JP5046522B2 - Water absorbent resin and method for producing the same - Google Patents

Description

  The present invention relates to a method for producing a water absorbent resin and a water absorbent resin. Specifically, the present invention relates to a method for producing a water-absorbent resin and a water-absorbent resin capable of reducing both fine powder generated in the process of producing the water-absorbent resin and reducing the amount of residual monomer in the obtained water-absorbent resin.

  In recent years, hygroscopic materials such as paper diapers, sanitary napkins, so-called incontinence pads, and the like have been widely used as constituent materials for water-absorbing resins intended to absorb body fluids. Examples of the water-absorbing resin include a crosslinked polyacrylic acid partial neutralized product, a hydrolyzate of starch-acrylic acid graft polymer, a saponified product of vinyl acetate-acrylic acid ester copolymer, an acrylonitrile copolymer or acrylamide. A hydrolyzate of a copolymer or a cross-linked product thereof, and a cross-linked product of a cationic monomer are known, and the shape thereof can be used in a sheet form, a fiber form, a film form, etc. (Particulate). As such powders (particles), for example, those having a weight average particle diameter of about 200 to 800 μm are widely used.

Properties required for such a water-absorbing resin include, but are not limited to, water absorption properties (water absorption capacity under no pressure, water absorption capacity under pressure, liquid permeability under pressure, and the like).
m or less fine particles) and the amount of residual monomer is required to be small. That is, fine powder becomes a factor that reduces liquid permeability due to clogging in absorbent articles such as diapers, and also reduces the surface cross-linking effect of the water-absorbent resin (even if surface cross-linking is performed, the absorption capacity under pressure, etc. It is difficult to improve the physical properties of the diaper), and when it is incorporated into an absorbent article such as a diaper, it is easily lost and it causes a problem that the working environment is deteriorated by dust. . On the other hand, the remaining amount of the residual monomer is desired to be as small as possible from the viewpoint of safety and odor.

Therefore, as a means for reducing the fine powder in producing the water-absorbent resin, the fine powder is classified and removed by a sieve, an air current or the like. However, the fine powder removed in the classification step may be as much as several percent to several tens of percent of the solid content in the polymerization gel obtained in the polymerization step, and in some cases as much as several tens of percent. This leads to a decrease in yield and requires a fine powder disposal cost, resulting in an increase in the production cost of the water absorbent resin. Although it is conceivable that the removed fine powder is used as it is for another application or sold without being discarded, the water-absorbent resin, which is a fine powder, has low physical properties and generally has little demand.
Thus, as a method for obtaining an inexpensive water-absorbing resin with a small amount of fine powder, many methods for reusing fine powder, that is, fine powder recycling methods have been proposed. As a fine powder recycling method, (I) a method in which fine powder is directly mixed with an aqueous monomer solution before polymerization (see Patent Document 1) and (II) a method in which fine powder is directly mixed with a gel in the middle of polymerization (patent) References 2 and 3), (III) A method in which fine powder is directly mixed with a polymerization gel obtained by polymerization, (IV) A fine powder is granulated with an aqueous liquid to form large particles, and then a polymerization gel obtained by polymerization is obtained. There is a method of mixing (see Patent Document 4). Among these, since the methods (I) to (III) use the fine powder as it is, it is difficult to mix the fine powder uniformly, and the fine powder absorbs monomer, water, and the like. There is a risk of performance degradation. Therefore, the method (IV) in which fine powder is granulated and used is considered preferable. In the method of (IV), in order to make fine particles by binding fine powder with water as a binder in general, it is usually necessary to dry the aqueous liquid used, but drying of the granulated particles obtained from the fine powder, In the drying process in the original production line, that is, the process for drying the polymer gel obtained by the polymerization, it is considered desirable from the viewpoint of production cost and efficiency to be performed together with the polymer gel. In addition, as an application of the method (IV), a method of pulverizing the gelled product obtained after making the fine powder into an integrated gelled product instead of particles can be considered. Since a large amount of water is contained in the gelation, a large amount of energy is required at the time of drying, and the production cost is increased.

On the other hand, as means for reducing the residual monomer in producing the water-absorbing resin, (i) a method of increasing the amount of the radical polymerization initiator added to the aqueous monomer solution during the polymerization, (ii) A method of adding to a polymer gel obtained after polymerization (see Patent Documents 5 and 6) is known. Among these, the method (ii) is considered preferable because the method (i) makes it difficult to control the polymerization and may cause a decrease in physical properties such as an increase in soluble content.
US Pat. No. 5,342,899 US Pat. No. 4,970,267 US Pat. No. 4,950,692 US Pat. No. 6,458,921 Japanese Examined Patent Publication No. 63-7203 JP 2004-517179 A

  However, in order to granulate and recycle the fine powder generated in the manufacturing process of the water absorbent resin by the method (IV), the inventor mixes the granulated particles obtained from the fine powder with the polymer gel and dries together. As a result, a new fact was found that the amount of residual monomer present in the dried product after drying (the amount per unit weight of the water-absorbent resin) was larger than the theoretical value. Further, in order to solve the problem of the residual monomer, the method (ii) is adopted in the fine powder recycling method of (IV), and a radical polymerization initiator such as persulfate is added to the polymerization gel to remove the residual monomer. Even when the reduction is attempted, a problem has been found that the effect of reducing the residual monomer is significantly reduced.

Considering that the residual monomer reduction effect is reduced by mixing the granulated particles obtained from fine powder with the polymer gel and drying together, the amount of radical polymerization initiator added to the polymer gel is increased. If this is done, it is possible to reduce the amount of residual monomer in the finally obtained water-absorbing resin to a desired level, but if a large amount of radical polymerization initiator is used, the resulting water-absorbing resin may be colored. This leads to another problem that the physical properties deteriorate.
As described above, in the production of the water absorbent resin, it is very difficult to achieve both reduction of fine powder generated in the production process and reduction of the amount of residual monomer in the obtained water absorbent resin, which has not been achieved. Was the current situation.

  Thus, the problem to be solved by the present invention is to provide a water-absorbing resin production method and a water-absorbing resin capable of reducing both fine powder generated during the production process and reducing the amount of residual monomer in the obtained water-absorbing resin. Is to provide.

  The present inventor has intensively studied to solve the above problems. As a result, instead of adding a radical polymerization initiator to the polymer gel as in the prior art described above, a pyrolytic radical polymerization initiator is added to the side of the granulated particles obtained from the fine powder generated during the production process of the water absorbent resin. In addition, when the obtained granulated particles and the polymer gel are allowed to coexist and dry, the same amount (finally, as compared with the case where the thermal decomposition type radical polymerization initiator is directly added to the polymer gel). It has been found that the residual monomer can be more effectively reduced by addition of the resulting water-absorbent resin (per unit weight). It has also been found that such an effect can be obtained in the same manner even when an oxidizing agent or a reducing agent is used instead of the thermal decomposition type radical polymerization initiator. The present invention has been completed based on these findings.

That is, the method for producing a water-absorbent resin according to the present invention includes a step of obtaining a polymer gel having water absorbency, and a fine powder having a weight average particle diameter in the range of 10 to 150 μm obtained in the production of the water-absorbent resin. A step of obtaining a granulated gel by adding an aqueous liquid containing at least one additive selected from the group consisting of a decomposable radical polymerization initiator, an oxidizing agent and a reducing agent; and the granulated gel And a step of allowing the polymer gel to coexist and drying.
The water-absorbent resin according to the present invention is a water-absorbent resin containing a polymer gel having water absorbency and a granulated gel, and the granulated gel has a weight average particle diameter of 10 to 150 μm. The ratio (A / B) between the solid content rate A (%) of the granulated gel and the solid content rate B (%) of the polymerized gel is 1/3 or more and 3 or less. The residual monomer is 0 or more and 500 ppm or less. The manufacturing method of this water absorbing resin is not limited. An example of the manufacturing method of this water absorbing resin is the manufacturing method described in this application.

  According to the present invention, it is possible to achieve both a reduction in fine powder generated during the production process and a reduction in the amount of residual monomer in the resulting water-absorbent resin. Specifically, according to the present invention, the fine powder generated in the production process of the water-absorbent resin is effectively reused while the additive for reducing the residual monomer (from the thermal decomposition type radical polymerization initiator, the oxidizing agent and the reducing agent). It is possible to obtain a water-absorbing resin having good physical properties with a small amount of residual monomer without increasing the amount of use of at least one selected from the group consisting of: That is, the method for producing the water-absorbent resin of the present invention is a method for efficiently reducing the residual monomer, and also has the effect on the production cost of reusing fine powder as in the conventional fine powder reuse method by granulation. It is obtained.

