Specification
The title of the invention: Mars out the enhanced super-absorbent resin and a method of manufacturing
Art
[1]
This application claims the benefit of priority based on January 7, character call Korea Patent Application No. 10-2015-0001839, 2015, all contents disclosed in the literature of the Korea patent application is included as a part of this specification.
[2]
To the present invention improves the out Mars improved superabsorbent resin and relates to a manufacturing method thereof, wherein the out chemical conversion and more particularly improved superabsorbent polymer comprises a super-absorbent resin, the fine particles and water out of the superabsorbent resin Mars characterized in that in order to prevent the high-absorbent resin or agglomeration (caking) of the particles or by controlling the temperature of the water during the aging (aging) time when the input stirred water.
BACKGROUND
[3]
Superabsorbent resin (Superabsorbent Polymers, SAPs) is a synthetic polymeric material having the ability to absorb water of 500 to 1000 times of its own weight or so, to start to put to practical use in sanitary fittings, now paper Children's diaper, in addition to the sanitary hygiene products such as sanitary materials such as a material for maintaining the freshness and foment in the gardening soil for repair filler, civil engineering, building materials index, seedling sheet for food distribution sector it is widely used. Accordingly, it is a super-absorbent resin (Super Absorbent Polymer, SAP) is the market value's getting more and more widened its application range is known to have an excellent absorption capacity when compared to conventional absorbent material to high. In particular, there is a high water-absorbent resin with superior water absorption capacity, is often used in infant diapers, adult diapers, such as sanitary material use, a high water-absorbing resin present in a diaper, especially when applied to the sanitary material is to serve to absorb urine and maintain. On the other hand, super-absorbent resin in the process of manufacturing the diaper will receive an intense pressure and physical impact, a drop in physical properties in this process has the disadvantage that as a result appeared severely fall the performance of the diaper.
[4]
In this connection, however, discloses a method for manufacturing such a water-absorbent resin of the conventional techniques, including the water-insoluble inorganic fine particles, etc. in Korea Patent Publication No. 2012-0081113 conventional call when the moisture of the surface of the superabsorbent resin increases in the surface by problems such that the viscosity is increased to the decrease in a flocculation, workability and productivity occurs above occurs, it was difficult to satisfy the high water content and high porosity at the same time point.
[5]
On the other hand, when room temperature and added water to the relatively high water-absorbent resin at a lower temperature, and is subjected to the temporal limitation of the water-absorbent resin spread on the surface. Therefore, to reduce the agglomeration phenomenon, there is a problem for the factor of reducing the productivity to be increased to aging (aging) time of the high water-absorbent resin not containing water is stabilized. Thus, when he put an additional water to the water-absorbent resin and uniformly as possible how the function is required, without bunching phenomenon (caking), also without bunching occurs, the function should not result in bunching under long-term loads. When introducing water to the superabsorbent polymer to fix this, does not occur agglomeration of the superabsorbent polymer and at the same time give it the property improvements and new features is the actual circumstances that the requirements and the development of efficient technology.
Detailed Description of the Invention
SUMMARY
[6]
The present invention for solving the problems of the prior art,
[7]
Superabsorbent resin out in accordance with the present invention Mars improved the load reduction in the production process, super-absorbent resin modify the surface to not increase the viscosity and degree of compaction according to the water absorption and maintain the particle size, do not have the workability decreases, the particle size and physical properties of the control for its object to facilitate.
[8]
In addition, the superabsorbent resin out in accordance with the present invention, chemical conversion is improved is when the input a large amount of water, by adjusting the temperature higher than room temperature in an elevated condition or significantly reduce the aggregation phenomenon of the water absorbent resin bunching is not occur, and aging ( by adjusting the aging) time as its object to prevent aggregation phenomena.
[9]
Accordingly, the present invention is high and while stored or transported to the final product, added water to the water-absorbent resin which can fundamentally prevent the inter-particle aggregation of the water absorbent resin, out to provide an improved superabsorbent polymer Mars is an object .
Technical Solution
[10]
The invention In order to achieve the above object,
[11]
A high water absorbent resin (A), to i) and ii) particles (B), and the out comprises water (C) Mars improved superabsorbent polymer has the characteristics of,
[12]
The particles (B) is the high includes the water absorbent resin (A) 100 parts by weight of 0.0001 to 15.0 parts by weight based on the water (C) is a super-absorbent resin (A), and to 100 parts by weight of the particles (B) about 0.1 to 20.0 parts by weight is contained, provides a heat treatment and aging (aging) time adjustment process at least the enhanced superabsorbent resin, characterized in that the out Mars prepared by one or more of the processing.
[13]
i) 300 to 1500 m 2 BET specific surface area / g (specific surface area),
[14]
ii) more than 50% porosity (porosity)
[15]
In another aspect, the present invention,
[16]
a) adding to said particles (100 parts by weight of 0.0001 to 15.0 parts by weight of the addition of the super-absorbent resin (A) to B) having the following properties i) and ii) a water absorbent resin (A); And
[17]
b) said step a) the tough, super-absorbent resin (A) and the particles (and the water (C) to B) the water absorbent resin (A) and the particles (B) 0.1 based on 100 parts by weight to 20.0 input to parts by weight It provides a method of chemical conversion comprising the out-enhanced super-absorbent resin, and heat treatment and aging (aging) time control processing of the at least one out by the processing steps for producing the chemical conversion improved superabsorbent polymer.
[18]
i) 300 to 1500 m 2 BET specific surface area / g (specific surface area),
[19]
ii) more than 50% porosity (porosity)
Effects of the Invention
[20]
Supplying of water to the superabsorbent polymer at room temperature or a relatively low temperature in the conventional process and because receiving the time limit of the moisture diffusion from the water-absorbent resin surface, has not been stabilized containing water to reduce agglomeration (caking) developing and due to problems such as increased time for the aging of the water-absorbent resin was a limit to the productivity decreases. Out in accordance with the present invention to improve such a problem, according to an improved superabsorbent polymer and a method of manufacturing the resistance, control the temperature of the highly water-absorbing resin, water or a stirrer, or when out of the high-absorbent resin added to the water to enhance the chemical conversion It can be prevented from bunching (caking) of the particles by controlling the aging (aging) time. At this time, each of the variables can be adjusted alone or in combination with the control one or more conditions. Thus, in an elevated condition by controlling the high temperature than at room temperature, or reduced aggregation phenomenon of the water-absorbent resin can be remarkably and aggregation does not occur, or adjusting the aging (aging) time has a characteristic of preventing the aggregation phenomenon.
[21]
In addition, out according to the invention the superabsorbent resin is flammable improved is high, and to modify the water-absorbent resin surface keep the particle size by not increase in viscosity or agglomeration of the water-absorbing, and thus the load decreases in the manufacturing process through increased processability , particle size, and it is easy to control physical properties.
[22]
Therefore, according to the present invention, and then added to the water-absorbent resin finally has the advantage that can be blocked between the bunching of the superabsorbent resin particles as fundamentally during storage or transfer to the product.
