This application claims the benefit of priority based on the Korea Patent Application No. 28 dated 10 October 2016 No. 2016-0141764 May, and all information disclosed in the literature of the Korea patent application are included as part of the specification.

The present invention, while basically maintaining the excellent absorption performance, represents an improved barrel-component, under high temperature / high humidity condition also relates to a superabsorbent resin and a method of manufacturing the ongjip and caking between particles is suppressed.

[Background Art]

The superabsorbent resin (Super Absorbent Polymer, SAP) is a synthetic polymeric material having the ability to absorb 500 to about a thousand times the water of its own weight, each developer SAM (Super Absorbency Mater i al), AGM ( Absorbent Gel Mater i al), including the ¾ and each is named as' another name. Superabsorbent polymer as described above is to begin commercialization of physiological equipment, currently freshness at Children diapers, etc. sanitary ware in addition to horticultural soil repair filler, engineering, construction index material, nursery sheets, food for distribution areas first, and It has been widely used for a material such as a poultice.

In most cases, these super-absorbent resins are widely used in the field of sanitary materials such as diapers and sanitary napkins. Within such hygienic material, the superabsorbent resin is usually to be included in a state spread in the pulp. However, the recent years, and more, and is continued effort to provide a thickness of the diaper such as sanitary materials, the content of pilpeu increased or as the part, further pilpeu is not used at all so-called pulp-less (pulpless) diapers of the proceeds are being developed actively.

In this way, the content of pilpeu reduced or, if the sanitary material of pulp is not used, be included at a relatively high water-absorbent resin is high bieul, such that is inevitably included in a multi-layer water-absorbent resin particles in the sanitary material. Thus to absorb a liquid such as whole super-absorbent resin particles hyoeul than ever in the urine contained in a multi-layer

In order, in which the well as it is necessary that the water-absorbent resin exhibit high absorption capability and the absorption rate by default, it is more necessary to indicate an improved barrel-component. That is, the super-absorbent resin is improved barrel must exhibit liquid, the urine, such as liquid and the first superabsorbent polymer particles of the surface layer which contacts to and absorbed and rapidly pass through the remaining liquid, this remaining liquid super-absorbent resin of the back layer the particles are able to quickly and effectively absorbed.

Accordingly, recently improved, but he is trying to develop a water-absorbent resin made of a multi-faceted, a situation that does not yet fully meet these technical requirements.

On the other hand, the super-absorbent resin is often therefore included in the sanitary material such as a diaper, exposure under the conditions of high temperature / high humidity. However, these high water-absorbent resin when, exposed to conditions of high temperature / high humidity according to the provided in the form of minute crosslinked particles having a high water absorption, in many cases this ungjip and caking (solidified) between the particles occurs. If this occurs ungjip and solidified, the manufacturing process used and reduces the workability, such as an increase in load, itdi can cause all of the difficulties in use of the superabsorbent resin. Thus even before and inorganic particles such as silica particles treated on the surface of the water absorbent resin ,, the Hung up or caking between the particles Kim 1 wateuna is small and characters attempt. Technical requirements of this, too, does not sufficiently cheungjok layer.

[Detailed Description of the Invention]

[SUMMARY]

In the present invention, while basically maintaining the excellent absorption performance, and to provide an improved barrel under denotes a liquid, Ko Un / humidity conditions and which also inhibit agglomeration and caking between particles, a water-absorbent resin and its production process.

[Technical Solution]

The present invention is a base resin powder including a first cross-linked polymers of water soluble ethylenically unsaturated monomer having at least partially neutralized acid; And is formed on the base resin powders, as a superabsorbent polymer comprising a surface cross-linking charge and a second cross-linked polymer of the first cross-linked polymer is added to the surface cross-linking agent-mediated cross-linking, it is dispersed in the surface cross-linked layer aluminum sulphate (aluminum sulfate) and that provides a super-absorbent resin containing the alumina are dispersed on the surface cross-linked layer.

The present invention also provides a water-soluble ethylenic base resin including a first cross-linked polymer of an unsaturated monomer having a powder at least partially neutralizing the acid; And

A super-absorbent resin to the first cross-linked polymer is formed on the base resin powder, a cross-linked layer includes a surface including a second cross-linked polymer cross-linking a surface cross-linking agent is added to the medium,

Aluminum salt that is dispersed in the surface cross-linked layer and a-alumina which is dispersed on the surface cross-linked layer,

To a method to measure expression and the transmission rate is 10 to 70 seconds of the first calculation, and the anti-caking efficiency of the formula 2 provides a super-absorbent resin is 75% to 100%:

[Equation 1]

Permeability (sec) = T S - the To

In the above formula (1).

Ts. (In seconds) is 0.9%, the super-absorbent resin of 0.2g salt (NaCl) to swell for 30 minutes saline solution absorption preparing a water-absorbent resin and the saline solution of 0.9% saline under the pressure of 0.3psi - meaning the time it takes to pass through the absorption super-absorbent resin,

T 0 (in seconds) is the salt-refers to the time it takes for the permeation of the saline solution of 0.9% under a 0.3psi pressure without superabsorbent polymer absorption, and

[Formula 2]

Anti-caking efficiency (%) = [W 6 (g) IW 5 (g)] * 100

In the formula 2,

W 5 (g) is that the initial weight (g) of the water absorbent resin, W 6 (g) has a diameter of 10 cm flask was then evenly applied to a plate temperature of 40土3 ° C, a constant temperature to maintain the humidity of 80 ± 3% level after holding for 10 minutes in a humidity chamber upside down the flask in the plate filter is a three Pater taping (tapping) an amount of superabsorbent polymer falling (g) after.

In addition, the present invention in the presence of an internal crosslinking agent, at least partially neutralized

A step of crosslinking polymerization of a water-soluble ethylenically unsaturated monomer having an acidic group to form a hydrogel polymer comprising a first cross-linked polymer; Forming a function of the gel polymer dried, pulverized and classified to a base resin powder; In the presence of a surface cross-linking solution containing aluminum sulphate and a surface cross-linking agent, said method comprising the surface cross-linked by heating a base resin powder to form a water-absorbent resin particles; And it provides a process for the preparation of superabsorbent polymer containing dry common summing phase alumina on said superabsorbent polymer particles.

Hereinafter, there will be more fully describes the collection of specific embodiments and the water-absorbent resin and its production process according to the invention. However, this total to be presented as an illustration of the invention, and thus not limited to the scope of the invention will, be apparent to the available are those of ordinary skill in the art the various modifications to the embodiments within the scope of the invention eu Additionally, the specification la special mention is a "contains" or "containing" is not also refers to including without limitation any component (or components), to exclude the addition of other component (or components) in the. It can not be interpreted.

. In addition ; The term "(super-absorbent resin particles) onto the" silver. Or it is formed on the surface of the particles. Partially embedded in the particle surface may mean that a part is formed as an exposed state on the surface of the particles.

The La 'in, "(surface cross-linked layer) to distinguish it also can mean that it is formed of a partially buried condition in a completely embedded state or it is formed by, at least the layer in the layer.

Meanwhile, according to one embodiment of the invention, the base resin comprises a first cross-linked polymers of water soluble ethylenically unsaturated monomer having at least partially neutralized acid

I HIG W ᄅ> ·, 犬

A super-absorbent resin to the first cross-linked polymer is formed on the base resin powder, a cross-linked layer includes a surface including a second cross-linked polymer cross-linking a surface cross-linking agent is added to the medium,

The superabsorbent resin containing aluminum sulfate is dispersed in the surface cross-linked layer (Aluminum Sul fate), and alumina are dispersed on the surface cross-linked layer is provided.

One embodiment the superabsorbent resin, the manufacturing method which will be described later, for example, by using the surface cross-linking solution containing a predetermined aluminum salt such as aluminum sulfate surface cross-linking is in progress, the production method is the alumina were dry heunhap thereafter it can be obtained through the like. Accordingly, one embodiment superabsorbent polymer is surface cross-linked aluminum sulfate having a uniformly dispersed structure in the layer, it may have a structure in which an alumina (particles) on the surface cross-linked layer are uniformly dispersed. .

The experimental results by the present inventors, such an embodiment the superabsorbent resin particles having structural characteristics beam SAT, pressurized while being absorbent capacity and the basic absorption characteristics and the absorption rate is excellently maintained, such as vortex removal time, and improved fluid permeability than previously known This indicates a cylindrical liquid and caking (solidification) preventing property was confirmed. The improved barrel-component and prevent caking properties, such properties are to be described later, for example, the permeability ' atda be defined by the physical properties such as and anti-caking efficiency.

