This application claims the benefit of priority based on the 10-2016- No. 0,178,407 patent to Korea in December 2016 and dated March 23, all the information described in the literature of the Korea patent application is included as part of the specification

The present invention and showing a solid addition to the basic absorption performance, improved absorption rate and the barrel-component relating to the water-absorbent resin and a production method thereof.

[Background Art]

The superabsorbent resin (Super Absorbent Polymer, SAP) is the group l 'C ¾ as a synthetic polymeric material having the ability to absorb 500 to about a thousand times the water of its own weight ), SAM (Super Absorbency Material each isomer), and each naming a different name, such as AGM (Absorbent Gel Material). Superabsorbent polymer as described above for starting to be put to practical use as a sanitary fittings, currently freshness at Children diapers, etc. sanitary ware in addition to horticultural soil repair filler, civil construction index material, a nursery sheet products for distribution areas first, and fomented It is widely used as a material such as.

The in many cases, there Such super-absorbent resin is widely used in hygienic material fields, such as diapers and sanitary napkins, for this purpose it is necessary to exhibit a high absorption capacity for such as moisture, should have absorbed moisture to an external pressure not get out, and in addition, it is necessary to exhibit excellent liquid cylinder (permeability) to absorb and maintain water in the form of volume expansion of (swollen) state.

Recently, in accordance with the demand for thin diaper becomes higher, they tend to increase the proportion of the water-absorbent resin in the diaper. Therefore, there is a need for a water-absorbent resin was combined with the performance of the fiber material is in charge of the diaper, the high absorption capacity of the water-absorbent resin to this, as well as to have a high absorption rate and the barrel-component. ■

In the manufacture of water-absorbent resin, generally it requires a step of crushing the hydrogel prepared by polymerizing a monomer of the water absorbent resin. Inde pulverizing the hydrogel is a process necessary for the production of water-absorbent resin and a powder or granular form, the process has a great influence on the physical properties of the superabsorbent polymer.

This has been in progress for a variety of research, Japan Patent No. 3415036 No. For example was disclosed a method of minimizing damage to the hydrogel during hydrogel crushed to reduce the number of components for causing a reduction in the absorption ratio. However, it is insufficient for a high absorption capacity as possible in the method to obtain, absorption rate of the level required in recent diaper.

As another example, in the PCT-JP201 1 -058829, but by controlling the gel pulverization energy, to achieve a high absorption rate in this case was a basic absorption capacity, for example, disadvantages which, under pressure / no pressure and absorption capacity is decreased.

This because, while maintaining the excellent performance of the underlying absorption, absorption magnification. And the liquid absorption rate through improved and developed technology that enables the delivery of water-absorbent resins have been continually required.

[Detailed Description of the Invention]

[SUMMARY]

The present invention is not only excellent in the basic absorption performance, and to represent the improved absorption rate and the barrel-component such as provide an absorbent resin and a production method thereof.

[Technical Solution]

The present invention is a water-soluble ethylenically unsaturated monomer having at least some of the neutralizing acid , the first base resin powder containing a cross-linked polymer; And it is formed on the base resin powders, as a superabsorbent polymer comprising the first surface cross-linked layer includes a second cross-linked polymer has 1 cross-linked polymer is added to cross-link the surface cross-linking agent as a medium, physiological saline (0.9 weight 0 / 0 . and 20cm absorption magnification (FHA) is 22.5g / g to 29g / g fixed height for teureum chloride or an aqueous solution), saline solution (0.685 parts by weight 0 / 0 flow induced (SFC) of 35 (in NaCl solution) - 10 - 7 cm 3 and -s / g) or more, under a pressure of 0.3psi, the superabsorbent resin 1 g of 0.9 weight 0 / sodium chloride and 0.01 0 / 0 absorbing rate aqueous solution 20 g Ethoxylated alcohol having a carbon number of 12 to 14 it takes to

The T-20 representing the time and providing a super-absorbent resin more than 180 seconds. The invention also, in which the way of another example, at least a water-soluble ethyl butene-based resin comprising a first cross-linked polymer of an unsaturated monomer having a powder partially neutralized acid of the water-absorbent resin; And it is formed on the base resin powder, the first as a super-absorbent resin to be cross-linked polymer comprises an additional crosslinking of the surface cross-linked layer includes a second cross-linked polymer to the surface cross-linking agent into the medium of normal saline solution (0.9 weight 0 /. and aqueous sodium chloride solution) absorption magnification (FHA) is 22.5g / g to 29g / g 20cm fixed height to physiological saline (0.9 wt. 0 / 0 centrifugation beam SAT (CRC) for half an hour on teureum chloride or aqueous solution) the 26 g / g to about 34g / g, and the physiological saline solution (0.685 parts by weight 0 / 0 induced (SFC), flow of aqueous sodium chloride solution) is 35 (- 10- 7 cm 3 -s / g) and more, the super-absorbent resin 1 g this provides a super-absorbent resin is a rate (FSR, free Swell rate) is 0.25 g / g / s to 0,40 g / g / s at the time of absorbing 0.9 g 20% by weight aqueous solution of sodium chloride.

In addition, the present invention comprises the steps including a first cross-linked polymer by cross-linking polymerization of the water-soluble ethylenically unsaturated monomer having in the presence of an internal crosslinking agent, at least an partially neutralizing acid to form a hydrogel polymer having a gel strength of at least 10000Pa; The method comprising the gel strength after the grinding function of the gel polymer gel to be ground to a 35% to 95% of the gel strength before the cutting; Forming a gel-pulverizing the dried hydrogel polymer increases, pulverized and classified to a base resin powder; And in the presence of a surface cross-linking agent, and including the step of heat treating the high and to the base resin powder surface cross-link the water-absorbent resin particles provides a method for producing a water-absorbent resin.

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, it is to be presented as an illustration of the invention and thus is not limited by the scope of the invention, it is apparent to those skilled in the art are possible are various modifications to the embodiments within the scope of the invention.

Addition of the addition, the specification also special la mention a "contains" or "containing", it is not in full; refers to including without limitation any component (or components) and the other component (or components) It can not be interpreted to exclude.

According to one embodiment of the invention, the water-soluble ethylenically unsaturated monomer and a base resin powder including a first cross-linked polymer having at least part of the neutralization acid; And is formed on the base resin powder, the low a superabsorbent polymer comprising a surface cross-linked layer M crosslinked polymer with additional crosslinking of the second cross-linking increases coalesces surface cross-linking agent as a medium, physiological saline (0.9 weight 0 / 0 is a chloride or an aqueous solution teureum) 20cm absorption magnification (FHA) is 22.5g / g to 29g / g fixed height to, physiological saline (0.685 weight zero inductive (SFC) of the flow / sodium chloride solution) 35 (- 10 " 7 cm 3 and -s / g) or more, under a pressure of 0.3psi, the superabsorbent resin 1 g of 0.9 wt. 0 /. sodium chloride and 0.01 wt. 0 /. absorb alcohol eteuk salicylate solution 20 g of a carbon number of 12 to 14 the superabsorbent resin T-20 is less than or equal to 180 seconds indicating the amount of time that is available.