Brief Description of the Drawings
[23]
When you put the present invention Mars improved high 1A is heated to compare the bunching difference of the superabsorbent resin particles due to the temperature of the water-absorbent resin were introduced into water, the experimental results in the case of FIG. 1B is added to water at room temperature the picture shown.
[24]
Figure 2 is when the out of the present invention, chemical conversion is enhanced and proceed straight caking test without aging (aging) for a water-absorbent resin to ensure the aggregation degree of the after aging (aging) time added water at room temperature conditions ( 0 a photograph showing an experimental result of min).
[25]
If 3 is given for 30 minutes of the aging (aging) in order to verify the out degree of aggregation according to the after aging (aging) time that the chemical conversion is enhanced and the water absorbent resin added with water at room temperature, the condition of the present invention (30 min) of a photograph showing an experimental result.
[26]
4 is a graph showing the particle size distribution according to aging (aging) time out of Mars improved superabsorbent polymer of the present invention.
[27]
Figure 5 is a graph showing the particle size distribution according to the input temperature of the water out of the chemical conversion is enhanced super-absorbent resin of the present invention.
Best Mode for Carrying out the Invention
[28]
Hereinafter, the present invention will be described in detail.
[29]
[30]
Out in accordance with the present invention Mars enhanced super-absorbent resin,
[31]
A high water absorbent resin (A), to i) and ii) particles (B), and the out comprises water (C) Mars improved superabsorbent polymer has the characteristics of,
[32]
The particles (B) is the high includes the water absorbent resin (A) 100 parts by weight of 0.0001 to 15.0 parts by weight based on the water (C) is a super-absorbent resin (A), and to 100 parts by weight of the particles (B) about 0.1 to 20.0 parts by weight is contained, by the heat treatment and aging treatment at least one of the treatment (aging) time control is characterized in that manufacture.
[33]
i) 300 to 1500 m 2 BET specific surface area / g (specific surface area),
[34]
ii) more than 50% porosity (porosity)
[35]
[36]
More specifically, the heat treatment is high-absorbent resin (A) and the particles (B); agitator; And can be water heated to at least any one or more temperatures selected from the group with 26 ~ 95 ℃ made, the object of temperature control for temperature raising is highly water-absorbing resin and particles wherein the fine, is used in water or stirring process during aging (aging) It can control the temperature of the agitator and the like. When the heat treatment in the above range, then put into water than the superabsorbent resin in 15 ~ 25 ℃ the aggregation between particles deolhae has the advantage of reducing the aging (aging) time. This means that the process time can be shortened as well as a simplified process. In the temperature range lower than the range can not be obtained an effect of reducing the aging time, the temperature higher than the above range and to increase the absorption rate of the water absorbent resin is difficult to increase the evaporation of water or even moisture.
[37]
In the present invention, one implementation, the high is 60 ~ 70 ℃ temperature of the superabsorbent polymer (SAP) which during the manufacturing process of the absorbent resin, passed through a cooler and classifying after the surface cross-linking of, separately and processed to increase the temperature of the water-absorbent resin When the input directly in the water phase, even if not all appear the effect described above can be not necessary the addition of the additional energy.
[38]
[39]
Further, the aging (aging) time adjustment process is added water (C) to the superabsorbent resin (A) and particles in the 15 ~ 25 ℃ (B) and at a temperature of 26 ~ 95 ℃ for 1 to 120 minutes 5 ~ 1500 by stirring the rpm to characterized in that aging (aging), when the aging (aging) treatment in the above range, can inject water to the superabsorbent resin, and not the agglomeration occur in the course of up to packing prevent bunching phenomenon .
[40]
Also, the function is not high even if aggregation occurs in the water-absorbent resin, there are cases that aggregation occurs under the long-term continuous loading, it is possible to prevent this from occurring. The potential range than the aging (aging) lead to a shorter time when the aggregation between particles, and the case that the above range than aging (aging) time is lengthened, the unnecessary process is not economical.
[41]
Further, the heat treatment and aging (aging) when the time adjustment process to proceed at the same time, super-absorbent resin (A) and the particles (B); agitator; And water, and heating at least one or more temperatures selected from the group with 26 ~ 95 ℃ made, by stirring with 5 ~ 1500 rpm for 1 to 120 minutes at a temperature of 15 ~ 25 ℃ can be characterized in that aging (aging) is. In this case, the particle size was in accordance with the aging (aging) time distribution, the properties such as flowability and apparent density not a great change by aging (aging) time. These results Supplying of water to the superabsorbent resin in a heated condition means that the decrease in the amount of time required for aging than when put into water at room temperature considerably.
[42]
On the other hand, and at a temperature of room temperature of 15 ~ 25 ℃, even if input of water to the water-absorbent resin may be generated a phenomenon agglomeration (caking) increasing the time for aging (aging), This is due to problems such as the need to increase the aging time there may be a disadvantage that productivity is decreased.
[43]
[44]
The out Mars is improved and the particles having the property of the i) and ii) in the water-absorbent resin (B) has said high that contained water absorbent resin (A) 100 parts by weight of 0.0001 to 15.0 parts by weight based on the, and preferably, the high it contained water absorbent resin (a) 100 parts by weight of 0.001 to 2.0 parts by weight based on the more preferred, and most preferably comprises from 0.05 to 0.15 parts by weight. It is not sufficient to obtain the effect to lower than expected when the range of the included amount of particles (B), if it exceeds the above range, is to use the particles (B) in an excess amount is not economically preferred.
[45]
In general, high by the surface of the water absorbent resin is ttuimyeo hydrophilicity, etc. capillary forces, van der Waals forces between the hydrogen bond, the polymer cross section spread (inter-particaular diffusion) or particles by the water present between the particles during after moisture absorption drying rain becomes irreversible aggregation occurs. Therefore, there is high in essential use of water as in polymerization and the surface cross-linking step of the water-absorbent resin, because the agglomeration according to this generation, increase the internal load, may result in the risk of equipment failure. In addition, super-absorbent resin of the agglomerated state as described above has the disadvantage that because of the size to the particle size is not suitable for the application, to introduce the shredding process to reduce them to an appropriate particle size. In addition, there was a problem that since a strong force is applied in the pulverizing process may cause a decline in accordance with the physical properties superabsorbent resin crushing.
[46]
In order to solve the above problems, when a high is present on the surface of the water absorbent resin, attempt has been made to introduce a variety of fine particles which can serve to prevent the direct agglomeration between the resin particles, the fine particles have an excess is to be introduced aggregation but is prevented, there is a disadvantage that the absorption characteristics of the superabsorbent resin decreases.
[47]
In order to solve the above problems, fine particles to be introduced into the super-absorbent resin of the present invention has a particle size of 2 ~ 50 ㎚ ㎛. In addition, the fine particles 300 to 1500 m 2 / g, preferably 500 to 1500 m 2 / g, more preferably 600 to 1500 m 2 / g of BET specific surface area (specific surface area) can have a can. In addition, the contact angle is more than 125 ° for the second hydrophobic fine particles are water, preferably 140 ° or more may have a superhydrophobic more preferably more than 135 ° superhydrophobic. In addition, the particles (B) have a contact angle of about 2 ~ 50 ㎚ ㎛ particle size and the water may have a more than 125 ° superhydrophobic.