In particular, one embodiment the superabsorbent resin is conventional superabsorbent resin dry shake plus other inorganic particles such as silica, as previously known, or another type of know luma an iodonium salt such as conventional high water-absorbent resin which includes a surface cross-linked layer It compared has been found to be better than the show come through liquid and / or anti-caking properties. Such according to included the improved barrel-component is aluminum sulfate uniform surface cross-linked layer, it is possible to further improve the strength of the superabsorbent resin particles as a whole, and thus to be expressed, since the shape of the particles after liquid absorption can be maintained in accordance with It is predicted. In addition, it seems that the alumina is well maintained on the surface of the particle compared with the other inorganic particle such as silica to suppress agglomeration and caking between particles more effectively.

Thus, according to one embodiment, along with the excellent absorption performance, it may be more and showing an improved barrel-component and caking inhibitory properties provided by the water-absorbent resin, such a superabsorbent polymer is effectively a sanitary material a circle having a reduced pulp content It can be used eu

In such cases one embodiment the superabsorbent resin, the base resin powder is common and may have the same components and configurations as the base resin of the water-absorbent resin powder. The base resin powder may include a cross-linked polymer of acrylic acid and its salts and at least partially neutralizing the unsaturated monomer, it may be produced according to a different embodiment the manufacturing method to be described later.

However, such a base resin powder manufacturing condition of a manufacturing method described below, for instance, is adjusted such as the type and content and, jeunghap conditions of internal cross-linking agent, for 30 minutes for a physiological saline solution (0.9 weight% aqueous sodium chloride solution) centrifugation beam SAT (CRC) is more than 29g / g, there is a vortex removal time can be made to be more than 27 seconds.

According to prepare a base resin powder such physical properties to meet, and for such a base resin powder, proceed to such dry heunhap process, such as desired surface cross-linking step, and alumina, including aluminum sulphate by example one embodiment and obtaining a water-absorbent resin, one embodiment and the water-absorbent resin superior physical properties, for example, can exhibit a superior ability to absorb, or improved liquid tube and / or caking inhibiting properties.

The configuration of the base resin powder other than it is conventional and can be equal to the base resin of the water-absorbent resin powder, and additional description thereof will be omitted.

And, in the high water-absorbent resin wherein an implementation, wherein the surface cross-linked layer can be formed by using the surface cross-linking agent comprising a polyol compound, an alkylene carbonate compound and a polyhydric at least one selected from the group consisting of an epoxy compound . These surface cross-linking agent for cross-linking by adding to the first cross-linked polymer of the base resin powder surface may form a cross-linked surface layer, in such a surface cross-linked layer it may be included as a state in which aluminum sulphate, uniformly distributed.

Type of the surface crosslinking agent is not particularly limited and, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glyceryl the polyglycidyl ether, propylene glycol diglycidyl ether or polypropylene glycol polyvalent epoxy compounds such as diglycidyl ether; Alkylene carbonate compounds such as ethylene carbonate or propylene carbonate; Or ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propane dayieul, dipropylene glycol, polypropylene glycol, glycerin, polyglycerin. Butane has a polrieul-based compounds such as diols, heptane diols, nucleic diol teurimetilreul propane, penta EPO recall or a sorbitan ratio can be used without limitation. '

However, when used in combination with the aluminum sulfate hayeoteul form a surface cross-linking charge, so as to further improve the high-barrel liquid such as water-absorbent resin, more polyvalent epoxy compounds such as the surface crosslinking agent is ethylene glycol diglycidyl ether It can be appropriately used.

In addition, the one embodiment and the water-absorbent resin may further comprise an alumina that is dispersed in the surface cross-linked layer. According to Sikkim also comprises alumina together with aluminum sulphate in the surface cross-linked layer, and the it is possible to further improve the whole liquid including the water-absorbent resin.

On the other hand, or is distributed on the surface cross-linked layer, optionally with alumina contained in the surface cross-linking charge, for example, 80mVg higher / or 8 ( 2 / g to 180m 2 mounds acidic fumed having a specific surface area / g .. it can be appropriately used such as alumina, alumina meeting the these characteristics - the commercially available (for example, trade name: AEROXIDE Alu displayed to Step alumina, etc.) may be used using this alumina: ϊ ' ' water-absorbent resin a bucket of liquid and / or caking suppressing ^ ¾ during sex can further improve.

And, in the high water-absorbent resin one embodiment, the aluminum sulfate based on 100 parts by weight of the base resin powder, it may be included as part increased from 0.02 to 0.3. And When the content ranges of these aluminum sulphate is too small can be a barrel-component and / or caking inhibiting properties of the water absorbent resin not let enough, the larger struck or the content is mothayeo be a cross-linked structure of the surface cross-linked layer formed properly, rather high there are physical properties of the water absorbent resin may be deteriorated as a whole.

In addition, the alumina optionally contained within the cross-linked surface layer with the aluminum sulfate may be included as part 0.005 to 0.1 parts by weight based on 100 parts by weight of the base resin powder, an alumina dispersed over the surface cross-linked layer includes a base based on 100 parts by weight of the resin powders, it can be included as part 0.03 to 0.2 wt. By the content of this range it is satisfied, yet can be improved effectively, and the barrel-component suppressing caking properties of the superabsorbent polymer, it is possible to suppress the deterioration of the physical properties of the superabsorbent resin.

On the other hand, the above-mentioned super-absorbent resin can and can exhibit excellent liquid tube, this tube excellent liquid transfer property can be defined by the measurement method and the calculation of 10 to 70 seconds, or 15 to 68-second transmission rate with the following equation 1:

[Equation 1]

Permeability (sec) = T S - w To 0

In the formula 1,

Ts (unit: second) is to swell for 30 minutes and the solution of the water-absorbent resin 0.9¾ »salt (NaCl) of salt 0.¾-absorbing preparing a water-absorbent resin and the saline solution of 0.9% under a pressure of 0.3psi salt - meaning the time it takes to pass through the absorption super-absorbent resin,

T 0 (in seconds) is the salt-refers to the time it takes for the permeation of the saline solution of 0.9% under a pressure 0.¾si without superabsorbent polymer absorption.

The permeability of the salt water (0.9% NaCl aqueous solution) and swell is a measure of how well it passed through the water-absorbent resin, the literature (Buchholz, FiL. And Graham. Α.Τ '., "Modern Super absorbent Polymer Technology," John Wiley & Sons (i998). page 161 ) by the methods described, after the swelling of super-absorbent resin powder of 0.2g 30 bungan apply a pressure of 0.3psi taken for the transmission of 0.9% saline solution _ it is evaluated by measuring the time have. For a more detailed permeability measurement method will be described in detail in the Examples below.

In addition, the one embodiment and the water absorbent resin may be a caking prevention efficiency is 75% to 100% of the formula 2, when kept under high temperature / high humidity conditions as described above, aggregation and solidification (caking) is very unlikely It may represent a not good caking properties that suppress:

[Formula 2]

Anti-caking efficiency (%) = [W 6 (g) / W 5 (g)] * 100

In the formula 2,

W 5 (g) is the initial weight (g) of the superabsorbent polymer. W 6 (g) has a diameter of 10 cm flask, and then evenly applied onto the plate of silver is ± 3 40 ° C, a constant temperature to maintain the humidity level of 80 ± 3%

After holding for 10 minutes in a humidity chamber upside down the flask in the plate filter is a three Pater taping (tapping) an amount of superabsorbent polymer falling (g) after.

In addition, the super-absorbent resin may basically indicate the excellent absorption performance, and absorption speed. More specifically, the additive and the water-absorbent resin has a centrifuge beam SAT (CRC) for half an hour for the physiological saline (0.9 weight percent sodium chloride aqueous solution) can be in the 28 to 36g / g, or 29 to 35 g / g .

In this case, the centrifugal beam then SAT (CRC) is absorbed by the saline solution through the superabsorbent polymer in 30 minutes can be calculated by the following equation (3) of:

[Equation 3]

CRC(g/g) = { [W2(g) - Wi(g) ― Wo(g) ] /W0(g) }

In the formula 3,

W 0 and (g) is the initial weight (g) of the superabsorbent polymer, W g) without the use of super-absorbent resin, and by immersion for 30 minutes in physiological saline using a was then centrifuge absorption 3 minutes at 250G and a unit weight measured after dehydration, ' W 2 (g) are after then uses the centrifuge was absorbed and at room temperature in normal saline immersion absorbent resin for 30 minutes, dehydrated 3 minutes at 250G, and a water-absorbent resin including " a measuring device is a weight.