Hereinafter, the method for producing a water absorbent resin and the water absorbent resin according to the present invention will be described in detail. However, the scope of the present invention is not limited to these explanations, and the gist of the present invention is not limited to the following examples. Changes can be made as appropriate without departing from the scope.
The production method of the present invention includes a step of obtaining a polymer gel having water absorption (hereinafter also referred to as “polymerization step”). The subsequent steps are not limited, but usually, further, a step of drying the polymer gel (hereinafter sometimes referred to as “drying step”) and a step of pulverizing the dried polymer gel ( In general, the process includes a step of “pulverizing step” and a step of classifying the pulverized product (hereinafter also referred to as “classifying step”). Specifically, the production method of the present invention recycles fine powder obtained in the production of the water absorbent resin (for example, fine powder removed as waste in the classification step, etc.) to obtain a water absorbent resin with a small amount of residual monomer. Therefore, it can be said that this is a method suitable for continuously producing a water-absorbent resin.

That is, in the production method of the present invention, the fine powder having a weight average particle diameter in the range of 10 to 150 μm obtained in the production of the water-absorbing resin is added to a group consisting of a pyrolytic radical polymerization initiator, an oxidizing agent and a reducing agent. A gel (hereinafter referred to as “granulated gel” or “granulated particles”) that is granulated by adding an aqueous liquid containing at least one additive selected from the following (hereinafter also referred to as “essential additive”). It is important to dry the granulated gel and the polymer gel together. That is, the granulated particles obtained by mixing the fine powder and the aqueous liquid are subjected to a drying step together with the polymer gel obtained in the polymerization step.
In the present invention, the granulated particles are composed of a plurality of fine powders, and the average particle diameter of the granulated particles is 20 mm or less, preferably 0.3 to 10 mm, more preferably 0.35 to 5 mm. Therefore, when a huge gel-like material is obtained by mixing the fine powder and the aqueous liquid, it is necessary to further dry and grind.

From the viewpoint of drying load, the granulated particles preferably have a moisture content of 75% by weight or less, more preferably 70% by weight or less, and even more preferably 65% by weight or less (the lower limit is 0 More than 5% by weight, preferably more than 5% by weight). If the water content of the granulated particles is extremely higher than that of the polymer gel, drying may be partially incomplete when drying with the polymer gel. According to the knowledge obtained by the present inventors, in the conventional technique, when the granulated particles having a low water content are dried together with the polymer gel, the residual monomer amount of the resulting water-absorbent resin tends to increase more remarkably. From the monomer point of view, it is necessary to keep the moisture content of the granulated particles high even if a load is applied in the subsequent drying step, but according to the present invention, it remains even if the moisture content is relatively low. The monomer can be sufficiently reduced, and the application of the present invention becomes more significant when the water content is in the above range.

  The fine powder has a particle size smaller than the particle size of the water-absorbent resin to be obtained by the production method of the present invention, and as described above, is conventionally treated as waste. . In general, the weight average particle diameter (D50) of the water absorbent resin (specified by JIS standard sieve classification) is preferably 200 to 800 μm. For example, the weight average particle diameter of the water absorbent resin obtained by the production method of the present invention ( D50) is preferably in the range described later (200 to 450 μm). The fine powder is a residue obtained by removing the weight-average particle diameter (D50) of the obtained water-absorbent resin so as to be in the desired range described above. Specifically, as described above, the weight-average particle diameter (D50). ) Is in the range of 10 to 150 μm. Preferably, it is desirable to contain 70 to 100% by weight, more preferably 90 to 100% by weight, of particles having a particle size of substantially less than 150 μm (specified by JIS standard sieve classification). Further, the shape of the fine powder is preferably an indeterminate shape obtained by aqueous solution polymerization rather than a spherical shape obtained by reverse phase suspension polymerization in terms of granulation strength. Further, as will be described later, the fine powder may or may not have been subjected to a surface cross-linking treatment that is generally performed in the production of a water-absorbent resin. Or a mixture thereof.

In addition, all the fine powder obtained in manufacture of a water absorbing resin can be provided for the said granulation. Usually, the fine powder obtained in the classification step is mainly used. However, not only the fine powder obtained in the classification step, but also, for example, the fine powder removed by the back filter in each manufacturing process is used for the granulation. Moreover, the fine powder obtained by a separate process and the fine powder obtained by another manufacturing process (another manufacturing apparatus) can also be mixed and used. Further, the fine powder may have the same composition as the polymer gel that is dried together, or may have a different composition, but it is preferable to use a fine powder having the same composition derived from the polymer gel that is dried together. .
The temperature of the fine powder is preferably 35 ° C. or higher, more preferably 40 to 100 ° C., further preferably 45 to 80 ° C., from the viewpoint of mixing with an aqueous liquid and drying efficiency. . What is necessary is just to adjust the temperature of a fine powder suitably at each process of manufacture of a water absorbing resin by heat retention, heating, cooling.

  The aqueous liquid used when granulating the fine powder is a solution in which the essential additive is dissolved in a solvent, and the solvent is not particularly limited. For example, water or a hydrophilic organic solvent (for example, methyl alcohol) is used. Lower alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and t-butyl alcohol; ketones such as acetone; ethers such as dioxane and tetrahydrofuran; N, N-dimethylformamide Amides such as sulfoxides such as dimethyl sulfoxide) and the like. From the viewpoint of physical properties and granulation strength, it is preferably 90 to 100% by weight, more preferably 99 to 100% by weight, and particularly preferably water alone. The aqueous liquid may contain a small amount of other additives such as a crosslinking agent, a chelating agent and a surfactant as long as the effects of the present invention are not impaired. For example, as the cross-linking agent, the following types of surface cross-linking agents can be used, and reduction of water-soluble components and improvement of granulation strength can be expected by incorporating the cross-linking agent into the aqueous liquid.

The thermal decomposition type radical polymerization initiator that can be used as the essential additive contained in the aqueous liquid is one that can decompose and react with the monomer when dried in the presence of granulated particles and polymer gel. If there is no particular limitation, for example, potassium persulfate, ammonium persulfate, sodium persulfate, t-butyl hydroperoxide, hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, etc. Can be mentioned. Among these, peroxides are preferable, and persulfates such as sodium persulfate are particularly preferable. These thermal decomposition type radical polymerization initiators may be only one kind or two or more kinds.
The oxidizing agent that can be used as the essential additive contained in the aqueous liquid is not particularly limited as long as it can react with the monomer when dried in the presence of the granulated particles and the polymer gel. For example, inorganic oxidizers such as chlorate, bromate, chlorite, hypochlorite, persulfate, hydrogen peroxide, and t-butyl exemplified also as the thermal decomposition type radical polymerization initiator Examples thereof include inorganic peroxides such as peroxides and benzoyl peroxide, and organic peroxides. Among these, persulfate and hydrogen peroxide are preferable, and persulfate is particularly preferable. These oxidizing agents may be only one type or two or more types.

  The reducing agent that can be used as the essential additive contained in the aqueous liquid is an organic reducing agent as long as it can react with the monomer when dried in the presence of the granulated particles and the polymer gel. Or an inorganic reducing agent, which is not particularly limited, but is preferably an inorganic reducing agent, and sulfur, phosphorus, and nitrogen reducing agents are particularly preferable. Specifically, for example, sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfite (for example, sodium bisulfite, potassium bisulfite, ammonium bisulfite, etc.), pyrosulfite, dithione. Examples include acid salts, trithionates, tetrathionates, thiosulfates, nitrites, dimethyl sulfoxide, thiourea dioxide, phosphites, nitrogen-containing organic compounds such as amino acids and ethanolamines. Among these, sulfur-based reducing agents, in particular, sulfites, hydrogen sulfites, pyrosulfites, and dithionites are preferable. Examples of those salts include sodium salts, potassium salts, and ammonium salts. Of these, sodium sulfite and sodium hydrogen sulfite are particularly preferable. These reducing agents may be only one kind or two or more kinds.

Among the above-mentioned essential additives, a thermal decomposition type radical polymerization initiator is preferable, and in particular, it is preferable that persulfate is essential because an excellent residual monomer reducing effect can be exhibited.
The content of the essential additive in the aqueous liquid is not particularly limited, but is usually preferably 0.0001 to 1% by weight with respect to the fine powder. If the amount is less than 0.0001% by weight, the residual monomer may not be sufficiently reduced. On the other hand, if it exceeds 1% by weight, the final water absorbent resin obtained after drying may be colored.
The essential additive (particularly a thermal decomposition type radical polymerization initiator) may be used in the polymerization step. In that case, the content of the essential additive in the aqueous liquid is usually such that the amount per unit weight of the fine powder before granulation is the amount of the essential additive added in the polymerization step (per unit weight of the monomer component). 1 to 500% by weight, more preferably 5 to 400% by weight, and still more preferably 10 to 300% by weight. When the ratio of the essential additive contained in the aqueous liquid to the essential additive added in the polymerization step is out of the above range, the effect of the present invention is reduced. In the case described above (that is, when the essential additive is used in the polymerization step), the essential additive added in the polymerization step and the essential additive contained in the aqueous liquid are the same type. It may be a different kind.

