weighed, are accurate to 0.001 gram, Record weight.It is dissolved with sodium chloride solution, it is to be ensured that all samples all shift totally.Taper bottle stopper is capped, is stirred with electromagnetism Device is mixed when 500 ± 50r/min rotating speeds stirring 16 is small.Prepare-a 200 milliliters of sodium chloride solution to do compared with sample-batten The titration blank of part.Stop stirring after 16 hours, and deposit gel.Supernatant is filtered out with the Buchner funnel with filter paper, And collect no less than 50 milliliters of liquid.Standard NaOH solution is added in -50 milliliters of burets, 50 milliliters of blank of titration Sodium chloride solution, it is 10.0 to be titrated to pH value, and it is every-a terminal of 2.7. records to then proceed to be titrated to pH with standard hydrochloric acid solution The standard NaOH or the volume of titration with hydrochloric acid agent needed.Standard NaOH solution is added in buret, titrates 50 milliliters of sample filters Liquor, it is 10.0 to be titrated to pH value, and it is every-a terminal needs of 2.7. records to then proceed to be titrated to pH with standard HCl solution Standard NaOH or HCl titrant volume.

Carboxylic acid total amount (such as polycarboxylic acids), n in supernatant_COOH, it is represented with molar concentration, is provided by equation (1),

n_COOH=(V_NaOH, s-V_{NaOH, b})c_NaOH (1)

In formula,

V_NaOH,s----volume, milliliter, the sample supernatant filtered out, which is titrated to when pH is 10.0, with standard NaOH solution needs The volume wanted；

V_NaOH,b----volume, milliliter, NaOH solution blank solution, which is titrated to when pH is 10.0, with standard NaOH solution needs The volume wanted；

c_NaOH----concentration, mol/l do the titrant concentration for being titrated to the NaOH solution that pH is 10.0.

The total amount of carboxylate (ester), n in supernatant_tot, it is represented with mole, is provided by equation (2),

n_tot=(V_{HCl, s}-V_{HCl, b})c_HCl (2)

In formula,

V_HCl,sSample Filtrate solutions are titrated to 2.7 required HCl volumes by ----volume, milliliter from pH 10.0

V_HCl,bSodium chloride blank solution is titrated to 2.7 required HCl volumes by ----volume, milliliter from pH 10.0

c_HCl----concentration, mol/l do the concentration that titrant titrates pH HCl solutions used in from 10.0 to 2.7

The carboxylic acid total amount neutralized in supernatant, n_COONa, represented with mole, provided by equation (3)

n_COONa=n_tot-n_COOH (3)

The relative mass of carboxylic acid, m_COOH, represented with g, the relative mass of carboxylic acid sodium, m_COONa, represented with g

It is represented respectively with formula (4) and formula (5),

m_COOH=n_COOH×M_COOH×F_dil (4)

m_COONa=n_COONa×M_COONa×F_dil (5)

In formula,

M_COOHThe molal weight of ----acrylic acid, equal to 72g/mol

M_COONaThe molal weight of ----sodium acrylate, equal to 94g/mol

F_dil----dilution shadow, equal to 200/50=4

Extractable in super absorbent polymer, w are represented with mass fraction percentage, are provided with formula (6),

In formula,

m_s----quality, g, the weight of sample to be tested

4.5 swirl method infiltration rates

In 100 milliliters of beakers with stirrer, 50 ml NaCls are added in pipette, beaker is placed on magnetic It on power blender, is stirred with 500 ± 50r/min rotating speeds, confirms that liquid level generates and stablize whirlpool.Accurately weigh 2.000 grams of water imbibitions Resin is added in whirlpool, while starts timing with stopwatch, when liquid surface vortex disappears, and liquid level becomes horizontality, as Terminal records the time.

4.6 deodoriging properties

Test fluid is prepared

Fermentation urine

Crude urine is collected：Freshly voided urine (Male urine in 6h, and ensuring more than initial 3 grades of grades of stink), in order to ensure The representativeness of sample at least needs the mixed liquor of three people and three people's more than urines.

Fermentation condition：37 DEG C, in 55RH% climatic chambers, 16h.