[48]
In addition, the fine particle is more than 50% porosity (porosity), preferably have at least 90% porosity (porosity). Since out this chemical conversion improved superabsorbent polymer of the invention is to use the fine particles having the characteristics as described above, not only can reduce the water influence on the resin surface, because the use of the microparticles, considerably agglomeration It can be reduced, and can be relatively easily by the permeability is easily improved, and maintenance thereof howler quantity using a small amount of fine particles.
[49]
The particles to be added in the process of the super-absorbent resin produced according to the invention (B) has no If materials having the same properties as the limitation of its components, in particular silica (SiO 2 ), alumina, titania (TiO 2 ), carbon (carbon) may be used an inorganic oxide, an inorganic compound, an organic polymer, ion exchange resins, metals, metal salts, such as, but not limited to.
[50]
In addition to the process of adding the fine particles, used after my dispersing the monomer solution, the polymerization after the function gel was added to the dry mix, the surface cross-linking solution is within the dispersion or organic solvent that melts during the surface cross-linked to the primary dried resin particles after mixing, the surface cross-linking during the surface cross-liquid separation with water or an organic solvent which may be used to melt a method such as dry mixing in the final product of the dry mixing, or the surface cross-linking, this is not particularly limited.
[51]
[52]
The out Mars is enhanced in the high-absorbent resin with water (C) is high that contained water absorbent resin (A) and the particles (B) is preferably contained 100 parts by weight of 0.1 to 20.0 parts by weight with respect to, 1.0 to 10.0 parts by weight it is most preferred to be contained, and even more preferably, 2.5 to 7.5 parts by weight. Is less than the above range, the amount included in the water (C) not sufficient to obtain within the friability, the than the large viscosity of the resin surface (stickiness) is increased above the range, the ratio of the occurrence irreversible agglomeration (irreversible agglomeration) between the super-absorbent resin particles is the particle size is changed at the same time as the workability of the resin falls may cause problems difficult to use as a product.
[53]
In the manufacturing process of the high-absorbent resin it is used in several different ways, including water to make a polymerization medium, facilitating the dispersion of the cross-linking solution in the surface cross-linking process. In addition to the role of anti-static agents and plasticizers for the residual moisture of the final resin product, inhibits the very small super-absorbent resin fine particles (dust) formed in the application process to prevent the crushing of the high water-absorbent resin particles. In general, however, and a small amount even as the water-absorbent resin even upon addition of water, the viscosity of the resin surface by the absorbed water on the surface and (stickiness) is increased, the high ratio between the water-absorbent resin particles irreversible agglomeration (irreversible agglomeration) is generated do. This increase in viscosity and aggregation, reduce the load increases, such as workability (processability) of the manufacturing and application processes, and consequently increases the particle size of the water absorbent resin, causing a reduction in physical properties and productivity decreases. So far, high research on the water-absorbent resin is eoteumyeo is made the main study of the surface cross-linking for an increase in the polymerization step and the absorption capacity improvement over this, and high surface properties of the water absorbent resin or the pressure-absorbing ability, improvement of the transmission rate or a high water-absorbent resin bar surface characteristics change research is conducted in order to solve some problems, such as the prevention (anti-caking) hardened during storage of.
[54]
By the present invention, and by the addition of further water to the water-absorbent resin in the above range by increasing the water content and to the water to minimize physical damage to the high-absorbent resin to act as a plasticizer satisfy the water content and high porosity at the same time, the high-absorbent resin It can be increased within the friability. Using the water heated in the process, or the like and increasing the temperature of the water-absorbent resin, can be reduced and the injected water is spread on the water-absorbent resin speeds the aging time compared to existing. Therefore, if high water-absorbent resin is applied to the final products, such as diapers, for example, it has the advantage to minimize the deterioration of physical properties due to the crushing of the super-absorbent resin according to the compression of the feed air or strong diaper production process.
[55]
[56]
The superabsorbent resin (A) used in the above high-absorbent resin is improved out Mars
[57]
a) to the monomer composition including a water-soluble ethylenically unsaturated monomer and a polymerization initiator, a thermal polymerization or photo polymerization step to prepare the gel-like function polymer;
[58]
b) drying the gel-like function polymer;
[59]
c) said step of obtaining a water-absorbent resin particles by crushing the dried gel polymer functions; And
[60]
d) characterized in that the said high by the addition of the surface cross-linking agent to the water absorbent resin particles produced by a step of the surface cross-linking reaction proceeds.
[61]
For reference, the term superabsorbent resin particles described in the present invention is a drying and pulverizing the polymer gel-like function. More specifically, the function gel polymer is a water-absorbent resin and a material is the polymerization is complete, or more, including a large amount of moisture (50% or more) and the size of the solid jelly form 1cm in, is dried and ground to the functional gel polymer made with powder the particle. Therefore, the function corresponds to a gel-like polymer is the intermediate state of the process.
[62]
First, the super-absorbent resin used in the present invention (A) is a) to the monomer composition including a water-soluble ethylenically unsaturated monomer and a polymerization initiator, a thermal polymerization or photopolymerization subjected to a step of preparing the gel polymer function.
[63]
In order to manufacture the super-absorbent resin of the present invention, it is possible to prepare the polymer by step and a method commonly used in the art. Specifically, in the high-absorbent resin produced in the present invention, the monomer composition includes a polymerization initiator, when the photopolymerization method according to the polymerization method, contains the photopolymerization initiator, when the thermal polymerization methods include thermal polymerization It may include initiators and the like. However, even if the photopolymerization method may be a certain amount of heat by radiation, such as ultraviolet irradiation occurs, and also includes so the heat of a certain degree with the progress of the exothermic polymerization reaction occurs, further a thermal polymerization initiator.
[64]
A thermal polymerization initiator to be used in high-production method of the water-absorbent resin according to the present invention although there is no particular limitation, and preferably a persulfate-based initiator, an azo initiator, at least one selected from the initiator, the group consisting of hydrogen peroxide and ascorbic acid to It can be used. Specifically, the persulfate-based initiator of examples and sodium sulfate (Sodium persulfate; Na2S2O8), potassium persulfate (Potassium persulfate; K2S2O8), ammonium persulfate (Ammonium persulfate; (NH4) 2S2O8) and the like, and azo (Azo) based Examples of initiators include 2, 2-azobis- (2-amidinopropane) dibasic acid salt (2, 2-azobis (2-amidinopropane) dihydrochloride), 2, 2-azobis- (N, N- di-methylene) isobutoxy Thira Mai Dean dihydrochloride (2,2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride), 2- (carbamoyl-azo) isobutyronitrile nitrile (2- (carbamoylazo) isobutylonitril), 2, 2- azo bis [2- (2-imidazolin-2-yl) propane] dihydrochloride (2,2-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride), 4,4- azobis- (4-cyano valeric acid) and the like can be used (4,4-azobis- (4-cyanovaleric acid)).