A feature of the production method according to the present invention is that the essential additive is contained in an aqueous liquid. Although the effect on the addition amount is low as compared with this case, the essential additive (especially thermal decomposition type radical polymerization initiation) In addition to adding to the aqueous liquid, for example, the agent may be added to the polymer gel before being subjected to the drying step, or to the dried product (dry polymer gel) before being subjected to the pulverization step. You may add in the arbitrary processes in the manufacturing method of invention.
Although the usage-amount of the said aqueous liquid is not restrict | limited in particular, It is preferable to set it as 25 to 280 weight part with respect to 100 weight part of fine powder. More preferably, it is 200 weight part or less, More preferably, it is 150 weight part or less. When the amount of the aqueous liquid used exceeds 280 parts by weight, an integrated huge gel-like product is obtained, and it is necessary to further dry and pulverize the gel-like product to form granulated particles. A great load is applied. On the other hand, when the amount of the aqueous liquid used is less than 25 parts by weight, the granulation strength is insufficient, and it may not be possible to exhibit excellent characteristics in the final product, and the mixing becomes uneven and the structure is not uniform. The grain may be difficult.

  When granulating the fine powder, the fine powder and the aqueous liquid may be mixed. In particular, it is preferable to preheat the aqueous liquid during the granulation. It is a preferred embodiment to granulate by mixing the aqueous liquid and the fine powder at high speed. As a result, it is possible to obtain granulated particles having a directly controlled particle size, rather than an integrated giant gel, and as a result, it is necessary to further dry and pulverize the gel to obtain granulated particles. The problem that arises when a huge integrated gel is obtained, that is, a huge force is required for mixing, or the gel-like lump is kneaded, so that the main chain is cut or entangled. For example, the problem that the water-absorbing resin itself deteriorates can be avoided.

In a preferred embodiment of the granulation, the temperature at which the aqueous liquid is heated is usually 40 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and further preferably 70 ° C. or higher. The upper limit of the temperature is not more than the boiling point of the aqueous liquid, and the boiling point may be variously adjusted by changing the addition of salts and other solvents, pressure (decompression / pressurization), etc., but the temperature exceeds 100 ° C. However, since it does not change greatly, it is usually performed at 100 ° C. or lower. In addition, when the aqueous liquid is preheated, the essential additive is separately made into an aqueous solution having a relatively high concentration at room temperature or under cooling, and is heated relatively immediately before mixing with the fine powder. It is preferable to mix with a large amount of the aqueous liquid residue.
In a preferred embodiment of the granulation, in addition to heating the aqueous liquid in advance, it is preferable that the fine powder itself is also heated. The temperature at the time of heating this fine powder is also usually 40 ° C. or higher, preferably 50 ° C. or higher, and since it does not change greatly even if it exceeds 100 ° C., it is usually carried out at 100 ° C. or lower. In addition, when heating fine powder itself, the means in particular is not restrict | limited, For example, you may carry out by heat-retaining after heating by drying, and you may make it heat from the outside separately.

  In a preferred embodiment of the granulation, when the heated aqueous liquid and the fine powder are mixed at a high speed, the high speed mixing is a time in which the mixing of the aqueous liquid and the fine powder is completed and the granulated particles are generated. Means that. That is, the time from the contact point of the aqueous liquid and the fine powder to the generation of the granulated particles, in other words, the mixing time is short. The mixing time is preferably 3 minutes or less, more preferably 1 minute or less, and most preferably from 1 second to 60 seconds. When the mixing time is long, uniform mixing of the aqueous liquid and the fine powder becomes difficult, and an integrated huge gel is likely to be obtained. In addition, if the mixing time is long, the essential additive contained in the aqueous liquid is decomposed before the resulting granulated particles are subjected to the drying step together with the polymer gel, and a sufficient amount is obtained in the drying step. There is a risk that essential additives may not be present. Furthermore, if mixing is continued for a long time after completion of mixing, performance of the water-absorbing resin may be reduced, such as an increase in water-soluble content of the water-absorbing resin obtained or a decrease in water absorption capacity under pressure.

  As a means for achieving high speed mixing, a heated aqueous liquid can be put into the fine powder being stirred at once. That is, when the aqueous liquid is gradually added, for example, by spraying or the like, the fine powder may become large agglomerates or kneaded on the way, which may cause deterioration of the water absorbent resin. The heating time of the heated aqueous liquid is preferably 60 seconds or less, more preferably 30 seconds or less, and most preferably 10 seconds or less. In addition, as a means for achieving high-speed mixing, a method of adding fine powder to a heated aqueous liquid being stirred, contrary to the above, can also be mentioned. In this case, the charging time of the fine powder is preferably 60 seconds or shorter, more preferably 30 seconds or shorter, and most preferably 10 seconds or shorter. Further, as a means for achieving high speed mixing, there is a method in which fine powder and a heated aqueous liquid are simultaneously mixed at once. In this case, the charging time of both is preferably 60 seconds or less, more preferably 30 seconds or less, and most preferably 10 seconds or less. Moreover, it is also possible to obtain the granulated particles continuously by continuously charging them at the same time and mixing them at high speed. As described above, in consideration of the decomposition of the essential additive, it is preferable that the time until the granulated particles and the polymer gel coexist and be dried is as short as possible. When obtaining, it is a preferred embodiment to continuously mix the granulated particles with this and send it to the drying step in a short time.

The resulting granulated product is a granulated particle because of the fact that a plurality of individual particles are gathered and aggregated while maintaining the shape by an optical microscope, and the fact that they swell as a plurality of discontinuous particles during liquid absorption. I can confirm.
When the granulated particles and the polymer gel are dried together, the difference between the solid content ratio B (%) of the polymer gel and the solid content ratio A (%) of the granulated particles (or the polymer gel) The smaller the difference between the water content and the water content of the granulated particles, the better. Specifically, the ratio (A / B) of the solid content rate A (%) of the granulated particles (granulated gel) and the solid content rate B (%) of the polymer gel is usually 1/3 or more 3 Or less, more preferably 1/2 or more and 2 or less, further preferably 2/3 or more and 3/2 or less, and further preferably 4.5 / 5.5 or more and 5.5 / 4.5 or less. Particularly preferably, 1 (that is, substantially the same solid content) is good. When the ratio (A / B) of the solid content ratio B of the polymer gel and the solid content ratio A of the granulated particles is out of the above range, drying of both the mixture tends to be uneven, and either one is overdried or It may become undried and may cause manufacturing problems and quality problems.

The “solid content” is a residue obtained by removing a volatile component (mainly water) from a gel-like water-absorbing resin (polymerized gel or granulated gel), that is, a resin component of the water-absorbing resin. In the book, the weight of the solid content is referred to as “solid content”, and the ratio of the solid content to the weight of the gel-like water-absorbing resin containing a volatile component is expressed as “solid content ratio (%)”. . The “moisture content” is the ratio (%) of water contained in the gel-like water-absorbent resin and substantially corresponds to a value obtained by subtracting the solid content (%) from 100%.
When the granulated particles and the polymer gel coexist and are dried, the ratio of the granulated particles and the polymer gel (in other words, the amount of fine powder recycled relative to the solid content in the polymer gel obtained in the polymerization step) is The solid content in the granulated particles (granulated gel) (solid content of fine powder before granulation) is preferably 40% by weight or less based on the solid content in the polymer gel, It is preferable in order to be 35% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, and 15% by weight or less. In addition, the lower limit should just exceed 0 weight%. Usually, it can be said that it is not realistic from the viewpoint of production efficiency that the recycle amount of fine powder with respect to the solid content in the polymer gel obtained in the polymerization step exceeds 40% by weight.