List-component substitutes the preparation of urine

Take laboratory physiological saline (it is now with the current suggest with Quality Mgmt Dept configure physiological saline) be placed in 37 DEG C of baking ovens or In person's thermostat water bath, heat preservation is until solution temperature is 37 DEG C.

It is taken with-secondary property syringe in the conical flask of n-butylamine 0.1g to 100ml, is settled to 50g with 37 DEG C of physiological saline, adds Enter stirrer, sealed with preservative film, as 3min is stirred on magnetic stirring apparatus, is then placed into 37 DEG C of baking ovens or thermostatted water In bath, 15min is kept the temperature.

It is taken in the conical flask of n-butyl mercaptan 0.005g to 100ml with-secondary property syringe, is settled to 37 DEG C of physiological saline 50g, add in stirrer, sealed with preservative film, as 3min is stirred on magnetic stirring apparatus, be then placed into 37 DEG C of baking ovens or In thermostat water bath, 15min is kept the temperature.

Deodorization detects

SAP test methods：

The SAP for weighing 1.000 ± 0.0050 is placed in the special capsule of deodorization (confirmation before experiment, it is different whether experiment box has Taste), freshly voided urine 25g is rapidly added thereto, and sealing immediately (pays attention to：This process allows SAP to absorb urine naturally without mixing Liquid, it is therefore an objective to simulate actual use situations of the SAP in paper diaper).

It is positioned over 37 DEG C, in 55RH% climatic chambers, sensory evaluation is carried out after 30min.

Paper diaper are tested

Paper diaper are divided into 4 sections (being adjusted again with specific reference to paper diaper specification), are stayed with spare, comparative sample selections-sample, it will Paper diaper are put into seal box.Using intermediate site liquid feeding, pouring into urine rapidly, (liquid feeding mode need to discuss again and urine additive amount Need to be determined according to specific), it seals immediately, is positioned over 37 DEG C, in 55RH% climatic chambers, sense organ is carried out after 30min and is commented Estimate.

Stink is assessed

Tester opens sample lid, and nose is gently fanned apart from bottleneck 5cm, and with hand, hears stink degree, and recorder Member's record, each sample terminate sealing from lid is opened to detection, and 30s is not to be exceeded in the time.

Evaluation criteria is as follows：

5：Strong odor；4：Very big stink；3：It is easy to perceptible stink；2：(be able to know that is very light stink Which kind of stink)；1：Faint stink (presence that this stink can be perceived)；0：There is no smell.

Production Example 1

By pipeline acrylic acid/sodium acrylate mixed monomer solution, (acrylic acid/sodium acrylate molar ratio is 2.2/ 7.8), acrylic acid/sodium acrylate monomer concentration is 44.0wt%, and monomer solution flow is 8689kg/h.Monomer solution temperature is 80~90 DEG C.Polyethyleneglycol diacrylate (the molecule that concentration is 11.3wt% is delivered at monomer solution pipeline branch mouth It measures 522), flow 72kg/h.It is in addition, water-soluble by the azo-bis-isobutyrate hydrochloride that delivery pump melting concn is 6.17wt% Liquid (flow 50kg/h) and the sodium persulfate aqueous solution (flow 60kg/h) that concentration is 4wt% form initiator mixing turbid, and The mixing turbid is delivered to by monomer solution pipeline branch mouth in monomer, carries out polymerisation.Reaction solution is sprayed onto reaction bed, shape Into monomer solution (the suspended particulate grain size containing suspended particulate<100 microns, in 80~90 DEG C of monomer solutions, in 1 minute Insoluble, meltage is less than 0.01wt%), temperature of reaction system raises rapidly, and temperature change is 90~150 DEG C, and foaming agent exists It is decomposed under the temperature conditionss, obtains porous structure aqueous gel shaped polymer.

Then, aqueous gel shaped polymer is crushed, makes its grain size below 10 millimeters.And gel particle is sprawled It is dried on a wire mesh, obtains cross linked porous structural polymer.Porous crosslinked polymeric after drying is ground carefully Granulation, and sieved, the water-absorbent besin particles 1 with specified particle diameter are obtained,

By above-mentioned 100 parts by weight water-absorbent besin particles and 0.736 parts by weight include 1,2- propylene glycol, 1,4- butanediols, Ethylene glycol diglycidylether and water (weight ratio 12.4:7.4:0.9:79.3) blending surface cross-linking agent solution is mixed It closes, and surface treatment 50 minutes is carried out at 165 DEG C, obtain water-absorbing resins 2.