Further, the water absorbent resin is a physiological saline solution for one hour under a pressure of about o .3psi (0.9 weight% aqueous sodium chloride solution) absorption capacity (0.3 AUP) may be from 20 to 33g / g, or 24 to 30 g / g have. In addition, the superabsorbent polymer is coming from the pressure absorption capacity (0.3 AUP) of 10 to 25g / g, black for 1 hour at 7psi for physiological saline may be from 10 to 22 g / g, Therefore, under conditions of high load also it can exhibit an excellent absorbing performance.

The absorption capacity under pressure (AUP) is 0.3 psi throughout the superabsorbent polymer in an hour or

After absorbing the physiological saline solution under pressure of 0.7 ps i, it can be calculated according to the following formula 4:

[Expression 4]

AUP (g / g) = [W 4 (g) - W 3 (g)] / W 0 (g)

In the formula 4,

W 0 (g) is the initial weight (g) of the superabsorbent polymer, W 3 , and (g) is the total weight of the device being capable of imparting a load to the weight and the high water-absorbent resin having a high water-absorbent resin,

W 4 (g) is a load (0.3 ps i or 0.7 ps i) under the above for 1 hour and after absorbing the saline solution to the water-absorbent resin, and the weight and the absorbent resin and the device being capable of imparting the load to the water-absorbent resin the sum of the weights.

In addition, the one embodiment and the water absorbent resin may be a vortex time of 25 to 35 seconds, removed, along with the above-described absorption performance. This vortex removal time may be when sikyeoteul stirring and the physiological saline was added to the water-absorbent resin, as meaning that the missing time swirl (vortex) of liquid by the rapid absorption, defines a rapid rate of absorption of the superabsorbent resin.

This vortex removal time, for example, high above the normal saline solution (NaC solution of 0.9% by weight?), Under stirring followed by the addition of a water-absorbent resin, a liquid resulting from the agitation: extinguish swirl (vortex), result in a smooth surface measuring the amount of time ' can be calculated by the method.

On the other hand, the above-described one embodiment and the water-absorbent resin is typically at least a portion of the carboxylic acid such as acrylic acid and its sodium salt neutralized with a common compound such as a sodium salt, neutralizing at least a part. Cross-linking polymerization of the water-soluble ethylenically unsaturated end ryangjae having an acid group in the presence of an internal cross-linking agent by can be obtained. More specifically, the high, then the water absorbent resin and a base resin powder to the surface cross-linking solution containing the post by crosslinking polymerization of said monomer in the presence of an internal cross-linking agent obtained a base resin powder, the surface crosslinking agent and aluminum sulfate surface cross-linking, alumina and the like can be obtained by dry mixing.

More specifically, by controlling the type and content of the polymerization condition of the internal cross-linking agent deungol, for example, then to obtain a base resin powder that meets the 29g / g or more centrifugation beam SAT (CRC), and more than 27 seconds vortex removal time, whereby about there, as progression to a given surface cross-linking process and the dry process heunhap, implement one that exhibits good physical properties and the above-described embodiment to obtain a water-absorbent resin.

According to another embodiment of the invention, in the presence of an internal crosslinking agent, to form a hydrogel polymer comprising a first cross-linked polymer by cross-linking polymerization of the water-soluble ethylenically unsaturated monomer having at least partially neutralized acid; The function drying the gel polymer, pulverized and classified to a base resin powder " to form; and in the presence of a surface cross-linking solution containing aluminum sulphate and a surface cross-linking agent, by heating a base resin powder surface cross-linking superabsorbent polymer particles forming at; and high including the common dry summing phase alumina on the superabsorbent polymer particle is provided a method for producing a water-absorbent resin.

Hereinafter, it will be described in detail an example of a manufacturing method of such a superabsorbent resin in each step.

In the production method, first, in the presence of an internal cross-linking agent, by cross-linking polymerization of the water-soluble ethylenically saturated monomer block may form a hydrogel polymer.

At this time, as the water-soluble ethylenically unsaturated monomer is acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, ethanesulfonic acid 2-yl acrylate, to be ethanesulfonate, 2-methacrylamide, 2- ( meth) acid, or 2 一 (meth) acrylamide-2-methyl anionic monomers and their salts of the sulfonic acid with an acrylic; ( "Meth) acrylamide, N- substituted (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, meteuk when polyethylene glycol (meth) acrylate or polyethylene glycol (meth) acrylate and the non-ionic hydrophilic monomer containing; And (Ν, Ν)-dimethylaminopropyl (meth) an amino group-containing unsaturated monomer of acrylamide and their quaternary cargo-dimethylaminoethyl (meth) acrylate or (Ν, Ν); at least one selected from the group consisting of It can be used. Of these, it may be used an alkali metal salt such as acrylic acid or a salt thereof, e.g., the at least a portion of the acrylic acid neutralized acrylic acid and / or its sodium salt, and having excellent physical properties than using these monomers producing a water-absorbent resin the becomes possible.

When using the acrylic acid and its alkali metal salt as a monomer, it may be used to jeunghwa with a basic compound such as acrylic acid and caustic soda (NaOH). In this case, the neutralization degree of the water-soluble ethylenically unsaturated monomer may be adjusted to 50 to 95% or from 70 to 85%, this range the beam SAT excellent without risk of precipitation when neutralized at a high it is possible to provide a water-absorbent resin.

Among monomers common compound including the water-soluble ethylenically unsaturated monomer, the concentration of the water-soluble ethylenically unsaturated monomers, 20 to 60% by weight of the total monomers common compounds each containing a raw material and a solvent to be described later, or 40 to 50 wt. may be in%, it can be considered, such as the polymerization time and conditions banung to the appropriate concentration. However, the high surface concentration of the monomer is too low, a low yield of the water-absorbent resin may be a problem in economical efficiency, whereas the concentration is too high when a part of the monomer precipitates or polymerized hydrogel low crushed during grinding efficiency of increased polymer It can cause process problems and the like that appear and there is a physical property of the water absorbent resin may be deteriorated.

The internal cross-linking agent for introducing a basic cross-linked structure in the base resin powder, it is possible to use all without limitation in the internal cross-linking agent having a crosslinkable functional group and the release from conventional use in the production of water-absorbent resin. However, and by introducing a suitable crosslinking structure in the base resin powder in order to improve the physical properties of the water absorbent resin, more specifically, and as appropriate to achieve the physical properties of the above base resin powder improved barrel-component of the water absorbent resin and a caking suppressing in order to express the characteristics, the internal cross-linking agent having a carbon number of 8 to 30-bis (meth) acrylamide / 2 carbon atoms of to 30 polyol poly (meth) acrylate and a polyol of a carbon number of 2 to 30 (meth) allyl It may be 1, or more selected from the group consisting of ether. A more specific example of such an internal cross-linking agent, polyethylene glycol diacrylate (PEGDA), glycerol diacrylate, glycerol triacrylate, unmodified or ethoxylated trimethylolpropane triacrylate (Ethoxyl ated-TMPTA), nucleic acid-diol di acrylate, and triethylene glycol at least one selected from the group consisting of a diacrylate. These internal cross-linking agent is included at a concentration of lead 01 to 0.5% by weight relative to the monomer mixture, it is possible to cross-link the polymerized polymer.

In addition, the monomers common compound may further comprise a polymerization initiator that were commonly used for the production of superabsorbent polymer.

Specifically, the polymerization initiators according to the polymerization method, or a thermal polymerization initiator

You can use the photo-polymerization initiator by UV irradiation. However, even in the photo-polymerization method, since the amount of heat generated by the irradiation such as ultraviolet irradiation, and further a certain amount of heat generated with the progress of the polymerization reaction heat, further

It may comprise a thermal polymerization initiator.

The photopolymerization initiator is a compound capable of forming a radical by light such as ultraviolet rays, it may be used without any limitation in its configuration. The photo-polymerization initiator include, for example, benzoin. Ether (benzoin ether), dialkyl acetophenones (dialkyl acetophenone), hydroxyl-alkyl ketones (hydroxyl alkylketone), phenyl glyoxylic rate (phenyl glyoxylate), benzyl dimethyl ketal (Benzyl Dimethyl Ketal). . Acylphosphine (acyl phosph ine) and alpha-may be at least one selected from the group consisting of amino-ketone (a -aminoketone). On the other hand, liicirin TP0, i.e., 2, 4, 6-trimethyl-eu to commercial Specific examples of the acylphosphine-benzoyl-trimethyl phosphine oxide, (2,4,6-trimethy 卜 benzoyl-trimethyl phosph ine oxide) or IRGACURE 819 , that is, bis (2, 4, 6-trimethyl-benzoyl) phenyl phosphine oxide (bis-tr imethylbenzoyl He) can be "for -phenylphosphineo ^ 人.