Considering that the recycle amount of fine powder is 40% by weight at the highest, the amount of the essential additive used by adding to the aqueous liquid is the water absorption obtained after drying the granulated particles together with the polymer gel. The total amount of the resin is very small, and at most, it is less than 0.3% by weight. When the amount of fine powder recycled is about 10% by weight, it is less than 0.1% by weight. That is, compared with the case where all the essential additives to be used are added to the polymer gel to reduce the residual monomer to a desired level, the production method of the present invention in which the essential additives are added to the aqueous liquid is very The residual monomer can be reduced to the desired level with a small amount of essential additive.
In the production method according to the present invention, the granulated particles and the polymer gel coexist and are dried. Preferably, drying is performed in a state where at least a part of the granulated particles and at least a part of the polymer gel are in contact with each other. Or preferably, the granulated particles are mixed with the polymer gel and dried. The granulated particles may be dried in a state where they are homogeneously mixed with the polymer gel, or may be dried in a state where the granulated particles are lightly mixed with the polymer gel or are hardly mixed. That is, in the production method according to the present invention, as described above, the residual monomer can be sufficiently reduced even if it is dried in a lightly mixed state or in a hardly mixed state, even if it is not mixed homogeneously. It can be done. Specifically, for example, for the polymer gel flowing in a pipe connected to an apparatus for performing a drying process or on a conveyor belt, the granulated particles are merged in the pipe or supplied onto the conveyor belt. All you have to do is just dry together. In the conventional technology for reducing residual monomer by adding persulfate to the polymer gel, it is important to uniformly distribute the additive such as persulfate throughout the polymer gel, which requires separate mixing operations. In some cases, it is suggested that the mechanism for reducing the residual monomer is different. That is, in the production method according to the present invention, it can be said that the essential additive contained in the granulated particles is not homogeneously mixed with the polymer gel in the form of granulated particles and acts to reduce the residual monomer. It is thought that some sort of effect is exhibited. Of course, it goes without saying that there is no problem even if the granulated particles are uniformly mixed with the polymer gel.

In addition, the drying method, conditions, etc. at the time of drying by making a granulated particle and a polymerization gel coexist are described in detail in the drying process mentioned later.
Hereinafter, the polymerization step essential in the production method according to the present invention, and the drying step, the pulverization step, and the classification step performed as necessary will be described in detail.
(Polymerization process)
The polymerization step is a step of generating a polymer gel having water absorption by polymerizing a monomer that can become a water-absorbent resin by polymerization. The polymerization method used in the production method according to the present invention is not particularly limited, and bulk polymerization and precipitation polymerization can also be performed. However, from the viewpoint of performance and ease of control of polymerization, the monomer is used as an aqueous solution. Aqueous polymerization or reverse phase suspension polymerization is preferred.

  Although it does not specifically limit as said monomer, For example, what is shown below is mentioned. For example, (meth) acrylic acid, (anhydrous) maleic acid, itaconic acid, cinnamic acid, vinyl sulfonic acid, allyl toluene sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, 2- (meth) acrylamide-2-methylpropane Anionic unsaturated monomers such as sulfonic acid, 2- (meth) acryloylethanesulfonic acid, 2- (meth) acryloylpropanesulfonic acid, 2-hydroxyethyl (meth) acryloyl phosphate and salts thereof; mercapto group-containing Unsaturated monomers; phenolic hydroxyl group-containing unsaturated monomers; amide group-containing unsaturated monomers such as (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylamino Propyl (meth) acrylate, N, N-dimethylaminopropyl (meth) amino group-containing unsaturated monomers such as acrylamide; and the like. These monomers may be used singly or may be used in combination of two or more, but acrylic acid and / or a salt thereof (for example, sodium, lithium, etc.) from the viewpoint of performance and cost of the water-absorbing resin obtained. , Potassium, ammonium, amines and the like, and sodium salt is preferable from the viewpoint of cost). The amount of acrylic acid and / or its salt used is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more, based on the total monomer components (excluding the internal crosslinking agent described later). Especially preferably, it is 95 mol% or more (the upper limit is 100 mol%). In the case where the monomer is an acid group-containing monomer, the neutralization rate is not particularly limited, and may be neutralized after polymerization, if necessary. In some applications, it is preferably 40 mol% or more and 90 mol% or less, more preferably 50 mol% or more and 80 mol% or less, in addition to the fact that neutralization after polymerization is not required.

In the polymerization step, the concentration of the monomer in the aqueous solution (hereinafter sometimes referred to as “monomer solution”) when the monomer is an aqueous solution is not particularly limited, but is 10 to 70% by weight. Within the range, the range of 20 to 60% by weight is more preferable. Moreover, when performing the said aqueous solution polymerization or reverse phase suspension polymerization, you may use together solvents other than water as needed, and the kind of solvent used together is not specifically limited.
In the polymerization step, polymerization can be performed using a radical polymerization initiator. The radical polymerization initiator is not particularly limited, and one or two or more types selected from those used in normal water-absorbing resin production are selected according to the type of monomer to be polymerized and polymerization conditions. Use it. For example, thermal decomposition type initiator (for example, persulfate such as sodium persulfate, potassium persulfate, ammonium persulfate; peroxide such as hydrogen peroxide, t-butyl peroxide, methyl ethyl ketone peroxide; azonitrile compound, azoamidine compound Cyclic azoamidine compounds, azoamide compounds, alkylazo compounds, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, etc. Azo compounds; etc.) and photodegradable initiators (for example, benzoin derivatives, benzyl derivatives, acetophenone derivatives, benzophenone derivatives, azo compounds, etc.). Among these, in view of cost and ability to reduce residual monomer, a thermal decomposition type initiator is preferable, and a persulfate is particularly preferable. In addition, a reducing agent that promotes the decomposition of the radical polymerization initiator may be used in combination, and a redox initiator may be obtained by combining the two. Examples of the reducing agent include (bi) sulfurous acid (salt) such as sodium sulfite and sodium bisulfite, L-ascorbic acid (salt), reducing metal (salt) such as ferrous salt, amines, and the like. Although it is mentioned, it is not particularly limited. More preferably, a photodegradable initiator and a thermal decomposable initiator are used in combination. The amount of the radical polymerization initiator used in the polymerization step is not particularly limited, but is usually preferably 0.001 to 2% by weight, and 0.01 to 0.05% by weight based on the monomer. It is more preferable. If the amount of the radical polymerization initiator used is less than 0.001% by weight, the amount of unreacted monomer increases, and therefore the amount of residual monomer in the resulting water-absorbent resin increases, which is not preferable, while 2% by weight If it exceeds%, the water-soluble component in the resulting water-absorbent resin increases, which is not preferable.

In the polymerization step, instead of using the radical polymerization initiator, the polymerization reaction may be carried out by irradiating the reaction system with active energy rays such as radiation, electron beams, and ultraviolet rays.
In the polymerization step, an internal crosslinking agent can be used as necessary. As the internal cross-linking agent, a conventionally known internal cross-linking agent having two or more polymerizable unsaturated groups or two or more reactive groups in one molecule can be used. Specifically, for example, N, N′-methylenebis (meth) acrylamide, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin Tri (meth) acrylate, glycerin acrylate methacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol hexa (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, triallylamine, polyallyloxy Alkane, (poly) ethylene glycol diglycidyl ether, glycerol diglycidyl ether, ethylene glycol, polyethylene glycol, propylene glycol And glycerin, 1,4-butanediol, pentaerythritol, ethylenediamine, ethylene carbonate, propylene carbonate, polyethyleneimine, glycidyl (meth) acrylate, and the like. One type or two or more types may be used. In particular, as the internal cross-linking agent, it is preferable to use a compound having two or more polymerizable unsaturated groups. The amount of the internal crosslinking agent used may be appropriately determined depending on the desired physical properties of the water-absorbent resin, but is usually in the range of 0.001 to 5 mol% with respect to the monomer. If the amount of the internal cross-linking agent used is too small, the gel strength tends to decrease and the soluble content tends to increase, and conversely if too large, the absorption capacity tends to decrease. The internal cross-linking agent may be added to the reaction system all at once or in divided portions.

In the polymerization step, if necessary, the reaction system may include various foaming agents such as carbonic acid (hydrogen) salts, carbon dioxide, azo compounds, inert organic solvents; starch / cellulose, starch / cellulose derivatives, and polyvinyl alcohol. , Hydrophilic polymers such as polyacrylic acid (salt) and crosslinked polyacrylic acid (salt); various surfactants; chain transfer agents such as hypophosphorous acid (salt); and the like that do not impair the effects of the present invention (For example, with respect to 100 parts by weight of the monomer, various foaming agents may be added in an amount of 30 parts by weight or less, the hydrophilic polymer is 30 parts by weight or less, and the chain transfer agent is 1 part by weight or less).
The polymerization temperature in the polymerization step is not particularly limited, but is usually preferably 10 to 140 ° C. If the polymerization temperature is less than 10 ° C, not only the polymerization time is prolonged and the productivity is lowered, but also the physical properties of the water absorbent resin may be lowered. On the other hand, if it exceeds 140 ° C, the physical properties of the water absorbent resin are deteriorated. May fall. The polymerization time is not particularly limited, and may be appropriately determined according to the kind of the monomer or polymerization initiator, the polymerization temperature, and the like. The polymerization is usually carried out under normal pressure for ease of apparatus and operation, but it is also a preferred embodiment to carry out under reduced pressure in order to lower the boiling temperature of the polymerization system.