By above-mentioned 100 parts by weight water-absorbing resins respectively with 1.317 parts by weight concentration be 10.3wt% aluminum sulfate solution And 0.184 parts by weight of silica (grain size is less than 100 nanometers) powder is mixed, and obtains water absorbency resin composition A, object Property parameter is shown in Table 1.

Production Example 2

By pipeline acrylic acid/sodium acrylate mixed monomer solution, (acrylic acid/sodium acrylate molar ratio is 2.2/ 7.8), acrylic acid/sodium acrylate monomer concentration is 44.0wt%, and monomer solution flow is 8689kg/h.Monomer solution temperature is 80~90 DEG C.Polyethyleneglycol diacrylate (the molecule that concentration is 11.3wt% is delivered at monomer solution pipeline branch mouth It measures 522), flow 72kg/h.It is in addition, water-soluble by the azo-bis-isobutyrate hydrochloride that delivery pump melting concn is 6.17wt% Liquid (flow 50kg/h) and the sodium persulfate aqueous solution (flow 60kg/h) that concentration is 4wt% form initiator mixing turbid, and The mixing turbid is delivered to by monomer solution pipeline branch mouth in monomer, carries out polymerisation.Reaction solution is sprayed onto reaction bed, shape Into monomer solution (the suspended particulate grain size containing suspended particulate<100 microns, in 80~90 DEG C of monomer solutions, in 1 minute Insoluble, meltage is less than 0.01wt%), temperature of reaction system raises rapidly, and temperature change is 90~150 DEG C, and foaming agent exists It is decomposed under the temperature conditionss, obtains porous structure aqueous gel shaped polymer B.

Table 1

Embodiment 1

Reference sample 1：

Reference sample used is powders A.

Embodiment 2:

The water-setting gum polymers 200g in Production Example 2 is taken, bamboo powder 1g is added thereto, then, aqueous gel shape is gathered It closes object to crush, makes its grain size below 10 millimeters.And gel particle is spread over and is dried on woven wire, it obtains more Hole cross-linked structure deodorization polymer.Grain refined is ground to porous crosslinked polymeric after drying, and is sieved, is had The water-absorbent besin particles of specified particle diameter.Above-mentioned 100 parts by weight water-absorbent besin particles and 0.736 parts by weight are included into 1,2- third Glycol, 1,4- butanediols, ethylene glycol diglycidylether and water (weight ratio 12.4:7.4:0.9:79.3) blending surface is handed over Connection agent solution is mixed, and surface treatment 50 minutes is carried out at 165 DEG C, obtains water-absorbing resins.

By above-mentioned 100 parts by weight water-absorbing resins respectively with 1.317 parts by weight concentration be 10.3wt% aluminum sulfate solution And 0.184 parts by weight of silica (grain size is less than 100 nanometers) powder is mixed, and obtains water absorbency resin composition

100g is taken again treated water-absorbing resins, be placed in the three-necked flask of 250ml, three-neck flask is then placed in height On fast mechanical agitator, rotating speed is adjusted to 200r/s and adds 0.5g toluene-sodium-sulfonchloramides thereto, rotating speed is adjusted to 400r/s mixes and use top Portion blender homogenizing about 10min.

Embodiment 3:

The water-setting gum polymers 200g in Production Example 2 is taken, bamboo powder 2g is added thereto, then, aqueous gel shape is gathered It closes object to crush, makes its grain size below 10 millimeters.And gel particle is spread over and is dried on woven wire, it obtains more Hole cross-linked structure deodorization polymer.Grain refined is ground to porous crosslinked polymeric after drying, and is sieved, is had The water-absorbent besin particles of specified particle diameter.Above-mentioned 100 parts by weight water-absorbent besin particles and 0.736 parts by weight are included into 1,2- third Glycol, 1,4- butanediols, ethylene glycol diglycidylether and water (weight ratio 12.4:7.4:0.9:79.3) blending surface is handed over Connection agent solution is mixed, and surface treatment 50 minutes is carried out at 165 DEG C, obtains water-absorbing resins.