For more on the various photoinitiators Reinhold Schwa lm book, "UV Coatings: Basics, Recent Deve 1 opment s and New Appl icat ion (Elsevier 2007 year)" and specify the language well pll5 i also not limited to the above example.

The photopolymerization initiator may it be included at a concentration of 0.01 to 1.0% by weight relative to the monomers common compound. When the concentration of such a photopolymerization initiator is too low, the polymerization rate - may ryeojil can be high concentration of the photopolymerization initiator is too high, the irregularity becomes small and the molecular weight properties of the water absorbent resin.

It is also possible to use the thermal polymerization initiator include a persulfate-based initiator, an azo-based initiator, a peroxide and at least one initiator selected from the group consisting of ascorbic acid. Specifically, as examples of the sulfate-based initiator it is sodium persulfate (Sodiuni persulfate; Na 2 S 2 0 8 ), potassium persulfate (Potassium persulfate; K 2 S 2 0 8 ), ammonium persulfate (A隱onium persulfate; (丽4) 2 S 208). And the like, examples of the azo (Azo) based initiators eu 2 2-azobis- (2-amidinopropane) dihydrochloride (2,2-azobis (2-amidinopropane) dihydrochlor ide), 2,2-azobis 一一 (N'N_ dimethylene) isobutoxy Thira Mai Dean dihydrochloride ^^ - azobis- ^ -diniethylene) isobutyramkline dihydrochlor ide), 2- (carbamoyl azo) isonitrile (2- (carbamoyIazo butyronitrile) isobutylonitril), 2 , 2-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (2,2- azobi s [2 eu (2-imidazol in-2-yl) propane] dihydrochlor ide), 4, 4-azobis- the like (4-cyano ballet rigs) (4, 4-azob i s- (4-cyanova 1 er ic acid)).

Than are well specified in The various thermal polymerization initiator Odi book, an 'Pr inc iple of Polymer i zat ion (Wi ley, 1981)', p203, not limited to the above example.

The thermal polymerization initiator may be contained in a concentration of 0.001 to 0.5% by weight relative to the monomers common compound. When the concentration of such a thermal polymerization initiator is too low, the additional thermal polymerization may be minimal effect of the addition of the thermal polymerization initiator hardly occurs, the number and the concentration of the thermal polymerization initiator is too high, become small and the molecular weight properties of the water absorbent resin uniform have.

In addition, the monomers common compounds may further comprise additives such as thickeners (thi ckener), a plasticizer, a preservation stabilizer, an antioxidant, a surfactant, if necessary. The additional additives may be used, without limitation, various additives commonly used in superabsorbent polymer-related areas.

On the other hand, a starting material such as the above-described water-soluble ethylenically unsaturated monomer, photopolymerization initiator, thermal polymerization initiator, an internal crosslinking agent and additives may be prepared in a solubilized form in the solvent.

The solvent that can be used this time, if it can dissolve the above-mentioned components can be used without limitation of its construction, for example, water, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol . Propylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl amyl ketone, cyclo hex rice, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, the may be used in combination with toluene, xylene, cellosolve butyl lactone, acid rain, methyl acetate, and cell Ν, Ν- 1 or more kinds selected from dimethylacetamide.

These solvents can be included in the remaining amount than the above-mentioned components, based on the total content of the monomer heunhap.

On the other hand, this method in the same monomer composition heat syndrome sum or photopolymerization to form the hydrogel polymer is also conventional polymerization method used, particularly in the configuration

There is no limitation.

Specifically, for example, polymerization of the monomer composition can be greatly depending on the polymerization energy source divided by the thermal polymerization and photo polymerization: When proceeding to normal thermal polymerization, agitation, such as a kneader (kneader) to facilitate bubbling axis It can proceed with in a half unggi. On the other hand, when the photopolymerization proceeds, the movable half can be conducted in a unggi provided with a conveyor belt. However, the above-described polymerization method is an example, the present invention is not limited to the above-described polymerization method.

Then, the polymerization temperature of the monomer mixture from about 40 to 90 ° it is possible to effectively induce the hydrogel polymer polymerization gasification and pores are formed in the volatile organic solvent is adjusted to C.

In this case, the means for achieving the polymerization temperature in the above range is not particularly limited. Supplying a heating medium or. It can be heated by supplying the heat source directly. The kind of the heating medium is available is to use a fluid such as an elevated temperature, such as steam, hot air, hot oil, but not limited to this eu, and the temperature of the heating medium supplied to consider the means, the rate of rise and temperature rise target temperature of the heating medium can be appropriately selected other hand, through the heating gas through the electricity to the heat source is directly supplied to: include a heating method, but is not limited to the above-described example.

The polymerization time of the monomer mixture to form a hydrogel polymer having a porous structure optimized is adjusted to 30 seconds to 10 minutes.

For example, in a reactor such as a kneader (kneader) having an axis stirred as described above. By supplying hot air, or heating the reactor hydrogel polymer obtained by the thermal polymerization in accordance with the form of a stirring shaft provided in the reactor, the hydrogel polymer to be discharged to half unggi outlet may be a few centimeters to a few millimeters form. Specifically, there is obtained the size of the hydrogel polymer may vary depending on the concentration and the injection rate of the monomer composition to be injected, it is usually a weight-average particle size is about 2 to 50 mm hydrogel polymer can be obtained.

In the case of the photo-polymerization proceeds in a reactor equipped with a movable conveyor belt, as described above, the shape of the obtained conventional hydrogel polymer may be a hydrogel polymer on a sheet with the width of the belt. At this time, the thickness of the polymer sheet is preferably supplied through the monomer composition depends on the concentration and the injection rate of the monomer composition to be injected, so that the polymer on the sheet with typically about 0.5 to about 5cm in thickness can be obtained. When supplying the monomer composition around the polymer thickness of the sheet is too thin, is not preferable lower and the production efficiency, when the polymer thickness on sheet exceeds 5cm, this, because of the excessively thick dukkae polymerization occur evenly throughout the thickness can not.

In this case usually the water content of the hydrogel polymer obtained in the same method may be 40 to 80% by weight. On the other hand, in this specification "water content" "refers to a value obtained by subtracting the weight of the total hydrogel in the dry state from the weight of the hydrogel polymer in an amount of water which accounts for the polymer weight increased polymer eu an Specifically, infrared heating through is defined as a value calculated by measuring the weight decrease due to evaporation of water in the polymer in the process of up and dried the temperature of the polymer. in this case, drying conditions at room temperature, about 180 ° 180 after raising the temperature up to C ° maintained at C the total drying time in such a way that by including 5 at a temperature ramping up step is set to 20 minutes to measure the water content.

And, after cross-linking polymerization of the above monomers, there can be obtained a base resin powder through a process such as drying, crushing and classifying, via a process such as this grinding and classifying, and is obtained from a base resin powder and the resulting water-absorbent resin to have a particle diameter of 150 to 850, it is suitable and provided the recombinant. More specifically, the base resin powder and has a high, at least more than 95% by weight of 150 to 850 particle diameter of the absorbent resin obtained therefrom, the fine powder having a particle size of less than 150 may be less than 3% by weight.

Thus, according to the regulated to a preferred range of particle size distribution of the base resin powder and the super-absorbent resin, the final manufactured superabsorbent polymer can already come well expressed than the above-mentioned physical properties.

On the other hand, in a more specifically for the progress of the drying, crushing and classification as follows:

First, in the function as drying the polymer gel it can be subjected to a further step of coarse ground before drying in order to increase the efficiency of the drying step, if necessary.

At this time, the crusher to be used is limited to the configuration, but, specifically, a vertical cutter (Vert i cal pulver i zer), turbo cutter (Turbo cut ter), turbo grinder (Turbo gr inder), rotary cutting mill ( crushing consisting Rotary cut ter mi ll), cutting mill (cut ter mill), disc mill (disc mill), a piece crusher (Shred crusher), crusher (crusher), the chopper (chopper) and source plate type cutter (disc cutter) but it may include any one selected from a device group, but is not limited to the above example.

The pulverized step may be pulverized so that the particle diameter of the hydrogel polymer from about 2 to about 10 隱 隱.

The particle size is milled to less than 2 mm is not easy technically because of the high water content of the hydrogel polymer, and may also appear to be ungjip each other between the ground particles developing. On the other hand, if the particle size is milled to 10 隱 excess, it can be minimal increase the efficiency effect of the drying step further comprises.