Depending on the ongoing experiments, the production method to be described later of the present inventors, by controlling the cross-linking polymerization conditions to obtain a hydrogel polymer having a high gel strength, to control the counter, grinding conditions a gel strength after the gel crushing to maintain a suitable range If one then, and after the subsequent process for producing the water absorbent resin, it was confirmed that the absorption capacity of the basic, as well as solid, liquid tube and the absorption rate can be greatly improved and the manufacture and provide a water-absorbent resin and completed the invention.

That is, by default, the gel strength is gained high hydrogel polymer, a gel, these functions, as the gel strength of the gel polymer to adjust the gel pulverization conditions to be maintained above a certain level, the base resin powder relative to exhibiting a high gel strength after grinding and it can be provided with a water-absorbent resin. Accordingly, one embodiment the superabsorbent resin can exhibit excellent liquid tube and, under pressure, such as excellent absorption performance, such as pressure, suction force, which is defined by a high FHA is defined by a relatively high SFC.

Further, by the gel crushing proceeds, since the number of the contained is large, the surface area pore base resin powder and the super-absorbent resin can be obtained, an implementation example super-absorbent resin, for example, physical properties such as the T-20 this was confirmed that can exhibit an enhanced absorption rate than that defined by the.

In addition, after obtaining the hydrogel polymer having a high gel strength, by default, in accordance with the control gel pulverization conditions maintaining the gel strength after grinding a certain level, one embodiment obtained through this method, the superabsorbent resin is a manufacturing process the number can reduce degradation of the performance of the generation and absorption in components for.

Accordingly, one embodiment is a super-absorbent resin, yet maintaining the excellent performance of the basic absorbent, and can exhibit such improved absorption rate and the barrel-component, it can be preferably applied to the diaper such as sanitary material having a thinner thickness.

Hereinafter, one embodiment that will be described in more detail on the water-absorbent resin.

The "superabsorbent resin" as referred to herein refers to a base resin powder comprising at least a first cross-linked polymers of water soluble ethylenically unsaturated monomer having a partially jeunghwa acid; And that means the water absorbent resin which is formed on the base resin powder, including the first cross-linking increases the surface cross-linked polymer layer that contains the second cross-linked polymer cross-linking a surface cross-linking agent is added to the medium.

The water-soluble ethylenically unsaturated monomer and may be any monomer that is commonly used in the manufacture of a water-absorbent resin. Non-limiting examples of the water-soluble ethylenically unsaturated monomer may be a compound represented by the following general formula (1):

[Formula ¾ Equation 1]

RrCOOM1

In the formula 1,

^ Is an alkyl group of 2 to 5 carbon atoms including an unsaturated bond,

M 1 is a hydrogen atom, or one divalent metal, an ammonium group or an organic amine salt. Suitably, the monomer may be at least one member selected from acrylic acid, methacrylic acid, and monovalent metal salts of these acids, the group consisting of a divalent metal salt, ammonium salt and organic amine salt. Thus, when using an acrylic acid or a salt of a water-soluble ethylenically unsaturated monomer advantageously superabsorbent improved to obtain a water-absorbent resin. In addition, one-propanesulfonic acid in the monomer to maleic anhydride, fumaric acid, crotonic acid, itaconic acid, ethanesulfonic acid one by one ethanesulfonic acid, 2-methacryloyloxyethyl 2-acrylate, 2- (meth) acrylate, or 2- ( meth) anionic acrylamide-2-methylpropanesulfonic acid monomer and its salts; (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) acrylamide, amino group-containing unsaturated monomers and their quaternary product of; use one or more selected from the group consisting of can.

Here, the water-soluble ethylenically unsaturated monomer having an acidic group, may be at least partially neutralizing the acid groups. Preferably it is used which is partially neutralized the monomers with an alkali substance such as sodium hydroxide, kalreum hydroxide, ammonium hydroxide.

In this case, the neutralization degree of the monomer is 40 to 95 mole 0 / 0 , or 40 to 80 mol%, or 45 to 75 mole 0 may be a /. Range of the degree of neutralization is can vary, but the neutralization degree of the precipitation is too high, the neutralized monomer, depending on the end properties may be difficult to jeunghap progresses smoothly, whereas if the degree of neutralization is too low as to fall the absorption capacity of the polymer largely not treated It can be represented by properties such as hard rubber.

The "first crosslinked polymer" means, means exist to crosslinked materials, meaning that the polymerization, including "the 'base resin powder, Aranda, this first crosslinking increases polymer of the above-described water-soluble ethylenically unsaturated monomer, the internal cross-linking agent do. In addition, the means to add a cross-linked material, a second cross-linked polymer "refers to a parameter of the first cross-linked polymer and the surface cross-linking agent, so that there is formed on the base resin powder. It will be described later to the surface cross-linking agent.

One embodiment is a super-absorbent resin excellent in absorption ratio, and the whole liquid absorption rate, which can be defined by the physical properties such as CRC, FHA, SFC, Τ-20 or FSR.

Specifically, in one embodiment the superabsorbent resin is a saline solution (0.9 weight 0 /. Aqueous sodium chloride solution) are at a 26 g / g centrifugation beam SAT (CRC) for half an hour to, preferably 26.5 g / g or more It is, or 27.0 g / g or more. CRC is sutok geotyieoseo superior to that upper limit is higher that value, but is 34 g / g or less, 32 g / g or less, 30 g / g or less, or 29.5 g / g or less, for example. Centrifugation beam SAT (CRC) for the physiological saline solution is then absorbed by the saline solution through the superabsorbent polymer in 30 minutes can be calculated by the following formula 1 of:

[Equation 1]

CRC(g/g) = {[W2(g) - W^g) - W0(g)]AA/0(g)}

In the formula 1,

W 0 (g) is the initial weight (g) of the superabsorbent resin,

W ^) is a weight measured after one and then impregnated for 30 minutes in physiological saline for non-woven fabric bag not loaded the water-absorbent resin at room temperature, dehydrated by using a centrifuge 3 minutes at 250G,

W 2 (g) is a weight measured after one and after the non-woven fabric into an envelope an absorbent resin impregnated for 30 minutes in physiological saline at room temperature, dehydrated by using a centrifuge 3 minutes at 250G.