[65]
In addition, the photopolymerization initiator used in the production method of the high-absorbent resin according to the invention There is no particular restriction, preferably benzoin ethers (benzoin ether), dialkyl acetophenones (dialkyl acetophenone), hydroxyl alkyl ketones (hydroxyl alkylketone), phenyl glyoxylic rate (phenyl glyoxylate), benzyl dimethyl ketal (benzyl dimethyl ketal), acylphosphine (acyl phosphine) and alpha-amino ketone (α-aminoketone) to the group consisting in selecting which one or more of the use can be . On the other hand, Specific examples of the acylphosphine, lucirin to commercial TPO, that is, 2,4,6-trimethyl-phosphine oxide may be used (2,4,6-trimethyl-benzoyl-phosphine oxide trimethyl) - benzoyl .
[66]
Further, in the method for producing a highly water-absorbing resin according to the present invention, the water-soluble ethylenically unsaturated monomers but if a monomer which is usually used in the high-absorbent resin produced is no particular limitation, preferably, the anionic monomers and their salts, non- -ionic hydrophilic-containing monomer, and an amino group-containing unsaturated monomer, and may be any one or more selected from the group consisting of quaternary his cargo. Specifically, acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloyl ethane sulfonic acid, 2-meth acryloyl ethane sulfonic acid, 2- (meth) acryloyl propane sulfonic acid, or 2 (meth) acrylamide-2-methylpropane sulfonic acid anionic monomers and their 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 (N, N) - dimethylaminoethyl (meth) acrylate or (N, N) - dimethyl-aminopropyl (meth) amino group-containing acrylamide unsaturated monomer, and preferably at least one selected from the group consisting of His quaternary cargo it can be used, it can be used more preferably acrylic acid or its salt, in the case of acrylic acid monomer or a salt thereof, in particular has the advantage that the absorbability is improved to obtain a high water-absorbent resin.
[67]
And, the method of manufacturing a super-absorbent resin according to the present invention, can include a certain amount of the water-absorbent resin powder and fine powder, that is a polymer or resin powder is less than the particle size produced 150㎛ has the monomer composition for the effect according to the recycling and, specifically, may be added to the polymer or resin powder is less than the particle size of 150㎛ around the starting polymerization of the monomer composition, a polymerization reaction or after the initial start, middle, and late stage. This amount added is possible but only when, it is preferred for the final manufacturing properties prevent deterioration of the superabsorbent resin is to add 1 to 10 parts by weight for 100 parts by weight of the monomer contained in the monomer resin composition.
[68]
On the other hand, in the method of the super-absorbent resin produced according to the present invention, the concentration of the water-soluble ethylenically unsaturated monomers of monomer composition may be appropriately selected in consideration of the polymerization time and the reaction conditions, and the like, preferably 40 to 55% by weight It can be made. If less than 40% by weight concentration of the water-soluble ethylenically unsaturated monomer, and disadvantageous in economic aspect, if it exceeds 55% by weight, the grinding efficiency when grinding a function of the polymerization the gel polymer may appear low.
[69]
In this monomer composition, such as a thermal polymerization or photo polymerization if a polymerization method that is also conventionally used method of preparing a gel polymer functions, there is no limitation in its configuration. Specifically, the polymerization method if significant heat classified into polymerization and photopolymerization, may be the case to proceed with the conventional thermal polymerization proceeds in a reactor with a kneader (kneader) was stirred as the axis, proceeding to the photopolymerization according to the polymerization energy source, moving may proceed in a reactor equipped with a conveyor belt as possible, and the above-described polymerization method is an example, the invention is not limited to the above-described polymerization method.
[70]
For example, depending on the stirring shaft type provided in the thus obtained into a reactor such as a kneader (kneader) having stirring shaft, as described above, supplying hot air, or by heating the reactor to a heat polymerization function gel polymer is a reactor, the reactor outlet function gel polymer to be discharged may be a few centimeters to a few millimeters form. Specifically, the size of the resulting polymer gel is a function may appear to vary in concentration and addition rate of the monomer composition to be injected, and usually has a particle size can be obtained a gel-like polymer which is a function of 2 to 50 mm.
[71]
Further, when the photopolymerization proceeds from having a movable conveyor belt reactor as described above, usually in the form of a function obtained gel-like polymer may be a polymer gel sheet on the function with the width of the belt. At this time, the thickness of the polymer sheet is preferable to supply the monomer composition to be passed depending on the concentration and the addition rate of the monomer composition to be injected, the polymer on the sheet with a thickness of usually 0.5 to 5cm obtained. When the thickness of the polymer on the sheet fed a monomer composition so excessively thin, undesirable low production efficiency, when the polymer thickness on the sheet is greater than 5cm, due to the excessively large thickness, the polymerization reaction take place uniformly throughout the thickness can not.
[72]
Not necessarily a light source that can be used in the photopolymerization step is particularly limited, ultraviolet light sources are known which may cause photo-polymerization reaction can be used without any other restriction. For example, it is possible to use light of a wavelength of about 200 to 400nm, Xe lamp, can be used an ultraviolet light source such as a mercury lamp or a metal halide lamp. And, the photopolymerization step is about 0.1 mw / cm 2 to about 1 kw / cm 2 may be made for a strength of about 5 seconds to about 10 minutes. If the time and intensity of light applied to the photo-polymerization reaction it is too small or short, and the polymerization reaction may not occur sufficiently, is too large or long may be a quality deterioration of the superabsorbent resin.
[73]
Thereafter, in step b) subjected to a step for drying the polymer gel-like function.
[74]
Wherein a) the water content is usually a function of the gel-like polymer obtained in step is 30 to 60% by weight. On the other hand, the specification of the "water content" is the total function, a gel polymer by weight in total, and occupied means a value obtained by subtracting the weight of the polymer in the dry state in the weight of the function gel polymer in an amount of water (specifically, via infrared heating defines the process of looking up the temperature of the polymer dried to a value calculated by measuring the weight reduction of the evaporation of water in the polymer. in this case, the drying conditions after raising the temperature from room temperature to 180 ℃ shot by maintaining at 180 ℃ the drying time is set to 20 minutes including a temperature increase step 5 minutes, to measure the moisture content.)
[75]
Wherein a) the gel polymer resulting from the step function is I through a drying step, preferably, the drying temperature of the drying step may be 150 ℃ to 250 ℃. On the other hand, can be defined as the temperature of the drying reactor, including the polymer, and the heating medium in the temperature or drying step of the heating medium supplied to the "drying temperature" in the present specification is dried.
[76]
If the drying temperature is less than 150 ℃, milling process is excessively long drying time and is a fear that the physical properties of the highly water-absorbing resin to be the final form reduced, if the drying temperature exceeds 250 ℃, dried only excessively polymer surface, comprising further It may occur in the differential, and there is a possibility that physical properties of the highly water-absorbing resin to be the final form to be lowered. Preferably, the drying is at a temperature of 150 ℃ to 250 ℃, it may proceed in a temperature more preferably of 160 ℃ to 200 ℃.