Or pulverized as described above or carries out a drying of the polymer hydrogel for jeunghap immediately without passing through the pulverized step. The drying temperature of the drying step is 50 to 250 ° may be C. The dry silver is 50 ° is less than C, and the physical properties of the water absorbent resin to be the drying time is too longer and forming end. The risk of deterioration, and the drying temperature is 250 ° when it exceeds C, over-dried only polymer surface, may result in a differential in the formed later pulverization process, there is a high possibility that the physical properties of the water absorbent resin reduced to be finally formed. More preferably, the drying is 150 to 200 ° even at a temperature of C,. Preferably from 160 to 190 ° can be carried out at a temperature of C.

On the other hand, when the drying time, but in consideration of process efficiency could last deungol, 20 minutes to 15 hours, but is not limited to this.

The drying method of the drying step as long as it is also commonly used in the drying step of the hydrogel polymer may be used are selected, without limitation of its construction. Specifically, a method such as hot air supply, infrared irradiation, microwave irradiation, or the ultraviolet irradiation may be carried out a drying step. The water content after the drying phase, such polymers can be from 0.05 to 10% by weight.

Next, the steps of crushing the dried polymer obtained through this drying steps.

After the grinding step the resulting polymer powder may be a particle diameter of 150 to 850 / zm. Mill used for grinding to this particle size Specifically, a ball mill (ball mi 11), pin mill (pin mill), a hammer mill (hammer mill), screw mill (screw mill), a mill (rol l mi ll ), but you can use a disc mill, etc. (di sc mi ll) or the jog mill (jog mi ll), but is not limited to the above example.

And, on the other and such that the milling step after the last commercialized in order to manage the physical properties of the water-absorbent resin powder, may be subjected to a separate step of the classification according to the polymer powder obtained after grinding the grain size. Preferably the particle size is classified to 150 to 850 polymer, only the surface of polymer powder having such a particle diameter and can be commercialized after the crosslinking step banung.

On the other hand, and then proceed with the step of forming the above-mentioned base resin powder, the one embodiment and the water absorbent resin production method by heating the aluminum sulfate and the surface cross-linking agent, the base resin in the presence of a surface cross-linking solution containing the powder surface cross-linking It can include.

At this time, the type of the surface crosslinking agent and aluminum sulfate and the content deungeo for Γ, one embodiment described in relation to the water-absorbent resin and a bar thereof ; And thus it " . More on ■ explanation is omitted. For reference, the amount of aluminum sulfate in the surface cross-linking solution have already example above one embodiment the absorbent, resin jungwa: may correspond to the content of aluminum sulfate.

Further, the surface cross-linking liquid is water, ethanol, ethylene glycol, diethylene glycol: triethylene glycol, 1,4-butanediol, propylene glycol, ethylene glycol monobutyl ether. Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl amyl ketone, cyclo hex rice, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, the toluene, xylene, butyl as a lactone, a carboxylic ratio, may further include one or more solvents selected from the group consisting of acetate, Ν, Ν- dimethylacetamide and methyl cellosolve.

And, an implementation example and, together with the aluminum sulphate in the surface cross-linking the charge of the water-absorbent resin, as already mentioned above, optionally, and alumina may further contain, to this end, the surface cross-linking solution may further comprises alumina. The amount of alumina in the surface cross-linking solution may also, one embodiment and sangung the content of alumina in the surface cross-linked layer of the water absorbent resin.

Further, the surface cross-linking agent contained in the surface cross-linking solution may be used in an amount of 0.01 to 4 parts by weight based on 100 parts by weight of the base resin powder.

On the other hand, in the step of forming the cross-linked surface layer, in the surface cross-linking solution. It may further comprise a thickening agent. This cross-linking under the thickening agent present in adding the surface of the base resin powder can minimize the physical property degradation even after grinding.

More specifically, the thickener in may be used at least one selected of the polysaccharide and a hydroxy-containing polymer.

among these. The polysaccharides include the like can be used agarose-based thickener with gum-based thickening agents and selreul. Examples of the gum-based thickener, xanthan gum (xanthan gum), Arabic gum (arabi c gum), karaya gums (karaya gum), tragacanth gum (tragacanth gum), Gatti gum (ghat ti gum), guar gum (guar gum), locust to bean gum (locust bean gum) and four days Solarium seed gum (psyl l ium seed gum) and the like, and specific examples of the trehalose-based thickener in the selreul is hydroxypropylmethylcellulose selreul Osu. Ssaelreul as carboxymethyl agarose, agarose, methyl selreul as agarose, hydroxymethyl selreul. Hydroxide in a agarose, hydroxypropyl hydroxyethyl selreul selreul agarose, agarose-hydroxy-ethoxy ethyl methyl selreul as agarose, hydroxy propyl methyl cellulose, hydroxyethyl hydroxypropyl selreul as agarose, ethyl hydroxyethyl selreul. And: it may be mentioned agarose, such as methyl hydroxypropyl selreul. On the other hand, specific examples of the hydroxy-containing polymer is polyethylene glycol and polyvinyl alcohol round. And, " the surface crosslinking solution Na according to the type of the surface cross-linking agent, so that the surface cross-linking banung can take place more smoothly 2 S 2 0 5 further comprising a color transfer inhibitor commercialized by adding water, and further include a thermal initiator such as You may. '

On the other hand, the surface cross-linking step, the base resin powder in the presence of the above-described surface cross-linking solution 100 ° can be carried out by heat treatment over C. In particular, and have good overall physical properties for the production of water-absorbent resin, the surface cross-linking process conditions is from 100 to 180 ° it can be carried out at a temperature of from C 10 minutes to 60 minutes. In one specific example. Maximum reaction temperature of 100 ° or more C, or about 120 to 180 ° but may be a holding time of 10 minutes or more in terms of C, up to banung temperature.

Temperature raising means for the surface cross-linking reaction is not particularly limited. Supplying a heating medium, or can be heated to supply the heat source directly. At this time, as a type of available heating medium, but can use a fluid such as an elevated temperature, such as steam, hot air, hot oil, not limited to this, and the temperature of the heating medium supplied to the means of the heating medium,

It can be appropriately selected in consideration of the rate of temperature increase and temperature rise target temperature. On the other hand, as a heat source is directly supplied to the heating by the electrical heating through the gas, but a method, it is not limited to the above example.

After proceeding to the above-described surface cross-linking step, it may be carried out the step of dry mixing the alumina onto the superabsorbent resin with the surface cross-linked particles. At this time, the amount of the alumina can be embodiment previously described one embodiment and sangung the amount of alumina on the surface cross-linked layer of the water absorbent resin.

The types of used alumina has already as described above, information on how to and added to the water-absorbent resin particle such alumina is not limited in its construction. For example, into the alumina and super-absorbent resin particle bath banung heunhap dry, or may with a high mixer being continuously operated at a water-absorbent resin particles, and use common way is joined to the alumina supplied continuously deungol.

【Effects of the Invention】

According to the invention, basically excellent absorption performance and the rate of absorption " , indicating" also, more shows an improved barrel-component, under high temperature / high humidity conditions is also high is ungjip and caking between particles is suppressed water absorbent resin and providing a production method thereof It can be,

Such super-absorbent resin is reduced or the amount of the pulp, is preferably used in a diaper, such as sanitary material pilpeu is not used can be exhibited an excellent performance.

[Mode for Carrying out the invention]

Hereinafter, one present preferred embodiment to help understanding of the invention, the following examples are not limited to the following embodiments are intended as the scope of the invention to illustrate the invention.

In the Examples and Comparative Examples, physical properties of each of the superabsorbent resin (or the base resin powder) was measured and evaluated by the following method.

(1) particle size evaluation

Exemplary particle size of the super-absorbent resin used in the Examples and Comparative Examples were measured according to the European Nonwoven Industry Association (European Disposables and Nonwovens Association, EDANA) standard method EDANA WSP 220.3.

(2) centrifuging beam SAT (CRC, Centrifuge Retention Capacity)

Yu . The Examples and Comparative Examples and centrifuged beam SAT (CRC) due to, no load Heavy absorption ratio with respect to the water-absorbent resin according to the European Nonwoven Industry Association (European Disposables and Nonwovens Association, EDANA) standard EDANA WSP 241.3 was measured.

That is, the resin of Examples and Comparative Examples W 0 (g, about 0.3) after the insert uniformly on the envelope of the nonwoven fabric is sealed (seal), was submerged in the saline solution is a sodium chloride solution of 0.9 weight% at room temperature. After 30 minutes using a centrifuge after the envelope, leave for 3 minutes to dry 250G weight W of the bag 2 were measured in (g). Also after the same operation without the use of a resin was measured by mass Wi (g) at that time.