In addition, one super-absorbent resin according to the embodiment is under pressure of 0.3psi physiological saline (0.9 Increased 0 / 0 aqueous sodium chloride solution) was absorbed in 1 time measuring 20cm a fixed height absorption magnification (FHA) is 22.5g / g or more and , preferably 23g / g or more, 23.5 g / g or more, or 23.7 g / g and be at least, limit, but the upper limit, 29 g / g or less, 27 g / g or less, or 26 g / g for example or less. The FHA may be measured and calculated by the method described in the 7,108,916 patent of U.S. deungtyu example.

The FHA may define high pressure, the attractive force indicated by the example super-absorbent resin one embodiment, one embodiment the superabsorbent resin as comprising a base resin powder relative maintaining a high gel strength, excellent FHA and thus defined by which can exhibit excellent absorption performance under pressure.

Further, one embodiment the superabsorbent resin is physiological saline solution (0.685 parts by weight 0 /. Sodium chloride aqueous solution Room) inducing flow of the property (SFC, 1 (r 7 cm 3 .s / g) of 35 or more, preferably at least 40 , at least 45, or at least 47. SFC is, but is limited to the upper limit, for example a 150 or less, 140 or less, 130 or less, 100 or less, or 80 or less. induction the saline flow ability (SFC) is from before the person skilled in the art methods well known to, for example, can be measured and calculated according to the method disclosed in U.S. Patent No. 5,562,646 deungteuk arc column 54 to column 59.

The water-based resin is gohop atda, can exhibit excellent liquid transfer property is more improved SFC bucket and thus by definition, as a base resin powder comprises maintaining a high gel strength and, in the surface cross-linkage proceeds to contain the surface cross-linked layer.

Then, the example super-absorbent resin is one implementation. Under pressure of 0.3psi, and a water-absorbent resin is 1 g of sodium chloride and having a carbon number of 12 to 14 T-20 represents the time required to absorb the alcohol eteuk salicylate solution 20 g of less than 180 seconds, up to 170 seconds or less 160 seconds . T-20 is a restriction on the lower limit, but is less than 80 seconds in one example, over 90 seconds, 100 seconds, or longer than 120 seconds. The T-20 was, of 9 g of sodium chloride in distilled water to 1 L (0.9 wt. 0 /.) And 0.1 g of Lorodac (main component: alcohol ethoxylate of the linear carbon atoms of 12 to 14, CAS # 68439-50-9) (0.01 weight 0 to create an aqueous solution obtained by dissolving a /.), under pressure of 0.3psi and has water-absorbing resin 1 g can be calculated and measured as the time required to absorb these aqueous solution of 20 g. Specific measuring method of T-20 is described in detail on page 18, beginning on page 13 of heading European Patent Publication No. 2,535,027.

One embodiment superabsorbent polymer is a hydrogel polymer ≤ gel pulverization conditions optimized in the manufacturing process, may include a base resin powder having a large specific surface area. Therefore, the super-absorbent resin can exhibit an improved rate of absorption than those previously known.

Further, one embodiment the superabsorbent resin, and a water-absorbent resin 1 g of 0.9 weight 0 and / speed at the time of absorbing chloride or teureum aqueous solution of 20 g (FSR, free Swell Rate) is 0.25 g / g / s or more, preferably 0.27 g / g / s or higher, 0.28 g / g / s or more, or 0.29 g / g / s or more. The FSR is limitation but the upper limit, for example 0.40 g / g / s or less, 0.39 g / g / s or less, 0.38 g / g / s or less, 0.37 g / g / s or less, or 0.36 g / g / s or less.

The FSR range and also illustrating one implementation it is possible to define a high absorption rate indicated by the water-absorbent resin.

On the other hand, in the super-absorbent resin mentioned above one embodiment, the base resin powder, a first cross-linked polymer is teurimetilreul tri (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate contained in the , propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butane diol di (meth) acrylate, butylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, nucleic acid di (meth) acrylate, triethylene glycol di (meth) acrylate,

Tree of propylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, di-penta the EPO Li from the group consisting of the penta-acrylate, glycerol tri (meth) acrylate and penta-EPO to tetraacrylate selected polrieul poly (meth) acrylate-based first internal cross-linking agent; And an allyl (meth) acrylate 2 in the presence of an internal crosslinking agent, the monomer may be polymerized as a crosslinked polymer. By the application of more of these two kinds of particular internal cross-linking agent, an implementation example super-absorbent resin will contain a base resin powder after proceeding the like gel, crushing and grinding, maintaining a high gel strength, and therefore, more excellent tube-component and pressure, may exhibit such as absorption performance.

The above-described one embodiment and the water absorbent resin may have a particle size of 150 to 850 i. More specifically, the base resin powder and at least 95 parts by weight of the superabsorbent polymer, including this 0 / 0 or more has a 150 to 850 diameter, 150 / the derivative has a particle size of ηι less than 3 parts by weight 0 /. To be less than have.

On the other hand, and to meet the various properties embodiment described above one embodiment the water absorbent resin is cross-linked junghip , the condition is after the obtained hydrogel increases polymer showing a higher gel strength jokkeol, is adjustable, such as gel pulverization condition is gel strength after pulverization constant oil level can be finally made by ^ a particular production method.

According to another embodiment of the invention, there is provided a method of manufacturing the above-mentioned super-absorbent resin. This manufacturing method comprises the steps of including a first cross-linked polymer in the presence of an internal cross-linking agent, by cross-linking polymerization of the water-soluble ethyl butene unsaturated monomer having at least some of the neutralizing acid to form a hydrogel polymer having a gel strength of at least 10000Pa; The method comprising the gel strength after the hydrogel polymer pulverized be increased gel crushed to 35% to 95% of the gel strength before the cutting; The gel is comminuted function drying the polymer gel, thereby forming a crushing and classifying to a base resin powder; And in the presence of a surface cross-linking agent, and by heat treatment as a base resin powder surface cross-linking may include the step of forming a water-absorbent resin particles.

Hereinafter, the production method in detail for each step.

First, a different implement the manufacturing method includes forming a hydrogel polymer by increasing the cross-linking polymerization. Specifically, the monomer to the composition in the presence of an internal cross-linking agent comprises a water-soluble ethylenically unsaturated monomer and a polymerization initiator, a thermal polymerization or photo-polymerization to form a hydrogel polymer.

Water-soluble ethylenic unsaturated monomer contained in the monomer composition are as previously described.

Further, the monomer composition may include a polymerization initiator commonly used in the production of superabsorbent polymer. Non-limiting examples of the polymerization initiator include thermal polymerization initiator or a photopolymerization initiator may be used in accordance with the polymerization method. However, even in light of jeunghap method, since the amount of heat generated by UV irradiation, and further a certain amount of heat generated with the progress of polymerization heat generation banung banung, may be included to add a thermal polymerization initiator.