(Drying process)
The drying step is a step of drying the polymer gel obtained in the polymerization step or the granulated gel obtained from the polymer gel and fine powder. It is preferable that the polymer gel obtained in the polymerization step is usually subjected to a drying step in a particulate state of about 0.1 to 5 mm. The drying method in this drying process is not specifically limited, The method using a normal dryer and a heating furnace can be employ | adopted widely. The drying temperature is preferably a relatively high temperature, specifically, preferably 100 to 250 ° C, more preferably 120 to 220 ° C, and further preferably 150 to 200 ° C. The drying time is not particularly limited, and may be set so that the obtained dried product has a desired solid content rate. The dried product obtained in the drying step preferably has a solid content (weight loss on drying when heated at 180 ° C. for 3 hours) of 90% by weight or more from the viewpoint of ease of pulverization. In general, although it depends on the particle diameter of the polymer gel or granulated gel, the drying temperature, the air volume, and the like, it is usually preferably within 2 hours from the viewpoint of production efficiency.

(Crushing process)
The pulverization step is a step of pulverizing the polymer gel. The pulverization is usually performed on a dried product of the polymer gel obtained in the drying step, but may be performed on the polymer gel before drying obtained in the polymerization step. The pulverization is preferably performed so that more particles having a desired particle diameter (preferably, as described above, a weight average particle diameter of 200 to 800 μm) are obtained. There is no restriction | limiting in particular about the grinding | pulverization method, A conventionally well-known method is employable.
(Classification process)
The classification step is a step of classifying the pulverized product obtained in the pulverization step. In the classification step, a particle having a desired particle size (preferably, as described above, a weight average particle size of 200 to 800 μm) is selected to obtain a desired water-absorbent resin, and the above-described granulation is used. A fine powder is obtained as a residue. There is no restriction | limiting in particular about the classification method, A conventionally well-known method is employable.

In the manufacturing method of this invention, it is preferable to provide the process for bridge | crosslinking the particle | grain surface vicinity as needed with respect to the obtained water absorbing resin after the said classification process. Hereinafter, the surface crosslinking step will be further described.
(Surface cross-linking process)
As the surface cross-linking agent, a conventionally known surface cross-linking agent is preferably used. For example, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,3-propanediol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, polypropylene glycol, Glycerin, polyglycerin, 2-butene-1,4-diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,2-cyclohexanediol , Trimethylolpropane, diethanolamine, triethanolamine, polyoxypropylene, oxyethylene-oxypropylene block copolymer, pentaerythritol, sorbitol and other polyhydric alcohols Epoxy compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycidol; , Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine and other polyvalent amine compounds and their inorganic or organic salts (eg aziridinium salts); 2,4-tolylene diisocyanate, hexamethylene diisocyanate, etc. Polyvalent isocyanate compounds such as 1,2-ethylenebisoxazoline Xazoline compound; 1,3-dioxolan-2-one, 4-methyl-1,3-dioxolan-2-one, 4,5-dimethyl-1,3-dioxolan-2-one, 4,4-dimethyl-1 , 3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan-2-one, 1,3-dioxan-2-one, 4- Alkylene carbonate compounds such as methyl-1,3-dioxan-2-one, 4,6-dimethyl-1,3-dioxan-2-one, 1,3-dioxopan-2-one; epichlorohydrin, epibrom Haloepoxy compounds such as hydrin and α-methylepichlorohydrin; polyvalent metallization such as hydroxides or chlorides such as zinc, calcium, magnesium, aluminum, iron and zirconium Objects; and the like. Among these surface cross-linking agents, at least one compound selected from the group consisting of polyhydric alcohol compounds, epoxy compounds, polyvalent amine compounds and salts thereof, and alkylene carbonate compounds is preferred. These surface cross-linking agents may be used alone or in combination of two or more in consideration of reactivity. The surface cross-linking step may be performed twice or more in consideration of the effect. In that case, the second and subsequent times may be performed using the same surface cross-linking agent as the first time, or different surface cross-linking agents may be used. May be used.

  The amount of the surface cross-linking agent used is preferably in the range of 0.001 to 10 parts by weight with respect to 100 parts by weight of the solid content of the water-absorbent resin, although it depends on the compounds used and combinations thereof. More preferably within the range of ˜5 parts by weight. By using the surface cross-linking agent within this range, the cross-linking density near the surface of the water-absorbent resin can be made higher than the inside. When the amount of the surface cross-linking agent used exceeds 10 parts by weight, it is not preferable because not only is it uneconomical, but also the amount of the cross-linking agent becomes excessive in forming an optimal cross-linking structure as an absorbent. When the amount of the surface cross-linking agent used is less than 0.001 part by weight, it is not preferable because it is difficult to obtain an improvement effect in improving performance such as absorption capacity under pressure as an absorbent.

When performing surface crosslinking, it is preferable to use water as a solvent in mixing the water-absorbent resin and the surface crosslinking agent. The amount of water used depends on the type, particle size, water content, etc. of the water-absorbent resin, but is more than 0 parts by weight and preferably 20 parts by weight or less with respect to 100 parts by weight of the solid content of the water-absorbent resin. More preferably within the range of 5 to 10 parts by weight.
When surface crosslinking is performed, a hydrophilic organic solvent may be used in combination with the water absorbent resin and the surface crosslinking agent as necessary. Examples of the hydrophilic organic solvent that can be used here include those described above as those that can be contained in an aqueous liquid. The amount of the hydrophilic organic solvent used is preferably 20 parts by weight or less, preferably 10 parts by weight or less based on 100 parts by weight of the solid content of the water absorbent resin, although it depends on the type, particle size, water content, etc. of the water absorbent resin. The range of is more preferable.

When surface crosslinking is performed, it is preferable that after the water absorbent resin and the surface crosslinking agent are mixed, heat treatment is further performed to crosslink the vicinity of the surface of the water absorbent resin. That is, in order to cause the crosslinking agent to react in the vicinity of the surface of the water-absorbent resin, it is preferable to perform heat treatment in consideration of the reactivity of the crosslinking agent, the simplicity of the production apparatus, and the productivity. The treatment temperature of the heat treatment is preferably 80 ° C. or higher, although it depends on the surface crosslinking agent used. When the treatment temperature is less than 80 ° C., the heat treatment takes time, so that not only the productivity is lowered, but also the uniform surface cross-linking is not achieved, the absorption characteristics under pressure are reduced, the surface cross-linking agent Remaining easily.
In addition, fine powder may be generated again due to damage received in the process after the heat treatment in the surface crosslinking step. In such a case, a classification step similar to that described above is further provided until the final product is obtained. Thus, the fine powder may be removed, and the removed fine powder is preferably subjected to granulation together with the fine powder not subjected to the surface crosslinking step (fine powder obtained before the surface crosslinking step). At this time, the amount of fine powder classified after the surface cross-linking step is preferably 5% by weight or less, more preferably 3% by weight or less with respect to the amount of fine powder not subjected to the surface cross-linking step. . If the amount of fine powder classified after the surface cross-linking step exceeds 5% by weight, the strength of the granulated particles tends to decrease and the absorption capacity also tends to decrease.

For the water-absorbent resin obtained by the production method of the present invention, for example, disinfectant, antibacterial agent, fragrance, various inorganic powders, foaming agent, pigment, dye, hydrophilic short fiber, fertilizer, oxidation An agent, a reducing agent, an aqueous salt, and the like are appropriately added within a range that does not impair the effects of the present invention (for example, 30 parts by weight or less, and further 10 parts by weight or less with respect to 100 parts by weight of the water absorbent resin). Various functions can be given.
According to the production method of the present invention, it is possible to obtain a water-absorbing resin that achieves both reduction of residual monomer and fine powder, in other words, a water-absorbing resin with a small amount of residual monomer and a sharp particle size distribution. When applied, a high-performance water-absorbing resin can be obtained.

The water-absorbent resin obtained by the production method of the present invention has an unloaded load capacity (GV) of physiological saline of preferably 27 g / g or more, more preferably 30 g / g or more, still more preferably 33 g / g or more, Most preferably, it is 36 g / g or more. In general, if the absorption capacity under no load is less than 20 g / g, there is a possibility that high physical properties may not be exhibited when used for a diaper, while the upper limit of the absorption capacity under no load is not limited, but it is difficult to manufacture. In view of the fact that the cost increases because of the above, about 60 g / g is considered sufficient.
The water-absorbent resin obtained by the production method of the present invention has a water absorption capacity (AAP) under pressure of physiological saline under a load of 4.9 kPa, preferably 20 g / g or more, more preferably 22 g / g or more, still more preferably. Is 24 g / g or more, most preferably 26 g / g or more. In general, if the absorption capacity under pressure is less than 20 g / g, there is a possibility that high physical properties may not be exhibited when used in a diaper. On the other hand, the upper limit of the absorption capacity under pressure is not limited, but causes difficulty in production. Therefore, it is considered that about 35 g / g is sufficient considering the cost increase.