In this way use of the respective mass obtained according to the following equation 3 to calculate the CRC (g / g) it was confirmed beam SAT.

[Equation 3]

CRC(g/g) = {[¾(g) - Wi(g) - W0(g)]/ o(g)}

In the formula 3,

W 0 and (g) is the initial weight (g) of the superabsorbent polymer, W g) without the use of super-absorbent resin, and by immersion for 30 minutes in physiological saline using a was then centrifuge absorption 3 minutes at 250G and a unit weight measured after dehydration, W 2 (g) is that absorption and with physiological saline in the phase flooding the absorbent resin for 30 minutes, then using a centrifuge dehydrated 3 minutes at 250G, the superabsorbent polymer It is a weighing apparatus, including.

(3) absorption capacity under pressure (under Absorbing Pressure, AUP)

Examples and Comparative Examples that, the European Association for the nonwoven industry in the absorbent resins (European Disposables and Nonwovens Association) standard EDANA. Pressure absorbing power according to the process of the WSP 242.3: a (AUP Absorbency under Pressure) was measured.

First, in the cylindrical bottom of the replicon, the inner diameter of the stick 60隱was fitted with a stainless 400 mesh wire net. Under relative humidity conditions of temperature and 45% of 23土2 ° C in the iron mesh Examples and bars resin W obtained in Comparative Example 0 evenly sprayed (g, 0.90 g), and even with a load of 0.3 psi or 0.7 psi over the more piston (piston) which can impart a slightly smaller outer diameter was not there and the inner wall of the cylindrical flow隱than 60, the upper and lower motion undisturbed. The weight W of the device 3 was measured (g).

With a glass filter having a thickness of 5隱on the inside of the dish with a diameter of 150 Petro隱隱a diameter 125, a saline consisting of 0.90% by weight of sodium chloride was adjusted to the same level as the upper surface of the glass filter. On top of the filter paper 1 carried a diameter of 120睡. Carrying the measurement device over a filter paper, the solution was absorbed for 1 hour under a load. After 1 hour deuleoeul hitting the measuring device, the weight W 4 was determined (g). In this way use of the respective mass obtained by the following equation 4, to calculate the AUP (g / g) confirmed that the pressure absorbing ability.

[Expression 4]

AUP (g / g) - [W 4 (g) - W 3 (g)] / W 0 (g)

In the formula 4,

W 0 (g) is the initial weight (g) of the superabsorbent polymer., W 3 (g) it is high and the water-absorbent resin and the weight and the high total of the unit weight which can impart a load to the water-absorbent resin, W 4 ( g ) is a total of the apparatus weight to give the weight and load on the superabsorbent polymer of one and the period of time after absorption of saline solution to the water-absorbent resin, and water-absorbent resin under load (0.3 psi or 0.7 psi) eu

(4) Permeability

Permeability literature: 0.3psi load using a saline solution of 0.9% by the method described in (Buchholz, FL and Graham, A. T, "Modern Super absorbent Polymer Technology," John Wiley & Sons (1998), page 161) under was measured. If a more detailed description for the measuring method, the embodiments and the comparative example of the super-absorbent resin (hereinafter, referred to as the sample) from 300 to 600. The cylinder (Φ20 隱) takes the 0.¾ particles having a particle diameter of the prepared It was added. At this time, one end of the cylinder includes a stop-cock (stopcock), the upper and lower limits of the cylinder there is displayed

The upper limit is displayed at a position at which the (brine) solution of 40mL is filled, the lower limit is displayed at a position at which the (brine) solution of 20mL is filled.

50g of a 0.9% saline (NaCl) solution (sal ine solut ion) stop cock is put into the cylinder in the locked state and was allowed to stand for 30 minutes. If required then, to be level (level) of saline solution was added an additional saline solution to come to the upper limit of the cylinder. Next, now saline-added load of 0.3ps i on a cylinder comprising an absorption super-absorbent resin was allowed to stand for 1 minute. After opening the stop cock (stopcock) located below the cylinder to measure the time passing through the lower limit from the upper limit indicated in the 0.9% saline solution the cylinder. All measurements土1 24 ° was carried out under the relative humidity of the temperature and 50 ± 10% of the C.

And as for the time each sample ol (Ts) passing through the lower limit from the upper limit (T without added water-absorbent resin of 0 to measurement), and the product was calculated in accordance with the transmission (1).

[Equation 1]

Permeability (sec) = T s - T 0

In the formula 1,

Ts (unit: second) is to swell for 30 minutes and 0.2g of water-absorbent resin with 0.9% saline (NaCl) solution of brine - a saline solution of 0.9% under the absorption of preparing a water-absorbent resin, and pressure i the 0.3ps salt-refers to the time it takes to pass through the absorption super-absorbent resin, and to (in seconds) is the salt-refers to the time it takes for the permeation of the saline solution of 0.9% under a 0.3psi pressure without superabsorbent polymer absorption.

5 casing prevention efficiency (A / C efficiency, Anti "Caking efficiency)

Examples and Comparative that prepared in Example absorbing resin 2 g (W 5 ) of diameter 10 cm and then evenly applied to the flask and plate temperature 40 ± 3 ° C, humidity 80 ± 10 minutes in a constant temperature constant humidity chamber that maintains the 3% after holding the inverted plate on a filter flask Pater three taping (tapping), and then the amount (W falling absorbent resin while 6 were measured).

In this manner was calculated using the measured weight of the casing prevents the efficiency according to the following formula 2 is excellent in a higher efficiency levels.

[Formula 2]

Anti-caking efficiency (%) = [W 6 (g) IW 5 (g)] * 100

In the formula 2, W 5 (g) is that the initial weight (g) of the water absorbent resin, W 6 (g) has a diameter of 10 cm and then evenly applied to the flask and plate temperature 40土3 ° C, humidity of 80 ± 3% after holding for 10 minutes in a constant temperature and humidity chamber that maintains the level reversed the flask to the filter plate is 3 times Pater taping (tapping) and the falling amount of the water-absorbent resin (g) after.

(6) absorption rate (vortex test, Vortex-test)

Beaker, 100, insert the NaCl solution of 0.9% by weight 50 m, while stirring using a stirrer to 600 rpm, was added to the superabsorbent resin 2g prepared in Examples and Comparative Examples, respectively. And it eliminates the fluid swirl (vortex) generated by the stirring, a smooth surface result in., And measuring the time until the results are shown in the vortex removal time.

Preparation 1: Preparation of base resin powder A

Into a 2L glass beaker 450g of acrylic acid, 24% sodium hydroxide aqueous solution of 693.88 g poured slowly a common combined to prepare a first solution. At this time, the generation and junghwayeol, stirred at room temperature and the solution heunhap about 41 ° to the C . It was nyaenggak. Then, the addition of polyethylene glycol diacrylate (PEGDA 600) 0.225 g, surface active agent (S1670) 0. 16g, dioctyl sulfo succinate sodium salt (Dioctyl sul fosucc inate sodium sal t, A0T) 0.045g to 50g acrylic acid 2 solution; 4% sodium bicarbonate (Sodium bi carbonate, NaHC0 3 ) solution (third solution) 26g; 0.31% ascorbic acid (Ascorbi c ac id) Solution (4 solution) 35g; Lg hydrogen peroxide and potassium persulfate (Potass ium per sul fate) and a solution diluted with distilled water to 40 g 0.69g (solution 1: 5); in turn was added to the first solution.

This is the release of gel was added in the beaker and stirred Vat form straight chumyeon stops of the tray was poured into a (tray, width 15cm X 15cm vertical). Spilled gel and foam as not shear 20 seconds, and polymerization was proceeding slowly shrinking. A fully shrink polymer is torn out from 5 to 10 pieces transferred into a kneader (kneader) to close the Tous ¾ was performed for 5 minutes kneading. In the kneading process during 4 minutes from the initial

Open the lid after the injection of 3.5% potassium persulfate (Potassium persulfate) solution to 50g of increased internal kneader copolymers closed Tous ¾.

Then, using a meat chopper (meat chopper) was passed through the polymer in a hole having a diameter of 13 睡 was prepared with flour (crump).

Then, the dried powder (crump) in the air volume available Bon Festival transition in the vertical direction. The water content of the dried powder of about 2180 such that the eu than ° , and the hot air (hot air) of C to flow upward from the bottom for 15 minutes, and again flows downward from the upper side 15 minutes uniformly drying the powder (crump) It was.