[77]
On the other hand, when the drying time, in consideration of process efficiency, but limited in its configuration, may proceed for 20 minutes to 90 minutes.
[78]
[79]
And, this method of drying, such as drying step, too, so long as it is usually used in the drying step of the function polymer gel, is selected without limitation of its construction can be used. Specifically, the drying step may be carried out by means of a hot air supply, infrared irradiation, microwave irradiation, UV irradiation or the like. The water content of the polymer after the drying step, such progress may be 0.1 to 10% by weight.
[80]
On the other hand, production method of the high-absorbent resin according to the present invention is to increase the efficiency of the drying step, if necessary, may be subjected to a step of simply grinding before drying step. Comprising simply crushed before the drying step can be pulverized particle size of the function gel polymer so to 1mm to 15mm, is that the particle size of the polymeric grinding causes a less than 1mm is difficult technically because of the high water content of the function, the gel polymer, and also between the pulverized particles to agglomerate with each other and appear this phenomenon, when the particle size is milled to more than 15mm, it becomes negligible, the effect of further increasing the drying step according to the grinding efficiency.
[81]
For the step of simply crushing before the drying step, but grinder to be used 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), the cutting mill (cutter mill), disc grinders (Disc mill), pieces of shredders (Shred crusher), crusher (crusher), chopper (chopper) and one-plate type cutter (Disc cutter) as consisting of crushed It may include any one selected from the group unit, but is not limited to the aforementioned example.
[82]
In this case, as going through the step of grinding to increase the drying efficiency before the drying step, due to the high water content of the polymer, it may lead to a sticking phenomenon on the surface grinder. Thus, this in order to increase the efficiency of the grinding step before drying of the gel-like function polymer, when pulverized, can be further used as an additive capable of preventing sticking. Differential aggregation inhibitor, such as specifically used types of possible additives is limited but in the configuration, the steam, water, surfactants, inorganic powders such as Silica Clay or the like; Persulfate-based initiators, azo initiators, hydrogen peroxide and ascorbic mountains as a thermal polymerization initiator, an epoxy-based crosslinking agent, a diol (diol) stream cross-linking agent, 2 is one functional group, or three functional groups cross-linking agent comprises an acrylate functional group, a hydroxyl group 1 may best cross-linking of the functional group containing compound such as, but not limited to the above-described example.
[83]
[84]
Thereafter, the method of manufacturing a super-absorbent resin according to the present invention is subjected to after the drying step, c) to obtain a superabsorbent resin particles by crushing the dried gel polymer function. After the grinding step the obtained particle size of the superabsorbent resin particles is 150 to 850㎛. The present invention in accordance with high-absorbent resin in the production process in the method, such a particle size as pulverized to to use that mill specifically, pin mill (pin mill), a hammer mill (hammer mill), screw mill (screw mill), roll mill (mill roll), disc mill (mill disc) or the jog mill (jog mill) may be used for, and the like.
[85]
Thereafter, step d) and the surface cross-linking agent added to the water-absorbent resin particles in the surface cross-linking reaction proceeds. In the above step there is added to the surface cross-linking agent, the particle size composition of the surface cross-linking agent to be added to each of the super-absorbent resin particles according to size, may each be the same, and therefore may be added to another composition in the case.
[86]
Surface cross-linking agent to be added in a high production of a water-absorbent resin according to the present invention. If a compound reactable with the functional group possessed by the polymer is not restricted in its configuration. To improve the properties of the superabsorbent resin is preferably produced As the surface cross-linking agent, polyhydric alcohol compounds; Epoxy compounds; Polyamine compounds; Halo epoxy compounds; Halo-epoxy compounds of the condensation products; Oxazoline compounds; Mono-, di- or poly-oxazolidinone compounds; Fantasy urea compounds; Polyvalent metal salt; And it can be used at least one selected from the group consisting of an alkylene carbonate compound.
[87]
Specifically, examples of the polyhydric alcohol compound is a mono-, di-, tri-, tetra- or polyethylene glycol, mono propylene glycol, 1,3-propanediol, dipropylene glycol, 2,3,4-trimethyl-1,3 -pentanediol, polypropylene glycol, glycerol, polyglycerol, 2-butene-1,4-diol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,2-cyclohexane dimethanol may be used one or more selected from the group consisting of methanol.
[88]
In addition, an epoxy compound may be used, such as ethylene glycol diglycidyl ether and glycidol, a polyamine compounds include ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentamine, pentaethylene hexamine , it can be used one or more selected from the group consisting of polyethyleneimine, and polyamide polyamine.
[89]
And, a halo-epoxy compound can be used gave the chloro-epichlorohydrin, epi-bromo mohi gave methyl α- and epi Hi. On the other hand, a mono-, di- or poly-oxa to Jolly dinon compounds, for example may be used such as 2-oxazolidone dinon. And, as an alkylene carbonate compound is ethylene carbonate and the like can be used. Using them each alone, or may be used in combination with each other. On the other hand, to increase the efficiency of the surface cross-linking step, among these surface cross-linking agent is preferred to use, including the one or more polyhydric alcohol compound, and can more preferably be used an alcohol compounds having 2 to 10 carbon atoms of the polyhydric.
[90]
Then, the super-absorbent resin, but a mixture of the surface cross-linking agent as described above, the content of the surface cross-linking agent to be added to handle the polymer particle surface is suitably be selected according to the type and reaction conditions of the surface cross-linking agent should be added to the concrete, usually grinding particles based on 100 parts by weight, 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, can be used more preferably 0.05 to 2 parts by weight.
[91]
If the content of the surface cross-linking agent is too small, the surface cross-linking reaction does almost not occur, for a polymer of 100 parts by weight, when it exceeds 5 parts by weight, the surface cross-linking reaction due to excessive rather physical properties of the superabsorbent resin can be lowered.
[92]
At this time, a method of adding a surface cross-linking agent in the polymer is not limited in its configuration. Mixing the surface cross-linking agent into the polymer powder in the reactor, or a method for spraying a surface cross-linking agent in the polymer powder, and the like can be used for mixing the polymer and the crosslinking agent continuously supplied to a reactor such as a continuously operating mixer.
[93]
Further, the surface temperature of the polymer in the step of addition of the surface crosslinking agent is preferably 60 to 90 ℃.
[94]
And, according to one implementation, in order to proceed after adding the surface cross-linking agent to an elevated temperature to the reaction temperature for the surface cross-linking reaction between 1 minute and within 60 minutes, preferably, upon addition of the surface cross-linking agent, the temperature of the polymer itself of the present invention It may be 20 ℃ to 80 ℃. To indicate the temperature of the polymer itself, such as the drying step is conducted at a relatively high temperature is in progress the process comprising after continuously, and when shortening the process time, or is difficult to shorten the process time can heat the polymer separately is.