By above-mentioned 100 parts by weight water-absorbing resins respectively with 1.317 parts by weight concentration be 10.3wt% aluminum sulfate solution And 0.184 parts by weight of silica (grain size is less than 100 nanometers) powder is mixed, and obtains water absorbency resin composition

100g is taken again treated water-absorbing resins, be placed in the three-necked flask of 250ml, three-neck flask is then placed in height On fast mechanical agitator, rotating speed is adjusted to 200r/s and adds 0.5g toluene-sodium-sulfonchloramides thereto, rotating speed is adjusted to 400r/s mixes and use top Portion blender homogenizing about 10min.

Embodiment 4:

The water-setting gum polymers 200g in Production Example 2 is taken, bamboo powder 0.5g is added thereto, then, by aqueous gel shape Polymer crushes, and makes its grain size below 10 millimeters.And gel particle is spread over and is dried on woven wire, it obtains Cross linked porous structure deodorization polymer.Grain refined is ground to porous crosslinked polymeric after drying, and is sieved, is had There are the water-absorbent besin particles of specified particle diameter.Above-mentioned 100 parts by weight water-absorbent besin particles and 0.736 parts by weight are included into 1,2- Propylene glycol, 1,4- butanediols, ethylene glycol diglycidylether and water (weight ratio 12.4:7.4:0.9:79.3) blending surface Cross-linking agent solution is mixed, and surface treatment 50 minutes is carried out at 165 DEG C, obtains water-absorbing resins.

By above-mentioned 100 parts by weight water-absorbing resins respectively with 1.317 parts by weight concentration be 10.3wt% aluminum sulfate solution And 0.184 parts by weight of silica (grain size is less than 100 nanometers) powder is mixed, and obtains water absorbency resin composition

100g is taken again treated water-absorbing resins, be placed in the three-necked flask of 250ml, three-neck flask is then placed in height On fast mechanical agitator, rotating speed is adjusted to 200r/s and adds 1g toluene-sodium-sulfonchloramides thereto, by rotating speed be adjusted to 400r/s mix and use top Blender is homogenized about 10min.

Embodiment 5:

The water-setting gum polymers 200g in Production Example 2 is taken, bamboo powder 1g is added thereto, then, aqueous gel shape is gathered It closes object to crush, makes its grain size below 10 millimeters.And gel particle is spread over and is dried on woven wire, it obtains more Hole cross-linked structure deodorization polymer.Grain refined is ground to porous crosslinked polymeric after drying, and is sieved, is had The water-absorbent besin particles of specified particle diameter.Above-mentioned 100 parts by weight water-absorbent besin particles and 0.736 parts by weight are included into 1,2- third Glycol, 1,4- butanediols, ethylene glycol diglycidylether and water (weight ratio 12.4:7.4:0.9:79.3) blending surface is handed over Connection agent solution is mixed, and surface treatment 50 minutes is carried out at 165 DEG C, obtains water-absorbing resins.

By above-mentioned 100 parts by weight water-absorbing resins respectively with 1.317 parts by weight concentration be 10.3wt% aluminum sulfate solution And 0.184 parts by weight of silica (grain size is less than 100 nanometers) powder is mixed, and obtains water absorbency resin composition

100g is taken again treated water-absorbing resins, be placed in the three-necked flask of 250ml, three-neck flask is then placed in height On fast mechanical agitator, rotating speed is adjusted to 200r/s and adds 1g toluene-sodium-sulfonchloramides thereto, by rotating speed be adjusted to 400r/s mix and use top Blender is homogenized about 10min.

Table 2

Claims (10)

1. a kind of raising odor-resistant result method using polyacrylic acid water-absorbent resin component, the described method includes following：

(a) a kind of deodorization combination is provided, one of which component is plant component and another component is chemical constituent,

(b) plant component in the combination, the mode of deodorization can be that the smell neutralization of physics mode either covers or chemistry is anti- Should,

(c) plant component in the combination, be used alone can with the initial stink of substantially reduced body fluid,

(d) plant component is bamboo powder in the combination；

(e) bamboo powder in the combination, Particle size requirements in below 800um,

(f) chemical constituent in the combination is the substance that can be chemically reacted with body fluid,