Here, the photopolymerization initiator is, for example, benzoin ethers (benzoin ether), di-alkyl acetoacetate jjenon (dialkyl acetophenone), hydroxyl-alkyl ketones (hydroxyl alkylketone), phenyl glyoxylic rate (phenyl glyoxylate), benzyl dimethyl ketal (Benzyl Dimethyl ketal), acylphosphine (acyl phosphine) and alpha-wherein the at least one compound selected from the group consisting of amino Kerron (a-aminoketone) may be used. " In an embodiment of the authentication acylphosphine commercial iucirin TPO, i.e., 2,4,6-trimethyl-to-benzoyl-trimethyl phosphine oxide is used, (2,4,6-trimethyl-benzoyl-trimethyl phosphine, oxide) can. Wider range of light Reinhoid Schwalm book, with respect to the polymerization initiator: is disclosed in "UV Coatings Basics, Recent Developments and New Application (Elsevier 2007 year)" of the first page 15, and can refer to it.

Further, the heat polymerization initiator and has a sulfate-based initiators, azo initiators, hydrogen peroxide, and at least one compound selected from the group consisting of ascorbic acid may be used. Specifically, the persulfate-based initiator and sodium sulfate (Sodium persulfate; Na 2 S 2 0 8 ), potassium persulfate (Potassium persulfate; K 2 S 2 0 8 ), ammonium persulfate (Ammonium persulfate; (NH 4 ) 2 s 2 0 8 are exemplified, and so on). Further, azo (Azo) based initiators include 2,2-O Jovi 'Bus - (2-amidinopropane) dihydrochloride (2,2-azobis (2-amidinopropane) dihydrochloride), 2,2- azobis (Ν, Ν- dimethylene) isobutoxy Thira Mai Dean dihydrochloride (2, 2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride), 2- (carbamoyl-azo) isobutyronitrile (2- (carbamoylazo) isobutylonitril), 2,2- azobis [2- (2-imidazolin 2-yl) propane] dihydrochloride (2,2-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride), 4,4 eu-azobis- (4-cyano ballet rigs acid) ( 4,4-azobis (4-cyanovaleric acid)) the like are exemplified. Than it is disclosed in page 203 of "Principle of Polymerization (Wiley, 1981 year)" which is Odian book for various thermal polymerization initiator, and can refer to it.

The polymerization initiator is from about 0.001 to 1 parts by weight based on the monomer composition 0 / 0 may be added at a concentration of. That is, when the concentration of the polymerization initiator is too low and may slow the rate of polymerization is not preferable because it can be residual monomers are extracted in a large amount in the final product. On the other hand, it is not preferable because the resin properties such as the concentration of the polymerization initiator over the content of the component for the number becomes the polymer chains that make up the network shorter increased at higher pressure that water absorption capacity is reduced can be lowered.

On the other hand, the monomer composition includes a cross-linking agent ( "internal crosslinking agent") to improve the physical properties of the composition according to the polymerization of the water-soluble ethylenically unsaturated monomer. The cross-linking agent as for the internal cross-linked hydrogel polymer, can be used separately from the "surface cross-linking agent" to be described later.

Tokhi, in the other embodiment Sejo method, amido described above in combination of two or more ^ internal cross-linking agent, e.g., a poly (meth) acrylate-based first internal crosslinking agent, and allyl (meth) acrylate-based second internal cross-linking agent of polrieul using a combination, the higher gel strength, e.g., 10000Pa or higher, or 1 1000Pa or more, or is more than 120000Pa, in particular but not limited to a function having a gel strength of 50000Pa, alternatively no more than 40000Pa, alternatively no more than 38000Pa below the gel increased polymer the can get.

More specifically, the first internal cross-linking agent, teurimetilreul tri (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butane diol di (meth) acrylate, butylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, acid dayieul di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate,

Die penta and the EPO Li can be used at least one selected from the group consisting of the penta-acrylate, glycerol tri (meth) acrylate and penta-EPO to tetraacrylate, and the second internal cross-linking agent is allyl methacrylate or allyl It may be used, such as acrylate.

Further, the first internal cross-linking agent is the internal cross-linking agent and a monomer of 0.4 increase parts to 1 parts by weight based on the total 100 parts by weight of the monomer composition, or the like, or 0.5 increased portion to 0.9 increased portion, or 0.6 to lead 8 parts by weight of It may be included in an amount, and the second internal cross-linking agent may be included in an amount of 0.008 part by weight to 0.5 parts increase, or 0.01 to 0.1 part by weight, or from 0.01 to 0.05 parts by weight based on the total 100 parts by weight of the monomer composition. Thus, for adjusting the composition such as type and quantity range of the internal cross-linking agent other hand, as the control of water content of below hydrogel polymer, it is possible than to obtain effectively the hydrogel polymer indicates the gel strength of at least 10000Pa, an implementation that meets the example Physical properties and it can more effectively achieve a water-absorbent resin. However, the larger the amount of the internal cross-linking agent is too, can be a basic absorption performance of the super-absorbent resin decreases.

In addition, the monomer composition has an additive such as a thickener, a plasticizer, a preservation stabilizer, an antioxidant can be further included if necessary.

Then, this monomer composition can be a raw material such as the above-described monomers, jeunghap initiator, an internal crosslinking agent prepared in the form of a solution dissolved in a solvent.

At this time, a usable solvent as long as it can dissolve the above-described raw materials may be used without any limitation in its configuration. For example, as the solvent is water, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butane dieul, propyl ten 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, butyrolactone, carboxamide ratio of methyl cells may be used, such as cellosolve acetate, Ν, Ν--dimethylacetamide, or mixtures thereof.

And, forming a hydrogel polymer by polymerization of the monomer composition can be carried out in a conventional polymerization process, the process is not particularly limited. Non-limiting examples, the polymerization process is divided into large thermal polymerization and photo polymerization according to the type of the polymerization energy source, if the progress of the thermal polymerization may take place in half unggi with axis agitation, such as a kneader (kneader), light when proceeding the polymerization it may take place in a half unggi provided with a movable conveyor belt.

For example, it is possible to half unggi such as a kneader equipped with an agitator shaft to obtain a hydrogel polymer by charging, and a thermal polymerization by supplying hot air or heating in an banung exciting the monomer composition. At this time, depending on the form of a stirring shaft provided with a reactor hydrogel polymer discharged from the reactor outlet may be obtained with particles of a few millimeters to several centimeters. Specifically, the hydrogel polymer is obtained may be obtained in various forms, there is a normal (average increase) the particle diameter is 2 to 50 mm hydrogel polymer can be obtained depending on the concentration and the injection rate of the monomer composition to be injected.