  The water-absorbent resin obtained by the production method of the present invention has a weight average particle diameter (D50) preferably controlled to a relatively narrow range of 200 to 450 μm, more preferably 220 to 430 μm, and even more preferably 250 to 400 μm. And the content ratio of particles less than 150 μm is preferably controlled to 0 to 5% by weight, more preferably 0 to 3% by weight, still more preferably 0 to 1% by weight, and The logarithmic standard deviation (σζ) of the particle size is preferably controlled to 0.20 to 0.40, more preferably 0.20 to 0.38, and still more preferably 0.20 to 0.35. In the production method of the present invention, a water-absorbing resin having a specific particle size satisfying the above range can be obtained by performing a classification step before surface crosslinking and after surface crosslinking as necessary. . Furthermore, since the production method of the present invention recycles fine powder, the content of particles (fine powder) of less than 150 μm is small despite having a relatively small weight average particle size of 200 to 450 μm, that is, small. It is possible to obtain a water-absorbent resin having the contradicting physical properties of a particle diameter and a small amount of fine powder. If the weight average particle size (D50), the content ratio of particles less than 150 μm, and the logarithmic standard deviation (σζ) of the particle size are out of the above ranges, high physical properties may not be exhibited when used for diapers.

The water-absorbent resin obtained by the production method of the present invention preferably has an acrylic acid content determined by HPLC determination of 0 to 1000 ppm, more preferably 0 to 500 ppm, more preferably 0 to 200 ppm, and most preferably 0 to 100 ppm. It is. In general, if the acrylic acid content exceeds 500 ppm, the deodorizing action may be reduced critically, which is considered undesirable.
The use of the water-absorbent resin obtained by the production method of the present invention is not particularly limited, but for example, it is preferably used in an absorbent body or an absorbent article. Excellent performance in diapers using a large amount of water-absorbent resin).

The absorbent body using the water-absorbent resin obtained by the production method of the present invention can be obtained, for example, by molding a water-absorbent resin and, if necessary, hydrophilic fibers into a sheet shape, etc., and does not use hydrophilic fibers. In some cases, it can be obtained by fixing a particulate water-absorbing agent to paper or non-woven fabric. The content (core concentration) of the water-absorbent resin in such an absorber is desirably a high concentration, for example, 30 to 100% by weight, preferably 40 to 100% by weight, more preferably 50 to 100% by weight, The amount is preferably 60 to 100% by weight, particularly preferably 70 to 100% by weight. Moreover, it is desirable that the absorber is compression molded in a range of density 0.06 to 0.5 g / cc and basis weight 0.01 to 0.2 g / cm ² . Examples of the fiber base used include, for example, pulverized wood pulp, cotton linters and crosslinked cellulose fibers, rayon, cotton, wool, acetate, vinylon, and other hydrophilic fibers. Preferably, they are airlaid. What you did is good.
For example, in the water-absorbing agent according to the present invention obtained by taking the above production method as an example, the residual monomer amount obtained by the method described later is 0 or more and 500 ppm or less. Preferably they are 0 or more and 400 ppm or less, More preferably, they are 0 or more and 300 ppm or less, More preferably, they are 0 or more and 250 ppm or less, More preferably, they are 0 or more and 200 ppm or less, More preferably, they are 0 or more and 150 ppm or less. When the main component of the monomer used for the polymerization is acrylic acid and / or a salt thereof, the content of unreacted acrylic acid and / or a salt thereof is 500 ppm or less. When the residual monomer amount of the water-absorbing agent of the present invention exceeds 500 ppm, there is a possibility that a strange odor may be generated during swelling after absorption of human urine when actually used in an absorbent article such as a diaper. Considering the possibility of contact, there is a problem in terms of hygiene. Moreover, there is a concern that the powder scattering at the manufacturing site of the absorbent article may adversely affect the health of the worker.

Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. In the following, unless otherwise specified, “parts by weight” is simply referred to as “parts”, and “% by weight” is simply referred to as “%”.
The physical properties of the water-absorbent resins obtained in Examples and Comparative Examples were measured as follows. Each measurement was performed in the range of 23 ± 2 ° C.
<Absorption capacity under no load (GV: Gel Volume)>
About 0.2 g of the water-absorbent resin is accurately weighed (this weight becomes the “weight of the water-absorbent resin” of the following formula), and uniformly placed in a non-woven bag (60 mm × 60 mm), 0.9% sodium chloride It was immersed in an aqueous solution (saline). After 30 minutes, the bag was pulled up, drained at 250 × 9.81 m / s ² (250 G) for 3 minutes using a centrifuge, and the weight W1 (g) of the bag was measured. Further, the same operation was performed without using the water absorbent resin, and the weight W0 (g) at that time was measured. And it computed according to following Formula from these weight W1, W0.

GV (g / g) = [(W1-W0) / weight of water-absorbing resin] -1
<Residual monomer amount>
Weigh 1000 g of deionized water into a plastic container with a lid, add 0.5 g of water-absorbing resin to the water, stir for 2 hours, filter off the water-absorbing resin that has swelled and gelled using filter paper, and obtain the filtrate. Was analyzed by liquid chromatography. On the other hand, the monomer (acrylic acid) standard solution having a known concentration was analyzed in the same manner, and the amount of residual monomer (residual acrylic resin) in the water-absorbent resin was determined using the obtained calibration curve as an external standard and taking into account the dilution rate of the filtrate The amount of acid or its salt in terms of acrylic acid) was determined.

<Solid content of polymerized gel or granulated gel>
About 5 g of polymer gel or granulated gel is accurately weighed in an aluminum cup (diameter 52 mm) (this weight is defined as W0 (g)), dried in a windless dryer at 180 ° C. for 24 hours, and then the weight of the dried residue is measured. Measurement (this weight is defined as W1 (g)), and the solid content (%) was calculated from these weights W1 and W0 according to the following formula. However, when obtaining the solid content rate (%) of the dried polymer gel after the drying step, the drying time was shortened to 3 hours.
Solid content rate (%) = (W1 / W0) × 100
<Absorption capacity under pressure (AAP: Absorbency Against Pure)>
In accordance with the method described in U.S. Pat. No. 6,071,976, the water absorption capacity (60 minutes value) under pressure with respect to physiological saline at 50 g / cm ² (4.9 kPa) was measured.

<Logarithmic standard deviation of particle size (σζ) and weight average particle size (D50)>
According to the method described in WO 2004/069936, sieve classification was performed to determine the logarithmic standard deviation of particle size (σζ) and the weight average particle size (D50).
[Production Example 1]
Endless belt (effective length: 3.8 m, width: 60 cm) coated with fluororesin on the surface, heating means for keeping the bottom and surroundings of the endless belt at about 100 ° C., and for applying light necessary for the polymerization reaction to the endless belt A polymer gel was produced using a belt type continuous polymerization apparatus equipped with a UV lamp. That is, 48.5% sodium hydroxide aqueous solution was 396 g / min, acrylic acid was 493 g / min, 30% polyethylene glycol diacrylate (average molecular weight 487) aqueous solution (I) was 5.2 g / min, and 20% aqueous acrylic acid solution 97 Solution (II) prepared by dissolving 1.0 part of 1-hydroxycyclohexyl phenyl ketone and 1.1 part of 45% diethylenetriaminepentaacetic acid 5 sodium acetate aqueous solution in .9 part and water of 405 g / min Each was set to a flow rate, and continuously supplied to the mixer and mixed to prepare a monomer solution (the temperature of the monomer solution was stable at about 93 ° C.), and the monomer solution was further added by 2%. While adding an aqueous sodium persulfate solution at a flow rate of 27.4 g / min, the monomer mixture for polymerization (flow rate 1333 g / min, in the mixture) The belt is continuously fed on a belt running at a speed of 1 m / min with a monomer concentration of 45% and an amount of sodium persulfate in the mixture corresponding to 0.091% of the weight of the monomer component). Polymerization was performed to form a band-shaped polymer gel, and the generated band-shaped polymer gel was continuously peeled from the belt. The obtained band-shaped polymer gel was crushed by continuously adding it to a screw extruder (die hole diameter 13 mm) while adding water separately at a flow rate of 16.6 g / min to the extruder inlet. A polymer gel (11) was obtained. The solid content of the polymer gel (11) was 54%.