Then, a grinding the dried powder to the pulverizer, and then classified to obtain a base resin powder A of 150 to 850 particle size. The base resin powder A was found to represent the freshly centrifugation of 31g / g beams SAT (CRC), and 27 seconds of vortex removal time.

Preparation 2: Preparation of base resin powder B

Place the acrylic acid 450g in 2L glass beaker, the mixture poured into a 24% aqueous solution of caustic soda, and 693.88g slowly to prepare a first solution. At this time, the generation and junghwayeol, stirred at room temperature and the solution heunhap about 41 ° and then cooled to C. Thereafter, polyethylene glycol diacrylate (PEGDA 600) 0.225 g, surface active agent (S1670) 0.16g, dioctyl sulfo succinate sodium salt (sodium salt Dioctyl SLilfosuccinate, A0T) 0.045g The second solution was added to 50g of acrylic acid; 4% sodium bicarbonate (Sodium bicarbonate, NaHC0 3 ) solution (third solution) 26g; 0.31% ascorbic acid (Ascorbic acid) aqueous solution (Fourth solution) 35g; Lg and hydrogen peroxide and a solution of diluted sulfuric acid and potassium (Potassium persulfate), 0.69g of distilled water 40 g (Fifth solution); a turn, was added to the first solution.

This is the release of gel was added in the beaker and stirred Vat form straight chumyeon stops of the tray was poured into a (tray, width 15cm X 15cm vertical). Gel is poured and foamed in and out of 20 seconds, and the polymerization is in progress was carried out for 5 minutes kneading Close the lid and transferred into a kneader (kneader) for taking tear from 5 to 10 pieces is a polymer eu enough shrinkage was slowly retracted. In the kneading process, open the lid, when four minutes has passed from the initial closed the lid and then injected into the internal kneader of 3.5% potassium persulfate (Potassium persulfate) aqueous solution of 50g polymer.

Then, using a meat chopper (meat chopper) was passed through the polymer to the hole diameter of 13mni was prepared with flour (crump).

Then, in the available Bon Festival flow rate transition and down the powder (cr讓p) the drying was eu 180 the water content of the dried powder is less than or equal to about 2% ° a hot air (hot ai r) of C upward from the lower 15 minutes a flow and allowed to flow back downward from the upper 15 minutes uniformly drying the powder (crump).

after,. The dried powder is ground in grinder, and then classified to obtain a base resin powder A of 150 to 850 / particle size. The base resin powder A was found to exhibit centrifugation of 37g / g beams SAT (CRC), and 39 seconds of vortex removal time.

Example 1: Preparation of Superabsorbent Polymer

In the 150g of the base resin powder A obtained in Production Example 1 at a high speed mixer to obtain a surface cross-linking solution with the following composition.

Surface cross-linking solution with respect to the base resin powder, water, 3,6% by weight, the methane

3.6% by weight, polyethylene glycol diglycidyl ester [(EX810), 0.2% by weight of aluminum sulphate (A1 2 (SC) 4 23% aqueous solution of 0.03% by weight of a), alumina (trade name: Alu 130)

0.03 ¾ thermal initiator as Na 2 S 2 0 5 0.05% by weight of color transfer inhibitor (trade name: HP ancolen bl) was 0.05% by weight of the sum of the common eu

Add this solution to the surface cross-linking the high-speed mixer and stirred for 30 seconds at 400rpm. Since, 135 ° at C for 35 minutes and the surface cross-linking banung.

Then, the alumina for the product of the surface cross-linking: by the (trade name Al 130 u) 1 0. The product was further added to the% by weight and traces obtained were combined classifier using the US standard 20 mesh screen and a 170 United States Standard mesh screen, particle size 150 to 850 and the water-absorbent resin was obtained.

These high to respectively measure the water-absorbent resin and the transmission rate, CRC, 0.3AUP, 0.7AUP, anti-caking efficiency, and eliminate vortex time are shown collectively in Table 1.

Example 2: Preparation of Superabsorbent Polymer

In the surface cross-linking solution composition, with respect to the base resin powder,

Aluminum sulphate (A1 2 (S0 4 was prepared in the super-absorbent resin of Example 2 in the same manner as in Example 1 except for using a 23% aqueous solution of 0.05% by weight of a).

These high to respectively measure the permeability of the water-absorbent resin, CRC, 0.3AUP, 0.7AUP, anti-caking efficiency, and eliminate vortex time are shown collectively in Table 1.

Example 3: Preparation of Superabsorbent Polymer

In the surface cross-linking solution composition, with respect to the base resin powder, aluminum sulphate (A1 2 (S0 4 to manufacture a super-absorbent resin of Example 3 in the same manner as in Example 1 except for using a 23% aqueous solution of 0.07% by weight of a) It was.

These high to respectively measure the permeability of the water-absorbent resin, CRC, 0.3AUP, 0.7AUP, anti-caking efficiency, and eliminate vortex time are shown collectively in Table 1.

Example 4: Preparation of Superabsorbent Polymer

In the base resin, 150g of a powder B obtained in Production Example 2 in a high speed mixer to obtain a surface cross-linking solution with the following composition.

With respect to the base resin powder surface cross-linking solution is 3.4% by weight of water, methanol 3.4% by weight, polyethylene glycol diglycidyl ester [(EX810) 0. 15% by weight of aluminum sulphate (A1 2 (S0 4 23% aqueous solution) 0.2 Na as the weight and thermal initiator 2 S 2 0 5 was 0.05% by weight of the sum of the traces.

Add this solution to the surface cross-linking the high-speed mixer and stirred for 30 seconds at 400rpm. Since, 140 ° was a surface cross-linking for 35 minutes at banung C.

Then, the alumina for the product of the surface cross-linking: The by (trade name A lu 130) 0. Product 1 was further added to the% by weight and traces obtained were combined classifier using the US standard 20 mesh screen and a 170 United States Standard mesh screen, particle size 150 to 850 and the water-absorbent resin was obtained.

These high to respectively measure the permeability of the water-absorbent resin, CRC, 0.3AUP, 0.7AUP, anti-caking efficiency, and eliminate vortex time are shown collectively in Table 1.

Example 5: Preparation of Superabsorbent Polymer

Alumina for the product of the surface cross-linking (trade name: Al u C) 0.05 wt ¾> which was to manufacture a super-absorbent resin of Example 5 in the same manner 'method as in Example 4 except that the processing further added.

These high to respectively measure the permeability of the water-absorbent resin, CRC, 0.3AUP, 0.7AUP, anti-caking efficiency, and eliminate vortex time are shown collectively in Table 1.

Example 6: Preparation of Superabsorbent Polymer

Alumina for the product of the surface cross-linking (trade name: Alu C), except that the treatment in addition is added to the 0.1 wt% to prepare a super-absorbent resin of Example 6 in the same manner as in Example 4. .

These high to respectively measure the permeability of the water-absorbent resin, CRC, 0.3AUP, 0.7AUP, anti-caking efficiency, and eliminate vortex time are shown collectively in Table 1.

Example 7: Preparation of Superabsorbent Polymer

Above for the product of the surface cross-alumina (trade name: Alu C), except 0.15 wt% geotol treated further added to the super-absorbent resin was produced in the embodiment in the same manner as in Example 4 Example 7.

The high permeability of the water-absorbent resin, CRC, 0.3AUP, are shown collectively in 0.7AUP, marking to each measuring Chemie King prevent removal efficiency and vortex time].

Comparative Example 1: Preparation of Superabsorbent Polymer

A super-absorbent resin of the comparative example 1 in the same manner as in Example 4 except that no additional alumina is added to the product of the surface cross-linking was prepared. These and to the permeability of the water-absorbent resin, CRC, 0.3AUP, 0.7AUP, anti-caking efficiency, and a vortex time comes to remove each of the measurement are shown collectively in Table 1.

Comparative Example 2: Production of super-absorbent resin

In the base resin, 150g of a powder B obtained in Production Example 2 in a high speed mixer and eu obtain a surface cross-linking solution with the following composition.

With respect to the base resin powder surface cross-linking solution is 3.7% by weight of water, methane and 4% by weight, polyethylene glycol diglycidyl ester [(EX810) 0.03% by weight eu

Polycarbonate was common in the sum of the polymer of 0.05% by weight.

Add this solution to the surface cross-linking the high-speed mixer and stirred for 30 seconds at 400rpm. Since, 140 ° was a surface cross-linking for 35 minutes at banung C.