[95]
In addition, the method of manufacturing a super-absorbent resin according to the present invention, heating the surface cross-linking agent itself to be added to the polymer to advance after the addition of the surface cross-linking agent to an elevated temperature to the reaction temperature for the surface cross-linking reaction for 1 minute to within 60 bun You may.
[96]
On the other hand, production method of the high-absorbent resin according to the present invention As you are after to 1 minute the temperature was raised to the reaction temperature for the surface cross-linking reaction proceeds within 60 minutes, the surface crosslinking reaction, improving the efficiency of the surface cross-linking process it can minimize the residual monomer content of the final resulting superabsorbent resin, and it is possible to obtain a highly water-absorbing resin having excellent physical properties. At this time, the temperature of the surface cross-linking agent to be added may be adjusted to 5 ℃ to 60 ℃, more preferably from 10 ℃ to 40 ℃. When less than the temperature 5 ℃ of the surface cross-linking agent, the effect of shortening the temperature raising rate of the surface cross-linking reaction of the surface cross-linking agent elevated temperature and negligible, the temperature of the surface crosslinking agent exceeds 60 ℃, the surface cross-linking agent is not evenly dispersed in the polymer can not. In the present specification, the surface cross-linking reaction temperature may be defined as the overall temperature of the surface crosslinking agent with the polymer to be added for crosslinking reaction.
[97]
And, is not limited to that configuration of a heating means for the surface cross-linking reaction. Specifically, the heating medium supply, or may be directly heated by means of electricity, but the present invention is not limited to the above example. A heat source that can be used is specifically steam, electricity, ultraviolet rays, infrared rays, etc., it may be used to heat the heated fluid and the like.
[98]
On the other hand, in the method of the super-absorbent resin produced according to the invention, after the temperature increase is made for the cross-linking reaction, the cross-linking reaction is between 1 minute and preferably 5 minutes to 40 minutes 60 minutes, most preferably for 10 minutes to 20 minutes It may proceed. When case the cross-linking reaction time is less than one minute is too short, this may not see sufficient crosslinking reaction, and the cross-linking reaction time exceeds 60 minutes, and the physical properties of the superabsorbent polymer to excessive surface cross-linking reaction can be rather deteriorated, may occur due to long-term residence in the reactor, it shredded polymer.
[99]
[100]
In addition, out Mars improved superabsorbent resin composition of the present invention produced by the above is characterized in that chamber water content (Moisture content) is less than 0.1% by weight.
[101]
[102]
Out in accordance with the present invention an improved method for producing a superabsorbent resin is flammable.
[103]
a) adding to said particles (100 parts by weight of 0.0001 to 15.0 parts by weight of the addition of the super-absorbent resin (A) to B) having the following properties i) and ii) a water absorbent resin (A); And
[104]
b) said step a) the tough, super-absorbent resin (A) and the particles (and the water (C) to B) the water absorbent resin (A) and the particles (B) 0.1 based on 100 parts by weight to 20.0 input to parts by weight this method produces at least one or more of the treatment process and heat treatment and aging (aging) time control step for producing the chemical conversion improved superabsorbent polymer; includes.
[105]
i) 300 to 1500 m 2 BET specific surface area / g (specific surface area),
[106]
ii) more than 50% porosity (porosity)
[107]
[108]
More specifically, the heat treatment of the step b) is a super-absorbent resin (A) and the particles (B); agitator; And can be water heated to at least any one or more temperatures selected from the group with 26 ~ 95 ℃ input made, the subject of heated temperature control that is highly water-absorbing resin and the fine particles, water or aging (aging) during the stirring process It can control the temperature of the stirrer and the like used. When the heat treatment in the above range, then put into water than the superabsorbent resin in 15 ~ 25 ℃ the aggregation between particles deolhae has the advantage of reducing the aging (aging) time. This means that the process time can be shortened as well as a simplified process. In the temperature range lower than the range can not be obtained an effect of reducing the aging time, the temperature higher than the above range and to increase the absorption rate of the water absorbent resin is difficult to increase the evaporation of water or even moisture.
[109]
In the present invention, one implementation, the high is 60 ~ 70 ℃ temperature of the superabsorbent polymer (SAP) which during the manufacturing process of the absorbent resin, passed through a cooler and classifying after the surface cross-linking of, separately and processed to increase the temperature of the water-absorbent resin When the input directly in the water phase, even if not all appear the effect described above can be not necessary the addition of the additional energy.
[110]
[111]
In addition, aging (aging) time adjustment process is the superabsorbent resin (A) and particles in the 15 ~ 25 ℃ (In the water (C) to B) and a temperature of 26 ~ 95 ℃ for 1 to 120 minutes in the above step b) from 5 to to characterized in that aging (aging) and stirred to 1500rpm, if the aging (aging) treatment in the above range, and grafted to the water in the water-absorbent resin and prevent bunching phenomenon because no aggregation occur in the course of up to packing can do.
[112]
Also, the function is not high even if aggregation occurs in the water-absorbent resin, there are cases that aggregation occurs under the long-term continuous loading, it is possible to prevent this from occurring. The potential range than the aging (aging) lead to a shorter time when the aggregation between particles, and the case that the above range than aging (aging) time is lengthened, the unnecessary process is not economical.
[113]
In addition, heat treatment and aging (aging) time adjustment process in step b) is a super-absorbent resin (A) and the particles (B); agitator; And water, and heating at least one or more temperatures selected from the group with 26 ~ 95 ℃ made, by stirring with 5 ~ 1500 rpm for 1 to 120 minutes at a temperature of 15 ~ 25 ℃ can be characterized in that aging (aging) is. In this case, the particle size was in accordance with the aging (aging) time distribution, the properties such as flowability and apparent density not a great change by aging (aging) time. These results Supplying of water to the superabsorbent resin in a heated condition means that the decrease in the amount of time required for aging than when put into water at room temperature considerably.
[114]
On the other hand, and at a temperature of room temperature of 15 ~ 25 ℃, even if input of water to the water-absorbent resin may be generated a phenomenon agglomeration (caking) increasing the time for aging (aging), This is due to problems such as the need to increase the aging time there may be a disadvantage that productivity is decreased.
[115]
[116]
The out Mars is improved and the particles having the property of the i) and ii) in the production of a water-absorbent resin (B) is more preferably that the high-containing 0.0001 based on 100 parts by weight to 15.0 parts by weight of the water absorbent resin (A) It said high that the water-absorbent resin contains (a) 100 parts by weight of 0.001 to 2.0 parts by weight based on the more preferred, and most preferably comprises from 0.05 to 0.15 parts by weight. It is not sufficient to obtain the effect to lower than expected when the range of the included amount of particles (B), if it exceeds the above range, is to use the particles (B) with an excess is economically not preferred.