And, one another example, if the progress of photopolymerization of the monomer composition in the movable half unggi provided with a conveyor belt has a hydrogel polymer in the form of a sheet can be obtained. In this case it is the thickness of the sheet may vary depending on the concentration and the injection rate of the monomer composition to be injected, to the entire sheet evenly to ensure the production speed, etc., yet to be jeunghap, which typically jokkeol to a thickness of 0.5 to 10 cm desirable.

This hydrogel polymer is formed in the same manner is increased 38 to 60 0 / 0 , or 40 to 55 weight 0 / 0 may have a moisture content of. Here, the water content is a weight occupied by the water on the total weight of the hydrogel polymer, it may be a value obtained by subtracting an increase of the dry polymer from the weight of the hydrogel polymer. More specifically, it can be defined as the value calculated by measuring the weight decrease due to evaporation of water in the polymer increases in the course of heating up through infrared drying the temperature of the polymer. At this time, the drying conditions after 180 raising the temperature from room temperature to about 18CTC ° by total drying time in such a manner as to maintain the C comprises five minutes the temperature rising step can be set to 20 minutes.

The function is controlled by the water content of the above-mentioned range of the gel polymer it may, as well as the previously described gel before pulverized gel strength than 10000Pa may be achieved more effectively, be carried out after the gel crushing effectively. Specifically, the above water content is added to the hydrogel polymer is a gel-crushing device at the jokkeol state, the gel pulverization conditions to be described later in accordance with the regulated, as well as a high gel strength range before the gel crushing may be achieved more easily, the gel strength after the gel crushing is able to be maintained at 35% to 95% of the gel strength before the cutting, or 50% to 90%, or 60% to 88%. As a result, the base resin powder and a high-spreads the high internal surface area of ​​the water-absorbent resin comprising the same water-absorbent resin is also, that the base resin powder and a superabsorbent polymer maintains a high strength while exhibiting an excellent absorption rate exhibit such excellent tube-component It can be so.

On the other hand, after forming a gel polymer by the above-described functions are cross-linked polymerization, the gel crushing the hydrogel polymer of the water content is controlled. The pulverized gel can proceed the gel strength after grinding so that 35% to 95% of ¾ strength before grinding. In a specific example, clearing up the gel strength after crushing may be as 5000Pa to 30000Pa, or 10000Pa to 28000Pa, This allows one may be that to meet the physical properties of the embodiment effectively obtained than the water absorbent resin.

In the gel pulverization step, the grinder to be used is, but is limited to the configuration. Specifically, a vertical cutter (Vertical pulverizer), turbo cutter (Turbo cutter), a turbo grinder (Turbo grinder), rotary cutting mill (Rotary cutter mill), cutting mill (Cutter mill), disc mill (Disc mill ), fragment crusher (Shred crusher), crusher (crusher), the chopper (chopper) and one-plate type cutting (but may include any one selected from the crushing device group consisting of Disc cutter), but is not limited to the above example .

On the other hand, the gel pulverization of the hydrogel polymer, there is the shear force and the compressive force applied to the functional gel polymer action, as in other implementations the manufacturing method jokkeol these gel pulverization conditions, achieve a gel strength range after the above-described ¾ grinding can do.

More specifically, the gel crushing may be carried out inside the grinder containing an extruder equipped with a perforated plate such as a screw-type extruder therein. At this time, the plurality of the diameter of 9 to 18mm, 10 to 15mm or holes formed in the perforated plate

Have to, this is through the perforated plate and the extruder may be carried out to a gel pushing the pulverized hydrogel polymer. This allows, the function mozzarella polymer gel after grinding proceeds to maintain an appropriate level of gel strength, yet, the gel polymer is crushed effectively after the crushing are able to have a large surface area.

In other words, when proceeding to the grinding process described above the gel, it is the surface area of ​​the milled hydrogel polymer significantly increased. Specifically, it is in the comminuted hydrogel polymer, the ratio of the number of blood shear particles of 0.40 or more 0.95 or less. The "blood shear particle" means, a means for three or more particles having a depth of 10 or more recesses or pores observed on the milled hydrogel increases polymer particles, and the 'blood ratio of the number of shear particle "means, pulverized hydrogel increase the total number of polymer particles prepared and the blood refers to the number of shear particles. May be blood shear particles are generated in physical properties such as the absorption rate of the water absorbent resin further improves the high-surface-area widened as described above, a superabsorbent polymer that meets one embodiment various physical properties can be produced more efficiently.

On the other hand, the hydrogel of the gel polymer is pulverized, the particle size of the hydrogel polymer may be performed such that 0. 1 mm to 10 mm. That is, the hydrogel polymer to an increase in drying efficiency is preferably ground to a particle of less than 10 mm. Hajimin ·, since excessive grinding when aggregation between particles may occur, the function ¾ increasing polymer is preferably ground to a gel than 0.1 mm particles.

In addition, the gel pulverization of the hydrogel polymer is increased, the water content may be due to relatively low performed on the surface of the gel appears, the grinder to stop sticking phenomenon hydrogel polymer increases. In order to minimize this phenomenon, if necessary, steam, water, a surfactant, ungjip agent (for example clay, silica and the like); Persulfate-based initiators, azo initiators, hydrogen peroxide, thermal polymerization initiator, an epoxy-based crosslinking agent, a diol (did) flow cross-linking agent, two functional groups, or three cross-linking agent of the first functional group containing a crosslinking agent, a hydroxyl group which is a functional group or more acrylate functional groups etc. may be added to the hydrogel polymer.

After the above-described gel pulverization, it is possible to dry the hydrogel polymer. The drying is 120 to 250 t ' can be carried out at a temperature of, preferably, 140 to 200 ° C, more preferably 150 to 190 ° C. At this time, the silver is dried may be defined in, or silver is the drying step of the thermal medium to be supplied for drying a drying temperature in the half unggi including a heat medium and a polymer. Since the process efficiency if the drying temperature is low, the drying time longer decrease, is preferably not less than drying The silver is 12 (C in order to prevent this. On the contrary, if the drying temperature is higher than necessary is dried excessively the surface of the hydrogel polymer subsequent there can be a loss of fine powder generation increases in the grinding process step, there are the physical properties of the final resin it can be reduced, and dry silver is preferably 25 (rc or less in order to prevent this.

At this time, the drying time in the drying step may be not particularly limited, in consideration of the physical properties of the process hyoeul and resin, to ¾ tank of 20 minutes to 90 minutes at the drying temperature.

The drying may be done using a conventional medium, for example, may be performed through a method such as the hot air supplied to the pulverized hydrogel polymer, infrared irradiation, microwave irradiation, or UV irradiation.