Next, 2000 g of the polymer gel (11) (solid content 1080 g) was spread on a wire mesh, and 180 ° C. using an aeration flow batch dryer (“Type 71-S6” manufactured by Satake Chemical Machinery Co., Ltd.). Dry with hot air for 30 minutes. Next, the obtained dried product is pulverized with a roll mill, and then the particles passing through the sieve are classified using a JIS standard sieve (Z8801) having an opening of 850 μm to obtain a particulate water-absorbing resin (P1). It was.
[Production Example 2]
Except that the dried product was pulverized with a roll mill whose clearance between rolls was narrower than the roll mill of Production Example 1, and then the particles passing through the sieve were classified using a JIS standard sieve having an opening of 150 μm. In the same manner as in Production Example 1, a fine powdery water absorbent resin (P1 ′) was obtained.

Next, 300 g of finely powdered water-absorbing resin (P1 ′) is placed in a 5 L mortar mixer (manufactured by West Japan Testing Machine Co., Ltd.) kept warm in an 80 ° C. water bath, and the stirring blade of the mortar mixer is rotated at a high speed of 60 Hz / 100 V. Then, 420 g of water as an aqueous liquid for granulation was heated to 80 ° C. and then charged at a stroke. Within 10 seconds after charging, the finely powdered water-absorbing resin (P1 ′) and water are mixed to form a granulated product in a paraffin state. By taking out after 1 minute from the charging, a granulated gel having a particle size of 3 to 10 mm. (21) was obtained. The granulated gel (21) had a solid content of 42%.
Next, 2000 g of the granulated gel (21) obtained by repeating the granulation (of which the solid content (corresponding to the amount of fine water-absorbent resin (P1 ′)) is 833 g) is spread on a wire mesh, Using a batch dryer (“Type 71-S6” manufactured by Satake Chemical Machinery Co., Ltd.), it was dried with hot air at 180 ° C. for 30 minutes. Subsequently, it grind | pulverized with a roll mill, and the particle | grains which passed this sieve were classified using the JIS standard sieve (Z8801) of 850 micrometers of openings after that, and the particulate water-absorbing resin (P2) was obtained.

[Production Example 3]
16.7 g of polymer gel (11) obtained in Production Example 1 (solid content 900 g) and 333 g of granulated gel (21) obtained in Production Example 2 (of which solid content (fine powdered water absorbent resin (P1 ′)) 139g) is mixed in a lightly mixed state and spread on a wire mesh, and 180 ° using an aeration flow batch dryer (“Type 71-S6” manufactured by Satake Chemical Machinery Co., Ltd.). It was dried with hot air at 30 ° C. for 30 minutes. Subsequently, it grind | pulverized with a roll mill, and the particle | grains which passed this sieve were classified using the JIS standard sieve (Z8801) of 850 micrometers of openings after that, and the particulate water absorbing resin (P3) was obtained.

[Example 1]
In Production Example 2, instead of 420 g of water used as an aqueous liquid for granulation, 0.069 g of sodium persulfate was added to 420 g of water (corresponding to 0.023% with respect to the fine water absorbent resin (P1 ′)), Except having used the aqueous liquid which melt | dissolved the amount of sodium persulfate used by the superposition | polymerization process (equivalent to 25% with respect to the weight of a monomer component), it is the same as that of manufacture example 2. Thus, a granulated gel (22) having a particle size of 3 to 10 mm was obtained. The granulated gel (22) had a solid content of 42%.
Next, 1667 g (solid content 900 g) of the polymer gel (11) obtained in Production Example 1 and 333 g of the granulated gel (22) (of which the solid content (fine powdered water absorbent resin (P1 ′) 139g, containing 0.032g of sodium persulfate) and spreading on a wire mesh, 180 using a ventilating batch dryer ("Type 71-S6" manufactured by Satake Chemical Machinery Co., Ltd.) Dry with hot air at 30 ° C. for 30 minutes. Subsequently, it grind | pulverized with a roll mill, and the particle | grains which passed this sieve were classified using the JIS standard sieve (Z8801) of 850 micrometers of openings after that, and the particulate water-absorbing resin (1) was obtained. Of the total amount of sodium persulfate contained in the particulate water-absorbing resin (1), sodium persulfate added in addition to the amount used in the polymerization step (0.091% based on the weight of the monomer component). The amount is 0.0031% with respect to the total solid content of the water-absorbent resin (1), and the total amount is added as an aqueous liquid when obtaining a granulated gel.

[Comparative Example 1]
In the same manner as in Production Example 1, a strip-shaped polymer gel was generated, and the generated strip-shaped polymer gel was continuously peeled from the belt. The obtained strip-shaped polymer gel was placed in a screw extruder (die hole diameter 13 mm), and a 0.13% sodium persulfate aqueous solution was separately supplied at a flow rate of 16.6 g / min (the weight of the monomer component in the monomer mixture for polymerization). Was added to the extruder inlet at a rate of 0.0035% relative to the extruder) to obtain a roughly crushed polymer gel (12). The solid content of the polymer gel (12) was 54%.
Next, 1667 g of the polymer gel (12) (containing 900 g solid content, 0.032 g of sodium persulfate (added to the polymer gel)) and 333 g of the granulated gel (21) obtained in Production Example 2 , Solid content (corresponding to the amount of fine water-absorbing resin (P1 ') is 139g) and lightly mixed and spread over a wire mesh, and aeration flow dryer (Satake Chemical Machinery (
Co., Ltd. “Type 71-S6”) was dried with hot air at 180 ° C. for 30 minutes. Subsequently, it grind | pulverized with a roll mill, and the particle | grains which passed this sieve were classified using JIS standard sieve (Z8801) with an opening of 850 micrometers then, and the particulate water-absorbing resin (C1) for a comparison was obtained. Of the total amount of sodium persulfate contained in the particulate water-absorbent resin (C1), sodium persulfate added in addition to the amount used in the polymerization step (0.091% based on the weight of the monomer component). The amount is 0.0031% with respect to the total solid content of the water absorbent resin (C1), and the total amount is added when obtaining the polymer gel.

[Reference Example 1]
2000 g of the polymer gel (12) obtained in Comparative Example 1 (containing 1080 g of solid content and 0.038 g of sodium persulfate (added to the polymer gel)) was spread on a wire mesh, and an air flow batch dryer (Satake) It was dried with hot air at 180 ° C. for 30 minutes using “Type 71-S6” manufactured by Chemical Machinery Co., Ltd. Subsequently, it grind | pulverized with a roll mill, and the particle | grains which pass through this sieve were classified using JIS standard sieve (Z8801) with an aperture of 850 micrometers, and the particulate water-absorbing resin (R1) as a reference was obtained. Of the total amount of sodium persulfate contained in the particulate water-absorbing resin (R1), sodium persulfate added in addition to the amount used in the polymerization step (0.091% based on the weight of the monomer component). The amount is 0.0035% with respect to the total solid content of the water absorbent resin (R1), and the total amount is added when obtaining the polymer gel.

[Example 2]
In Production Example 2, instead of 420 g of water used as an aqueous liquid for granulation, 0.69 g of sodium persulfate was added to 420 g of water (corresponding to 0.23% with respect to finely powdered water-absorbing resin (P1 ′)). A granulated gel (23) having a particle size of 3 to 10 mm was obtained in the same manner as in Production Example 2, except that an aqueous liquid obtained by dissolving the lye was used. The solid content of the granulated gel (23) was 42%.
Next, in place of 333 g of the granulated gel (22) used in Example 1 (including 139 g of solid content (corresponding to the amount of finely powdered water absorbent resin (P1 ′)) and 0.032 g of sodium persulfate) And 333 g of the granulated gel (23) (including 139 g of solid content (corresponding to the amount of fine water-absorbent resin (P1 ′)) and 0.32 g of sodium persulfate) In the same manner as in Example 1, a particulate water-absorbing resin (2) was obtained. Of the total amount of sodium persulfate contained in the particulate water-absorbing resin (2), sodium persulfate added in addition to the amount used in the polymerization step (0.091% based on the weight of the monomer component). The amount is 0.031% with respect to the total solid content of the water absorbent resin (2), and the total amount is added as an aqueous liquid when obtaining a granulated gel.