[117]
In general, high by the surface of the water absorbent resin is ttuimyeo hydrophilicity, etc. capillary forces, van der Waals forces between the hydrogen bond, the polymer cross section spread (inter-particaular diffusion) or particles by the water present between the particles during after moisture absorption drying rain becomes irreversible aggregation occurs. Therefore, there is high in essential use of water as in polymerization and the surface cross-linking step of the water-absorbent resin, because the agglomeration according to this generation, increase the internal load, may result in the risk of equipment failure. In addition, super-absorbent resin of the agglomerated state as described above has the disadvantage that because of the size to the particle size is not suitable for the application, to introduce the shredding process to reduce them to an appropriate particle size. In addition, there was a problem that since a strong force is applied in the pulverizing process may cause a decline in accordance with the physical properties superabsorbent resin crushing.
[118]
In order to solve the above problems, when a high is present on the surface of the water absorbent resin, attempt has been made to introduce a variety of fine particles which can serve to prevent the direct agglomeration between the resin particles, the fine particles have an excess is to be introduced aggregation but is prevented, there is a disadvantage that the absorption characteristics of the superabsorbent resin decreases.
[119]
In order to solve the above problems, fine particles to be introduced into the super-absorbent resin of the present invention has a particle size of 2 ~ 50 ㎚ ㎛. In addition, the fine particle is 300 to 1500 m 2 / g, preferably 500 to 1500 m 2 / g, preferably 600 to 1500 m than 2 may have a (specific surface area) of the BET specific surface area / g. In addition, the contact angle is more than 125 ° for the second hydrophobic fine particles are water, preferably 140 ° or more may have a superhydrophobic more preferably more than 135 ° superhydrophobic. In addition, the particles (B) have a contact angle of about 2 ~ 50 ㎚ ㎛ particle size and the water may have a more than 125 ° superhydrophobic.
[120]
In addition, the fine particle is more than 50% porosity (porosity), preferably have at least 90% porosity (porosity). Since out Mars improved super-absorbent resin of the present invention using the fine particles having the characteristics as described above, not only can reduce the water influence on the resin surface, because it uses a porous second hydrophobic fine particles, the agglomeration can be remarkably reduced, and also relatively easy to increase the transmission rate by using a small amount of fine particles it can be easily maintained and the howler quantity thereof.
[121]
The particles to be added in the process of the super-absorbent resin produced according to the invention (B) has no If materials having the same properties as the limitation of its components, in particular silica (SiO 2 ), alumina, titania (TiO 2 ), carbon (carbon) may be used an inorganic oxide, an inorganic compound, an organic polymer, ion exchange resins, metals, metal salts, such as, but not limited to.
[122]
In addition to the process of adding the fine particles, used after my dispersing the monomer solution, the polymerization after the function gel was added to the dry mix, the surface cross-linking solution is within the dispersion or organic solvent that melts during the surface cross-linked to the primary dried resin particles after mixing, the surface cross-linking during the surface cross-liquid separation with water or an organic solvent which may be used to melt a method such as dry mixing in the final product of the dry mixing, or the surface cross-linking, this is not particularly limited.
[123]
[124]
The out Mars is enhanced in the high-absorbent resin with water (C) is high that contained water absorbent resin (A) and the particles (B) is preferably contained 100 parts by weight of 0.1 to 20.0 parts by weight with respect to, 1.0 to 10.0 parts by weight it is most preferred to be contained, and even more preferably, 2.5 to 7.5 parts by weight. Is less than the above range, the amount included in the water (C) not sufficient to obtain within the friability, the than the large viscosity of the resin surface (stickiness) is increased above the range, the ratio of the occurrence irreversible agglomeration (irreversible agglomeration) between the super-absorbent resin particles is the particle size is changed at the same time as the workability of the resin falls may cause problems difficult to use as a product.
[125]
In the manufacturing process of the high-absorbent resin it is used in several different ways, including water to make a polymerization medium, facilitating the dispersion of the cross-linking solution in the surface cross-linking process. In addition to the role of anti-static agents and plasticizers for the residual moisture of the final resin product, inhibits the very small super-absorbent resin fine particles (dust) formed in the application process to prevent the crushing of the high water-absorbent resin particles. In general, however, and a small amount even as the water-absorbent resin even upon addition of water, the viscosity of the resin surface by the absorbed water on the surface and (stickiness) is increased, the high ratio between the water-absorbent resin particles irreversible agglomeration (irreversible agglomeration) is generated do. This increase in viscosity and aggregation, reduce the load increases, such as workability (processability) of the manufacturing and application processes, and consequently increases the particle size of the water absorbent resin, causing a reduction in physical properties and productivity decreases. So far, high research on the water-absorbent resin is eoteumyeo is made the main study of the surface cross-linking for an increase in the polymerization step and the absorption capacity improvement over this, and high surface properties of the water absorbent resin or the pressure-absorbing ability, improvement of the transmission rate or a high water-absorbent resin bar surface characteristics change research is conducted in order to solve some problems, such as the prevention (anti-caking) hardened during storage of.
[126]
By the present invention, and by the addition of further water to the water-absorbent resin in the above range by increasing the water content and to the water to minimize physical damage to the high-absorbent resin to act as a plasticizer satisfy the water content and high porosity at the same time, the high-absorbent resin It can be increased within the friability. Using the water heated in the process, or the like and increasing the temperature of the water-absorbent resin, can be reduced and the injected water is spread on the water-absorbent resin speeds the aging time compared to existing. Therefore, if high water-absorbent resin is applied to the final products, such as diapers, for example, it has the advantage to minimize the deterioration of physical properties due to the crushing of the super-absorbent resin according to the compression of the feed air or strong diaper production process.
[127]
Further, according to the embodiment of the present invention after the step b), step c) The prepared out chemical conversion and comprising method produces a water-absorbent resin solidifying test (caking test) confirmed Mars; may include . Solidifying test (caking test) can be performed for several minutes to 50 hours or for 1 month, and can be performed under a load of 2.66 psi.
[128]
Is out Mars prepared by the method of manufacturing the improved super-absorbent resin may be characterized in that the chamber water content (Moisture content) is less than 0.1% by weight.
[129]
[130]
Mars out the improved high-high water-absorbent resin in the method for producing a water absorbent resin (A) is
[131]
a) to the monomer composition including a water-soluble ethylenically unsaturated monomer and a polymerization initiator, a thermal polymerization or photo polymerization step to prepare the gel-like function polymer;
[132]
b) drying the gel-like function polymer;
[133]
c) said step of obtaining a water-absorbent resin particles by crushing the dried gel polymer functions; And
[134]
d) characterized in that the said high by the addition of the surface cross-linking agent to the water absorbent resin particles produced by a step of the surface cross-linking reaction proceeds.
[135]
[136]
The water-soluble ethylenically unsaturated monomer may be at least one which is selected from anionic monomers and their salts, non-ionic hydrophilic-containing monomers, and amino group-containing unsaturated monomer, and the group consisting of His quaternary cargo, a polymerization initiator for the thermal polymerization is a persulfate-based initiators, azo initiators, hydrogen peroxide and may be at least any one selected from the group consisting of ascorbic acid, a polymerization initiator for the photopolymerization are benzoin ethers (benzoin ether), dialkyl acetophenones (dialkyl acetophenone) hydroxyl alkyl ketones (hydroxyl alkylketone), phenyl glyoxylic rate (phenyl glyoxylate), benzyl dimethyl ketal (benzyl dimethyl ketal), acylphosphine (acyl phosphine) and alpha-amino ketone (α-aminoketone) to the group consisting in the selection there can be more than one.