Further, these hinge construction is that the dry polymer amount of about 0.1 to 10 0, preferably carried out so as to have a water content of /. That is, the hamsueul of the dried polymer from 0.1% ! The decomposition (degradation) of the rise and cross-linking of the polymer increases Sejo cost due to excessive drying is not preferred it may occur is less than. And, if the hamsueul of the dry polymer more than 10% by weight is not preferable because it may cause a defect in the subsequent steps.

After the drying, it is possible to crush the dried polymer, may This allows the particle size and surface area of ​​the polymer can be adjusted to an appropriate range. The pulverization can be carried out the particle size of the pulverized polymer to MA 150 to 850?.

At this time, by using a crusher that can be used are conventional, such as pin mill (pin mill), a hammer mill (hammer mill), screw mill (screw mill), a mill (roll mill), disc mill (disc mill), a jog mill (jog mill) that the may be used.

In addition, the high end is commercialized in order to manage the physical properties of the water absorbent resin, the method comprising: selectively classified into particles having a particle diameter of 150 to 850 / mi in the polymer particles obtained through the pulverizing step may be further carried out.

On the other hand, the polymer particles (fine powder) having a particle size of less than 150 through the classification possible solvent used in the crosslinking polymerization step (e.g., such as water , it is possible to obtain a differential re-assembly by assembling a number of the solvent). The fine powder material assembly,

For example, added to a hydrogel polymer before drying between the hydrogel polymer increases, more specifically, the gel pulverization step immediately before to immediately after, and a drying step may be mixed.

The differential assembly may be re-heunhap to 100 parts by weight of 10 to 30 based on parts by weight, or a content of 15 to 28 parts by weight of the hydrogel polymer before the drying. Due to the additional input of this differential assembly member, and the internal surface area of ​​the base resin powder and the super-absorbent resin can be widened more, and a water-absorbent resin can exhibit a more enhanced rate of absorption. In addition, the control as a base resin powder and a suitable range and the strength of the water-absorbent resin by the differential input of the re-assembly of the above-described content range, there is an implementation example various physical properties can be achieved more effectively.

On the other hand, after the manufacture of the base resin powder through to the above-described classifying process it can be high in the presence of a surface crosslinking agent, and heat-treating the base resin powder surface crosslinking the water absorbent resin particles.

" The surface crosslinking is a second cross-linking agent in the presence of (surface cross-linking agent), said base number " to induce a crosslinking reaction on the surface of the powder upon, the surface of the surface-modified layer of the base resin powder from such a surface cross-linking (surface cross-linked layer ) it may be formed.

The surface cross-linking, for example, a can be carried out in a second cross-linking agent (surface cross-linked 1 I) was added and the combined common method of cross-linking reaction of the base resin powder containing.

Wherein the surface cross-linking agent may be used a compound as the functional group, and banung compound having the above-mentioned polymer, the alkylene carbonate compound or the polyhydric alkoeul, an alkylene carbonate having 2 to 5 is preferred. More preferably, as the surface cross-linking agent may be used ethylene carbonate. Further, with the surface cross-linking agent, it may be more such as silica (silica) and clay (clay) used. It is also possible to further add an acidic compound or a polymer or the like as needed to adjust the penetration rate and the depth of the surface cross-linking agent ¾.

At this time, the amount of the surface cross-linking agent may be suitably adjusted in accordance with Deng Ai type of crosslinking agent and the reaction conditions, preferably, the base resin powder 100 may be adjusted as part of 0.001 to 5 parts by weight relative to the weight section. When the too low amount of the surface cross-linking agent, a surface modification can not be achieved properly, the physical properties of the final resin can be lowered. Conversely an excess of the surface crosslinking agent is used because of the excessive surface cross-linking reaction is not preferable because the absorption capacity of the basic resin can be even reduced.

On the other hand, in the surface cross-linking step, wherein the surface cross-linking solution containing the surface crosslinking agent is joined into the base resin particles in the reaction tank common, a method of spraying a surface cross-linking solution containing the surface cross-linking agent to the base resin powder, the mixer being continuously operated at It was continuously supplied to a base powder and a resin, the surface cross-linking solution may be carried out by conventional methods such as methods common summing.

Further, the addition of water may be added upon the addition of the surface cross-linking agent. Thus, with the addition of the surface crosslinking agent with water and by being derivable a uniform dispersion of a surface cross-linking agent, it is possible to prevent the aggregation phenomena of the base resin powder it is, optimized than the penetration depth of the surface cross-linking agent to the base resin powder. Accounts for this purpose and effect, the amount of water added together with the surface cross-linking agent may be adjusted as part of 0.5 to 10 parts by weight per 100 parts by weight of the base resin powder.

In addition, the surface cross-linking step is from 100 to 250 ° can be carried out at a temperature of C. Further, the surface cross-linking may proceed for 1 to 120 minutes, preferably from 1 min to 100 min, more preferably from 10 minutes to 80 minutes. That is, in order to prevent the surface cross-linking reaction is induced, while the minimum excess banung when polymer particles damage the physical properties is reduced, the surface cross-linking step may be performed in the above-described conditions.

【Effects of the Invention】

Super-absorbent resin according to the present invention, yet can excellently maintain the basic ability to absorb, and can exhibit such improved absorption rate and the barrel-component, it can be preferably applied to the diaper such as sanitary material having a thinner thickness.

[Mode for Carrying out the invention]

Below, it is presented to a preferred embodiment for better understanding of the invention. However, the practice of the following examples are not intended to limit the invention to these may make to illustrate the present invention.

Example 1

And a manufacturing apparatus of the absorbent resin using a continuous production apparatus consisting jeunghap process, hydrogel milling step, drying step, pulverization step, the classification step, the surface cross-linking step, nyaenggak step, the classification step and the transporting step of connecting the respective steps It was.

(Step 1)

Into the cross-linking agent to the acrylic acid 100 parts by weight of polyethylene glycol diacrylate (weight-average molecular weight: ~ 500 g / mol) common IRGACURE 819 0.01 increase parts to 0.7 parts by weight (7000ppm) and allyl methacrylate 0.015 part by weight (150ppm) and a photoinitiator It was combined to prepare a monomer solution. Then, the above monomer solution was continuously fed to the metering pump, and at the same time 24 parts by weight 0 /. To prepare a monomer solution was continuously mixed by line portion 160 by weight aqueous solution of sodium hydroxide. At this time, the silver is increased by junghwayeol was adjusted to 40 ° C. In addition, after continuous in-line mixing unit 4 wt% sodium persulfate aqueous solution increased 6, having a weir at both ends , it was continuously fed to a continuous polymerization groups having a flat belt on jeunghap. After UV irradiation for 1 minute, and subjected to heat polymerization by 2-minute while to prepare a function ¾. The water content of such hydrogel was identified as 45% by weight.