Example 3
In Production Example 2, instead of 420 g of water used as an aqueous liquid for granulation, 0.69 g of sodium hydrogen sulfite was added to 420 g of water (corresponding to 0.23% with respect to the finely powdered water absorbent resin (P1 ′)). A granulated gel (24) having a particle size of 3 to 10 mm was obtained in the same manner as in Production Example 2, except that an aqueous liquid obtained by dissolving the lye was used. The solid content of the granulated gel (24) was 42%.
Next, in place of 333 g of the granulated gel (22) used in Example 1 (including 139 g of solid content (corresponding to the amount of finely powdered water absorbent resin (P1 ′)) and 0.032 g of sodium persulfate) In addition, 333 g of the granulated gel (24) (including 139 g of solid content (corresponding to the amount of fine powder water-absorbent resin (P1 ′)) and 0.32 g of sodium hydrogen sulfite) was used. In the same manner as in Example 1, a particulate water absorbent resin (3) was obtained. The amount of sodium bisulfite added was 0.031% with respect to the total solid content of the water absorbent resin (3), and the total amount was added as an aqueous liquid when obtaining a granulated gel. It is.

[Comparative Example 2]
In the same manner as in Production Example 1, a strip-shaped polymer gel was generated, and the generated strip-shaped polymer gel was continuously peeled from the belt. Then, the obtained band-shaped polymer gel was put into a screw type extruder (die hole diameter 13 mm), and a 1.3% sodium persulfate aqueous solution was separately supplied at a flow rate of 16.6 g / min (the weight of monomer components in the monomer mixture for polymerization). Was added to the extruder inlet at a rate of 0.035% relative to the extruder) to obtain a coarsely polymerized polymer gel (13). The solid content of the polymer gel (13) was 54%.
Next, 1667 g of the polymer gel (13) (containing 900 g of solid content, 0.32 g of sodium persulfate (added to the polymer gel)) and 333 g of the granulated gel (21) obtained in Production Example 2 , Solid content (corresponding to the amount of fine water-absorbing resin (P1 ') is 139g) and lightly mixed and spread over a wire mesh, and aeration flow dryer (Satake Chemical Machinery ( Co., Ltd. “Type 71-S6”) was dried with hot air at 180 ° C. for 30 minutes. Subsequently, it grind | pulverized with the roll mill, and the particle | grains which passed this sieve were classified using JIS standard sieve (Z8801) with an aperture of 850 micrometers after that, and the particulate water-absorbing resin (C2) for a comparison was obtained. Of the total amount of sodium persulfate contained in the particulate water-absorbing resin (C2), the amount of sodium persulfate added in addition to the amount used in the polymerization step (0.091% based on the weight of the monomer component). The amount is 0.031% with respect to the total solid content of the water absorbent resin (C2), and the total amount is added when obtaining the polymer gel.

[Reference Example 2]
2000 g of the polymer gel (13) obtained in Comparative Example 2 (containing 1080 g of solid content and 0.38 g of sodium persulfate (added to the polymer gel)) was spread on a wire mesh, and an air flow batch dryer (Satake) It was dried with hot air at 180 ° C. for 30 minutes using “Type 71-S6” manufactured by Chemical Machinery Co., Ltd. Next, the mixture was pulverized with a roll mill, and then the particles passing through the sieve were classified using a JIS standard sieve (Z8801) having an opening of 850 μm to obtain a particulate water-absorbing resin (R2) as a reference. Of the total amount of sodium persulfate contained in the particulate water-absorbing resin (R2), sodium persulfate added in addition to the amount used in the polymerization step (0.091% based on the weight of the monomer component). The amount is 0.035% with respect to the total solid content of the water absorbent resin (R2), and the total amount is added when obtaining the polymer gel.

  Tables 1 and 2 show the absorption capacity under no load (GV) and the amount of residual monomer for each of the water absorbent resins obtained in the above production examples, examples, comparative examples and reference examples.

From Tables 1 and 2, the following is clear.
That is, first, Production Example 1 is a case where only the polymer gel is dried without recycling the fine powder (residual monomer amount 350 ppm), whereas Production Example 2 in which only the granulated gel obtained by granulating the fine powder is dried. Then, it can be seen that the residual monomer is increased to 430 ppm. Next, when the polymer gel and the granulated gel were dried together in Production Example 3 and the fine powder was recycled, the residual monomer amount was 530 ppm, which was larger than Production Example 1 and Production Example 2, and It can be seen that the amount is significantly larger than the residual monomer amount (361 ppm) theoretically determined from the results obtained in Production Example 1 and Production Example 2 in consideration of the mixing ratio of the polymer gel and the granulated gel.

Example 1 is a case where sodium persulfate was added to the granulated gel when recycling the fine powder. According to this, the amount of residual monomer was 350 ppm, which is very small compared to Production Example 3, and Production Example 1 It is clear that this is the same as when no fine powder is recycled. Moreover, it can be seen from Example 2 that if the amount of sodium persulfate added to the granulated gel is increased, the amount of residual monomer is further reduced as compared with the case where the fine powder of Production Example 1 is not recycled.
On the other hand, in Comparative Example 1 in which the same amount of sodium persulfate as in Example 1 was added to the polymerization gel, it was found that the residual monomer amount was 530 ppm, which was not reduced compared to Production Example 3. Further, even in Comparative Example 2 in which the amount of sodium persulfate added to the polymer gel is increased, the amount of residual monomer is smaller than that in Production Example 3, but the amount of residual monomer is smaller than that in Production Example 1 where the fine powder is not recycled. It turns out that there will be more.

  Example 3 is an example in which sodium bisulfite was added to the granulated gel when recycling the fine powder. Similar to the example in which sodium persulfate was added to the granulated gel, the amount of residual monomer was compared with that in Production Example 3. It turns out that it decreases.

  From the above, according to the present invention, it is clear that the recycling of fine powder and the reduction of residual monomer can both be achieved very effectively.

Example 4
By removing fine powder of less than 150 μm from the water absorbent resin (1) obtained in Example 1 using a JIS standard sieve of 150 μm, the total amount of the water absorbent resin (1) having a particle diameter of 850 μm to 150 μm. ') Got. Next, to 100 parts of the water-absorbent resin (1 ′), after mixing a surface cross-linking agent composed of a mixed liquid of 0.34 parts of 1,4-butanediol, 0.56 parts of propylene glycol and 3 parts of water, The obtained mixture was heat-treated at 210 ° C. for 30 minutes to obtain water-absorbing resin particles whose surfaces were crosslinked. When the physical properties of the water-absorbent resin particles were measured, the absorption capacity under no load (GV) was 31 g / g, the absorption capacity under load (AAP) was 26 g / g, the residual monomer amount was 300 ppm, and the weight average particle diameter (D50). ) Was 420 μm, the content of particles (fine powder) less than 150 μm was almost 0% by weight, and the logarithmic standard deviation (σζ) of the particle size was 0.35.

The method for producing a water-absorbent resin and the water-absorbent resin according to the present invention can be suitably applied to the production of absorbent articles such as sanitary materials including absorbents such as paper diapers, sanitary napkins, and incontinence pads.

Claims (7)

A step of polymerizing a monomer mainly composed of acrylic acid and / or a salt thereof to obtain a polymer gel having water absorption;
Fine powder obtained in the production of the water-absorbent resin obtained from the polymer gel and having a weight average particle diameter in the range of 10 to 150 μm is at least selected from the group consisting of a thermal decomposition type radical polymerization initiator, an oxidizing agent and a reducing agent. A step of obtaining a granulated gel by adding an aqueous liquid containing an additive capable of reacting with one monomer;
A method for producing a water-absorbent resin, comprising a step of drying the granulated gel and the polymer gel together.   The method for producing a water absorbent resin according to claim 1, wherein the aqueous liquid is heated in advance before being added to the fine powder.   The method for producing a water absorbent resin according to claim 1, wherein the additive contains a persulfate.   In the step of drying by coexisting the granulated gel and the polymer gel, the ratio of the solid content ratio A (%) of the granulated gel to the solid content ratio B (%) of the polymer gel (A / The method for producing a water absorbent resin according to any one of claims 1 to 3, wherein B) is 1/3 or more and 3 or less.   In the step of allowing the granulated gel and the polymer gel to coexist and drying, the solid content in the granulated gel is 40% by weight or less based on the solid content in the polymer gel. Item 5. A method for producing a water absorbent resin according to any one of Items 1 to 4. A water-absorbent resin comprising a polymer gel having water absorbency obtained by polymerizing a monomer mainly composed of acrylic acid and / or a salt thereof, and the granulated gel, wherein the granulated gel is the polymer It consists of fine powder obtained in the production of a water-absorbent resin obtained from a gel and the weight average particle diameter is in the range of 10 to 150 μm, and the solid content ratio A (%) of the granulated gel and the solid content ratio of the polymer gel A water absorbent resin having a ratio (A / B) to B (%) of 1/3 or more and 3 or less and a residual monomer of 0 or more and 500 ppm or less.   The water-absorbent resin according to claim 6, which is produced by the production method according to claim 1.