These high to respectively measure the permeability of the water-absorbent resin, CRC, 0.3AUP, 0.7AUP, anti-caking efficiency, and eliminate vortex time are shown collectively in Table 1.

Comparative Example 3: Preparation of Superabsorbent Polymer

In the surface cross-linking solution composition, with respect to the base resin powder, aluminum sulphate (A1 2 (S0 4 a) 23% aqueous solution instead of aluminum tri-lactate 22 compared to the same manner as in Example 1 except that the% aqueous solution of Example 3 and to prepare a water-absorbent resin.

These high to respectively measure the permeability of the water-absorbent resin, CRC, 0.3AUP, 0.7AUP, anti-caking efficiency, and. Vortex removal time are shown collectively in Table 1.

[Table 1]

Referring to Table 1, the embodiment of super-absorbent resin of Comparative Example and the ability to absorb at least the same level (CRC and AUP) and absorption rate, indicating a (vortex removal time) also, and more excellent tube-component (permeability) and caking i prevention It is confirmed as indicating the efficiency.

Claim

Water-soluble ethylenic base resin including a first cross-linked polymer of an unsaturated monomer having a powder at least partially neutralizing the acid; And

The resin powder is formed on the base, wherein the first cross-linked polymer containing a surface cross-linked layer and a second cross-linked polymer cross-linking the surface cross-linking agent is added to the medium - a superabsorbent resin,

Aluminum sulfate is dispersed in the surface cross-linked layer (Aluminum

Sul fate), and super-absorbent resin which comprises the alumina that are distributed on said surface cross-linked layer.

ί claim 2;

The method of claim 1, wherein the surface cross-linking agent is a superabsorbent polymer comprising one or more selected from the group consisting of a polyol compound, an alkylene carbonate compound and polyvalent epoxy compound.

[Claim 3]

The ' according to item 1, wherein the superabsorbent polymer further comprises alumina is dispersed in the surface cross-linked layer.

[Claim 4]

The method of claim 1 wherein the aluminum sulfate and the water-absorbent resin contained based on 100 parts by weight of the base resin powder, 0.02 to 0.3 parts by weight.

[5.]

The method of claim 1, wherein the alumina is a high water-absorbent resin contained based on 100 parts by weight of the base resin powder coming from 0.03 to 2 parts by weight.

[Claim 6]

The method of claim 1, wherein the following formula measuring method and a transmission rate of 10 to 80 seconds of the first calculation,

A physiological saline solution is centrifuged beam SAT (CRC) for half an hour on (0.9 weight percent sodium chloride aqueous solution) is 28 to 36g / g,

A physiological saline absorption capacity under pressure (0.3 Al] P) is 20 to 33g / g for 1 hour at a 0.3ps i on (0.9 weight% aqueous sodium chloride solution),

To formula (2) anti-caking efficiency of 75% to 100% of the super-absorbent resin:

[Equation 1]

Permeability (sec) = T S - T 0

In the formula 1,

Ts (unit: second) is 0. ¾ of the high absorbent resin 0.9% salt (NaCl) to swell for 30 minutes a solution saline-saline solution of the absorbent preparing a water-absorbent resin, and 0.9% under a pressure of 0.3psi the brine-means the time it takes to pass through the superabsorbent polymer absorption,

T 0 (in seconds) is the salt-refers to the time it takes for the saline solution of 0.9% transmission 0.3ps i under pressure without super-absorbent resin and absorbed.

[Formula 2]

Anti-caking efficiency (%) = [W 6 (g) IW 5 (g)] * 100

In the formula 2,

W 5 (g) is the initial weight (g) of the superabsorbent polymer. W 6 (g) are evenly coated and then the temperature 40土3 to diameter 10 cm flask dish ° upside down the flask dish on filter Pater After holding for 10 minutes in a constant temperature and humidity chamber for holding a C, humidity of 80 ± 3% level 3 a taping times (tapping) an amount of superabsorbent polymer falling (g) after.

[Claim 7]

The method of claim 6 wherein the superabsorbent polymer is removed vortex time of 25 to 35 seconds.

[8.]

The method of claim 6, wherein the saline solution absorption capacity of the superabsorbent resin is a pressure (AUP 0.7) of 10 to 25g / g for 1 hour at a 0.7ps i on (0.9 weight% aqueous sodium chloride solution).

[9.]

Water-soluble ethylenic base resin including a first cross-linked polymer of an unsaturated monomer having a powder sanseongga at least partially neutralized; And

A super-absorbent resin to the first cross-linked polymer is formed on the base resin powder, a cross-linked layer includes a surface including a second cross-linked polymer cross-linking a surface cross-linking agent is added to the medium,

Aluminum salt that is dispersed in the surface cross-linked layer and a-alumina which is dispersed on the surface cross-linked layer,

Formula 1 and methods to measure and calculate the transmission rate is 10 to 70 seconds, and, the anti-caking efficiency of the formula 2 75% to 100% super-absorbent resin:

[Equation 1]

Permeability (sec) = T S - T 0

In the formula 1,

Ts (unit: second) is a saline solution of 0.9% saline under the preparation of the salt eu absorbing superabsorbent resin to swell for 30 minutes and 0.2g of water-absorbent resin with 0.9% saline (NaCl) solution, and i pressure 0.3ps - meaning the time it takes to pass through the absorption super-absorbent resin,

To (in seconds) is the salt-refers to the time it takes for the saline solution of 0.9% transmission 0.3ps i under pressure without superabsorbent polymer absorption, and

[Formula 2]

Anti-caking efficiency (%) = [W 6 (g) IW 5 (g)] * 100

In the formula 2,

W 5 (g) is the initial weight (g) of the superabsorbent polymer and, W 6 (g) is a constant temperature and humidity keeping then evenly applied to the diameter 10 cm flask plate temperature 40 ± 3 ° C, humidity 80 ± 3¾ level 10 minutes after which the filter plate to turn over the flask three times Pater taping (t apping) amount (g) a super-absorbent resin falls in the chamber and then held there for.

[10.]

In the presence of an internal crosslinking agent, to form a hydrogel polymer comprising a first cross-linked polymer by polymerizing a water-soluble cross-linked ethylenically unsaturated monomer having at least partially neutralized acid;

Forming a function of the gel polymer dried, pulverized and classified to a base resin powder;

In the presence of a surface cross-linking solution containing aluminum sulphate and a surface cross-linking agent, said method comprising the surface cross-linked by heating a base resin powder to form a water-absorbent resin particles; And

Method for producing a superabsorbent resin to said high including the common dry summing step alumina in the water absorbent resin particles.

[Claim 111

11. The method of claim 10 wherein the water-soluble ethylenically unsaturated monomer is acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, crotonic acid , and itaconic acid, ethanesulfonic acid one by one ethanesulfonic acid, 2-methacryloyloxyethyl 2-acrylic, 2 - (meth) acid, or 2- (meth) acrylamide-2-methyl-negative Lee Eun-sung monomer and its salt of the sulfonic acid with an acrylic; (Meth) acrylamide, N- substituted (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methoxy polyethylene glycol (meth) acrylate or polyethylene glycol ( meth) non-ionic hydrophilic monomers containing acrylate; And (Ν, Ν), - dimethylaminoethyl (meth) acrylate or . (Ν, Ν) - dimethylaminopropyl (meth) an amino group-containing unsaturated monomer and its quaternary products of acrylamide; method of producing a superabsorbent polymer containing at least one selected from the group consisting of.

[12.]

The method of claim 10 wherein the internal cross-linking agent is a bis (meth) acrylamide, poly (meth) acrylate and polrieul poly (meth) allyl ethers of 2 to 10 carbon atoms of 2 to 10 carbon atoms polyol having 8 to 12 method for producing a superabsorbent polymer containing at least one selected from the group consisting of.

[13.]

11. The method of claim 10, wherein the base resin powder A method of manufacturing a super-absorbent resin to be pulverized and classified to have a particle diameter of 150 to 850μηι.

[14.]

11. The method of claim 10, wherein the surface cross-linking agent is a process for producing a superabsorbent polymer containing at least one selected from the group consisting of polyol compounds alkylene carbonate compound and polyvalent epoxy compound.

[15.]

The method of claim 10, wherein the method for manufacturing a super-absorbent resin to the surface crosslinking solution further comprises alumina.

[16.]

The method of claim 10, wherein the method for manufacturing a super-absorbent resin to the surface crosslinking solution further comprises a thermal initiator or a discoloration preventing agent.

[17.]

11. The method of claim 10, wherein the surface cross-linking step is the production of super-absorbent resin to be conducted at a temperature of 100 to 180t for 10 minutes to 60 minutes.