(Step 2)

A (C also includes a perforated plate comprising a plurality of holes having a diameter of 1 1 mm) mill with the finely divided material assembly as the hydrogel with an average size shown in, Table 1, after kkeoldan is less than or equal to about 300 mm in, which was triturated with each condition. Here, the differential assembly material was used as a differential re-assembly manufactured in step 4, below, charge ratio of 20, based on the weight of the hydrogel 0 were as shown in Table 1 to a /.

(Step 3)

It was then drying the hydrogel pulverized in the above step 2 at a flow rate as possible transition to the upper and lower dryer. The water content of the dried powder is less than or equal to about 2% to flow upward from the bottom for 15 minutes a hot air (hot air) of 18C C and again 15 minutes to flow downward from above uniformly drying the hydrogel for It was.

(Step 4)

Crushing the dried resin from step 3 to a mill and then classified to 150 to 850 urn to obtain a base resin of the size. On the other hand, through the classifier by assembling the polymer particles having a particle size of less than 150 um with water, and used as a differential re-assembly of the above-mentioned two steps.

(Step 5)

It was then banung a base resin of 100 parts by weight, the following 180t 'combined common and cross-linker solution was washed with water four parts increased, common parts of ethylene carbonate for 40 minutes plus 1 increased surface cross-linking was prepared in four steps. And, classifying the particle diameter of 150 to 850 / zm of the surface cross-linking and to obtain a water-absorbent resin after cooling the resulting product.

Examples 2 to 8 and Comparative Examples 1 to 4

The same manner as in Example 1 except that, unlike as to have the holes of a perforated plate directly ¾, hamsueul function mozzarella, charge ratio of the fine material assembly having a content range, a gel pulverizer of internal cross-linking agent in Table 1 and summarized and it was prepared by the water-absorbent resin.

The following Examples 1 to 8 and in Comparative Examples 1 to 4, the gel strength of the hydrogel of the gel before and after the pulverization was measured using the methods summarized in the following, the measurement results are shown collectively in Table 1 together.

* How the gel strength of the hydrogel measured

A. Preparation of a measurement target sample method:

First, the diameter of the measurement object hydrogel (gel before pulverized hydrogel sheet and the gel after the crushing hydrogel) were prepared in about 2 ~ 5mm size: about 2.5cm, a thickness. 180ΐ: prepared ¾ flooding a microbalance, and using the spray was evenly spray the appropriate amount of distilled water (this time, by measuring the initial water content of the hydrogel in advance (water content measuring conditions " Fit, 40 minutes) to the initial water content It computes the amount of water needed.). ¾ to uniformly adjust the water content inside the sample, sealed in plastic and stored at 12 hours or more phases.

B. How to measure:

Loading the hydrogel sample of the water content is adjusted between two plates of a rheometer (ARES-G2), and the sample is pressed in the two plates of Messenger 3N doedo contact force both on the front plate of the gap was set. Rest Time was given to stabilizing the sample for 5 minutes. Increasing the strain in the first 10 rad / s frequency of the measurement is confirmed that Strain constant Linear Viscoelastic Regime interval Storage Modulus (G ') and the Loss Modulus (G ").

Find the Strain value (usually 0.1%) of Linear Regime interval, at a constant frequency (10 rad / s) for 60 seconds to measure the viscoelasticity (G eu, G "). After the measurement three or more times, and the average of the G eu the value was calculated as gel strength (G ')

TABLE 1

7 inside association Ρ / Α: polyethylene glycol diacrylate / allyl methacrylate

Referring to Table 1, Examples 1 to 8 is adjusted the internal cross-linking agent type and content, moisture content, etc., gel pulverization before hydrogel this has a gel strength of at least 10000Pa, the gel grinder is controlled snout stencil hole diameter and hamsueul after crushing the gel to the gel strength to meet the range of 35 to 95% prior to the gel breaking.

On the other hand, Comparative Example 1 is the hamsueul the gel pulverization before hydrogel excessively high gel pulverization before / after the function will gel is indicative of a low gel strength, and Comparative Example 4. In addition, the internal cross-linking agent content of a low too low hydrogel before gel pulverized gel It indicates the intensity. Further, Comparative Examples 2 and 3 is out of the pore size of the porous plate failure to maintain a proper level, the gel strength after the gel crushing a suitable range of the gel grinder.

Experimental Example

Subjected to a physical property of each super-absorbent resin prepared in Examples and Comparative Examples were measured and evaluated in the following manner.

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

European non-woven fabric ^): the Industry Association (centrifugation beam SAT (CRC) due to no load Heavy absorption magnification according to the EDANA WSP 241 .3 European Disposables and Nonwovens Association, EDANA) standard was measured. Superabsorbent Polymer W 0 (g, about 0.2g) after the insert uniformly in the envelope of the nonwoven fabric is sealed (seal), the phase is 0.9 weight 0 was submerged in saline solution of sodium chloride solution /. 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). In addition, the mass was measured, then W ^ g) of after the same manner without using a super-absorbent resin. In this way use of the respective mass obtained by the following equation 1 to calculate the CRC (g / g) it was confirmed beam SAT.

[Equation 1]

CRC(g/g) = {[W2(g) - W^g) - W0(g)]/W0(g)}

(2) saline flow induced (SFC; saline flow conductivity)

Disclosed in U.S. Patent No. 5,562,646 arc column 54 to column 59

Measurement and was calculated according to the method.

(3) T-20

Lorodac of distilled water to 1 L 9 g sodium chloride and 0.1 g of lithium: Create the (main component rate, CAS # 68439-50-9 Ethoxylated linear alcohol of a carbon number of 12 to 14) dissolved in aqueous solution, under pressure of 0.3psi, superabsorbent Polymer 1 g this was calculated and determined as the time required to absorb these aqueous solution of 20 g. Specific measuring method of this T-20 is described in detail in European Patent Publication No. 2535027 call page page 13 to 18.

.

(4) FSR (Free Swell Rate)

FSR of the base resin powder or a super-absorbent resin is # 30 of the classifying minutes to the classified as # 50 by using the (for instance, having a particle size of 300 to 600), European Patent Publication No. 2535027 call page 22 to 23 were measured and calculated by the method described on the page.

(5) FHA

Under pressure of 0.3psi, the superabsorbent resin for 1 hour saline solution (0.9 weight for zero were measured after the absorption /. NaCl solution), were measured and calculated as the absorption ratio (FHA) fixed height 20cm. Other specific measurement and the calculation method was the same as the method described in the claim of U.S. 7,108,916 patent deungtok example.

The measurement carried out using the above Examples 1 to 8 and Comparative Examples

To the value shown collectively in Table 2.