(g) chemical constituent in the combination will not have an impact plant component,

(h) the combinatorial chemistry component can quickly react after being contacted with body fluid with the stink in body fluid,

(i) chemical constituent can be absorbed by unsaturated acrylic monomer together with body fluid,

(j) at least one kind can uniformly be present within unsaturated acrylic monomer in this two component, more than in height The surface of water-absorbing resins,

(k) addition manner in this two component in unsaturated acrylic monomer is multiplexing section, is repeatedly added,

(k) chemical constituent can be absorbed, the plant component can by super absorbent resin together not with gel reaction with body fluid Can be individual compound obtained by refining, from the easiness being added in water-absorbing resins in the form of being natural component And uniformly for the viewpoint of Combination, which is liquid or water-soluble preferably under room temperature (20-25 DEG C, particularly 25 DEG C) The form of liquid, it is more excellent although can be mixed into the form of a powder in water-absorbing resins for the natural component of solid under room temperature Choosing is mixed into water-absorbing resins in form of an aqueous solutions.

(l) product of the product and humoral response, it is safe and harmless, without smell.

2. according to the raising odor-resistant result method of claim 1 application polyacrylic acid water-absorbent resin component, which is characterized in that The aqueous solution of the unsaturation acrylic monomer and crosslinking agent is the water soluble salt of acrylic acid and/or acrylic acid as principal component Mixed solution.

3. according to the raising odor-resistant result method of the application polyacrylic acid water-absorbent resin component of claim 1 or 2, feature exists In the unsaturation acrylic monomer and cross-linking agent aqueous solution concentration are 25~60wt%.

4. according to the raising odor-resistant result method of claim 1 application polyacrylic acid water-absorbent resin component, which is characterized in that The crosslinking agent is selected from intramolecular contains the compound of multiple vinyl, intramolecular contains at least one vinyl compound and extremely Few one can have with the compound of the functional group of carboxyl reaction, intramolecular on the unsaturated monomer it is multiple can be with the insatiable hunger With the one or more in the compound of the functional group of carboxyl reaction on monomer.

5. according to the raising odor-resistant result method of claim 5 application polyacrylic acid water-absorbent resin component, which is characterized in that The crosslinking agent is selected from N, N '-methylene-bisacrylamide, trimethylolpropane tris (methyl) acrylate, two (first of ethylene glycol Base) acrylate, polyethyleneglycol diacrylate, polyethylene glycol two (methyl) acrylate, polyethylene glycol diallyl ether, season Penta tetra-acrylate, triarylamine, ethylene glycol diglycidylether, ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1, One or more in 4- butanediols, glycerine, pentaerythrite, polyethylene glycol and ethylene carbonate, preferably trimethylolpropane tris In (methyl) acrylate, polyethyleneglycol diacrylate, ethylene glycol diglycidylether, polyethylene glycol, 1,4- butanediols One or more, further preferred trimethylolpropane tris (methyl) acrylate, polyethyleneglycol diacrylate, ethylene glycol two One or more in glycidol ether.

6. according to the raising odor-resistant result method of claim 1 application polyacrylic acid water-absorbent resin component, which is characterized in that Extract (essential oil) that the plant component extracts, from natural goods for the natural goodses such as plant powder in itself, food processing industry or Plant residue or extraction residue for being obtained in the manufacturing process of food process industry as by-product etc..

7. according to the raising odor-resistant result method of claim 1 application polyacrylic acid water-absorbent resin component, which is characterized in that It it is 10~37 DEG C in temperature, the time is in 1~30 minute, deodorization combination can be with fast-acting.

8. according to the raising odor-resistant result method of claim 1 application polyacrylic acid water-absorbent resin component, which is characterized in that The described combination particle number average bead diameter is 0.1~900 micron.

9. according to the raising odor-resistant result method of claim 1 application polyacrylic acid water-absorbent resin component, which is characterized in that The deodorization combines dosage in terms of super absorbent resin, in the range of 0.005~20wt%.

10. according to the raising odor-resistant result method of claim 1 application polyacrylic acid water-absorbent resin component, feature exists In the deodorization combination is divided into two parts or multiple portions and is added in different workshop sections, preferably divides after wet gel crushes more Secondary multiple workshop section's additions.