TABLE 2

Referring to Table 2, Examples 1 to 8, yet not only has excellent fundamental absorption performance, which is defined as a CRC, and excellent tube-component to be defined by the pressure and suction and SFC is defined by the FHA, T-20 or FSR absorption defined by the sokdeu was also found to be excellent.

On the other hand, Comparative Examples 1 to 4 was confirmed compared with the embodiment, the whole liquid, to be poor, one or more of the absorption rate or absorption capacity under pressure.

[Claims]

[Claim 11

A base resin powder comprising at least a first cross-linked polymer of the water-soluble unsaturated monomer eril-series part having a neutralized acid; And

Above is formed on a base resin powder, a super-absorbent resin including the cross-linked surface layer of claim 1, including the cross-linked polymer is a second cross-linked polymer cross-linking a surface cross-linking agent is added to the medium,

Physiological saline (0.9 weight 0 and the absorption ratio (FHA) 20cm fixed height on /. Aqueous sodium chloride solution) is 22.5g / g to 29g / g,

Physiological saline (0.685 Increased 0 inductive (SFC) of the flow /. Chloride or thromboxane aqueous solution) is

- (10 35 "7 cm 3 and -s / g) or more,

Under pressure of 0.3psi, the superabsorbent resin 1 g of 0.9 wt. 0 /. Sodium chloride and 0.01 wt. 0 /. T-20 is less than or equal to 180 seconds indicating the rate aqueous solution 20 g of water-absorbing time of ethoxylates alkoeul having a carbon number of 12 to 14 superabsorbent polymer.

[Claim 2]

In the resistance : ¾ saline (0.9% by weight aqueous solution of sodium chloride) control] ι 30 bun centrifugation for beam SAT (CRC) is 26 g / g to 34g / g of superabsorbent polymer.

[Claim 3]

The method of claim 1 wherein the superabsorbent polymer 1 g of 0.9 wt. 0 /. Speed to absorb the aqueous solution of sodium chloride 20 g (FSR, free Swell Rate) is 0.25 g / g / s or more super-absorbent resin.

[Claim 4]

The method of claim 1, wherein the water-soluble ethylenically unsaturated monomer is acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, ethanesulfonic acid one by one ethanesulfonic acid, 2-methacryloyloxyethyl 2-acrylic, 2- (meth) acid, or 2- (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 polyethyl ten glycol (meth) non-hydrophilic monomer containing system, following the acrylate; And (Ν, Ν)-dimethylaminopropyl (meth) acrylate Ahmad amino group-containing unsaturated monomers and their quaternary product of-dimethylaminoethyl (meth) acrylate or (Ν, Ν); at least one selected from the group consisting of superabsorbent polymer containing.

[5.]

According to claim 1,

The first cross-linked polymer is teurimetilreul tri (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propyl ten glycol di (meth) acrylate, polypropylene ten glycol di (meth ) acrylate, rides be the di (meth) acrylate, t -butylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, acid dayieul di (meth) acrylate-laid, triethylene glycol di (meth) acrylate acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaacrylate the daeo penta EPO Li. ^ Glyceryl tri (meth) poly (meth) acrylate-based first internal cross-linking agent the polyol is selected from the group consisting of an acrylate and penta EPO tetra acrylate; And allyl (meth) acrylate in the presence of a second internal cross-linking agent, and the water absorbent resin in which the monomer comprises a cross-linked polymerized polymer.

[6.]

The method of claim 1 wherein the superabsorbent polymer has a particle size of 150 to 850.

[7.]

A base resin powder containing a low cross-linked polymers of water soluble ethylenically unsaturated monomer having at least partially neutralized acid; And

Above is formed on a base resin powder, a super-absorbent resin including the cross-linked surface layer of claim 1, including the cross-linked polymer is a second cross-linked polymer cross-linking a surface cross-linking agent is added to the medium,

Physiological saline (0 and absorption magnification (FHA) 20cm fixed height to 0.9% by weight aqueous solution of sodium chloride) is 22.5g / g to 29g / g,

Physiological saline (0.9 weight 0 and centrifuged beam SAT (CRC) for half an hour on /. Chloride or thromboxane aqueous solution) is 26 g / g to about 34g / g,

Saline solution (0.685 parts by weight 0 - (10-induced flow. / Sodium chloride solution), sex (SFC) is 35 "7 cm 3 and s / g) or more,

The superabsorbent polymer 1 g of 0.9 wt. 0 /. Chloride, sodium lithium solution velocity at the time of absorbing 20 g (FSR, free Swell Rate ) is 0.25 g / g / s to about 0.40 g / g / s at a high water-absorbent resin.

[8.]

In the presence of an internal crosslinking agent, a water-soluble ethylene-based group having at least partially neutralized acid i fire pohoe. The step of cross-linking polymerization of a monomer including first crosslinking increases polymer, forming a hydrogel polymer having a gel strength of at least 10000Pa;

The method comprising the gel strength after the grinding function of the gel polymer gel to be ground to a 35% to 95% of the Negev strength before the cutting:

The gel is comminuted function drying the polymer gel, thereby forming a crushing and classifying to a base resin powder; And

In the presence of a surface crosslinking agent, a method of manufacturing a superabsorbent polymer comprising the step of heat treating the high and to the base resin powder surface crosslinking the water absorbent resin particles.

[9.]

The method of claim 8, wherein the internal cross-linking agent comprises a poly (meth) acrylate-based first internal crosslinking agent, and allyl (meth) acrylate-based second internal cross-linking agent of a polyol,

Wherein the first internal cross-linking agent containing the internal cross-linking agent and the monomer

Super-absorbent resin is contained in an amount of 0.4 part by weight to 1 parts by weight based on 100 parts by weight of the monomer composition, and the second internal cross-linking agent is contained in an amount of 0.008 part by weight to lead 5 parts by weight based on 100 parts by increase of the monomer composition the method of manufacture.

[Claim 10]

10. The method of claim 8, wherein in the gel pulverization step, the hydrogel polymer has a water content of 38 to 60 increase%, the hydrogel polymer through the extruder equipped with a perforated plate having a plurality of holes having a diameter of 9 to 18mm method for producing a superabsorbent resin to gel fracture.

[Claim 11]

The method of claim 8, wherein the washing-step of recovering the fine powder having a particle size of less than 150 after the group classification step;

The step of reassembling the fine powder can be in the presence of a solvent; And

A re-assembly of the powder, and further comprising the step of mixing the polymer hydrogel ttwa before the drying,

The re-assembly process for producing a superabsorbent resin is used in 100 parts of increased content of from 10 to 30 parts by weight based on the dry line singgi hydrogel polymer.

[12.]

The method of claim 8, wherein the surface cross-linking agent is a method of manufacturing a superabsorbent polymer comprising a compound alkoeul compound or a polyvalent alkylene carbonate.