[137]
The drying step of step b) is performed at temperature of 150 ℃ to 250 ℃, the superabsorbent polymer particle size range of the particles obtained after the pulverization in the step c) may be 150 to 850㎛.
[138]
The surface cross-linking agent is a polyhydric alcohol compound; Epoxy compounds; Polyamine compounds; Halo epoxy compounds; Halo-epoxy compounds of the condensation products; Oxazoline compounds; Mono-, di- or poly-oxazolidinone compounds; Fantasy urea compounds; Polyvalent metal salt; And alkyl may be at least any one selected from the group consisting of alkylene carbonate compound.
[139]
[140]
Super-absorbent resin (A), the particle according to the method for producing the out-enhanced superabsorbent resin compatibility of the present invention in addition to the above described content (B), a detailed description of the water (C) is a superabsorbent with improved out herein Mars the distance the contents described with respect to the resin.
Mode for the Invention
[141]
As illustrated below. Where is embodiments of the invention which is disclosed below, but described in further detail on the basis of the present invention, the embodiments, the scope of the invention is not limited to these embodiments. The scope of the present invention were shown in the claims, and moreover, contain all modifications within the equivalent meaning and range of the claims and written. In addition, embodiments of the following Examples, "%" and "parts" representing the content in the comparative example is a weight standard unless otherwise noted.
[142]
Preparation : function gel polymer and the production of high absorbent resin
[143]
100g of acrylic acid, polyethylene glycol diacrylate as a cross-linking agent 0.3 g, initiator Diphenyl (2,4,6-trimethylbenzoyl) - phosphine oxide 0.033g, caustic soda (NaOH) 38.9g, and water at a rate of 103.9g by mixing, to prepare a monomer mixture. After that, it puts on a conveyor belt to continuously move the said monomer mixture is irradiated with ultraviolet rays (dose: 2mW / ㎠) by the UV polymerization proceeds for two minutes to obtain a hydrogel polymer. A function gelled polymer prepared according to the 5 * 5mm cut to size, dried in a hot-air drier at 170 ℃ temperature for 2 hours, pinmil a shredder and then sieve (sieve) superabsorbent has particle diameter size of from 150 to 850 ㎛ using to obtain a resin. After surface cross-linking agent to the administration of a liquid mixture consisting of ethylene carbonate 0.75g and 6.75g of water they were mixed for 60 seconds. Thereafter, US The mixture was reacted for 60 minutes at 190 ℃ pulverized and was obtained a water-absorbent resin, again, the fine grinding and measuring the particle size milled around the water-absorbent resin, and pinmil a shredder after size particle size using a sieve It is to obtain a super-absorbent resin of 150 to 850 ㎛.
[144]
Porous seconds was used as a hydrophobic fine particles of an airgel (JIOS社), particle size of the porous second hydrophobic microparticles airgel used is the average 5 μm, 720 m 2 having a BET specific surface area / g, the contact angle for water is 144 ° , and the porosity was 95%.
[145]
Aerogel is a measure of the size of the ISO 13320 Therefore, HELOS (Helium-Neon Laser Optical System) to use, free high-speed variable optical diffraction method (Laser Diffraction) by the particle size analysis was. The specific surface area was measured by BET equipment (Micromeritics 3Flex). Porosity formula tap density (ρ 1 as t and) true density (ρ s were derived via the relation).
[146]
[Equation 1]
[147]
공극률(porosity, %) = (1 - ρt / ρs)*100
[148]
True density measurements for the pycnometer (Accupyc II 1340) was used for, tap density is volumeter (Engelsmann Model STAV II) used in the measurement was.
[149]
The contact angle for water contact angle analyzer (KRUSS DSA100) a was used, specifically after pasted to the double-sided tape to the flat glass sheet was coated fine particles thereon in a single layer (Monolayer), the ultra pure water 5 ㎕ over monolayer a raising position and in the form of droplets, wherein the measurement is repeated 4 times the angle of the droplet with the glass plate after forming the mean value was calculated.
[150]
The superabsorbent resin compared to 600 ppm both porous seconds respectively compared and the hydrophobic fine particles in the course of stirring in a stirrer-absorbent resin 0 (P / D) of which corresponds to, 2.5, 5.0, added with water corresponding to 7.5% by weight It was, or the superabsorbent resin preparation 600, was charged with high water corresponding to 0, 2.5, 5.0, wt%, respectively water-absorbing resin in the process of stirring the amount porous second hydrophobic microparticles agitators corresponding to 1,000 ppm.
[151]
Example 1: out Mars Preparation 1 (temperature control) of the enhanced superabsorbent resin
[152]
And to put water in the water-absorbent resin and prevent the long time that has passed between particle aggregation occurs and the experiment was to increase the temperature of the water absorbent resin added with water. Insert the second porous hydrophobic fine particles of high-absorbency resin processes the airgel in an oven 600 ppm were added to water at about 60 ℃ tailored to insert the high-absorbent resin in a stirrer and then maintained at 70 ℃ 2.5% by weight. Since then 100 g of a sample by applying a load of 2.66 psi for an hour, it was confirmed whether or not a bunching of the superabsorbent resin.
[153]
To compare the differences in aggregation of the superabsorbent resin particles by the high temperature condition in the above experiment the temperature of the temperature of the water absorbent resin and a stirrer at room temperature was the experiment. As a result, and the conditions to increase the temperature In the water of the water-absorbent resin Fig. 1 (a) aggregation of the particles did not appear at all, in Fig. 1 (b) when added to water at room temperature, such as is under a load of 2.66 psi aggregation of particles that appear badly
[154]
Confirmed.
[155]
Example 2: out Mars improved superabsorbent polymer prepared 2 (of aging (aging) time control)
[156]
In the high water-absorbing resin, and a long time to prevent the aggregation between particles pass phenomenon occurs and the experiment was that the water-absorbent resin after aging (aging) time added water at room temperature conditions. In the porous second after water of 2.5% by weight of the superabsorbent resin treated with hydrophobic fine particles of airgel 600 ppm, in terms of the room temperature by using a stirrer such as a kitchen-aid it gave the aging time of 30 minutes. Samples not subjected to aging (Aging) was the control group of Example 2. The results also indicate the aging when conducted for straight caking test without (aging) (0 min) 2 was confirmed that was confirmed that the agglomeration of the superabsorbent resin particles severe, also apply pressure to the finger aggregation is maintained . On the other hand, when given 30 minutes aging (aging) of the same conditions (30 min) in Fig. 3 it was significantly reduce the aggregation of particles, also lightly applying a force with fingers was confirmed that aggregation is easily broken.
[157]
Example 3: out Mars manufacturing 3 (the temperature and the enhanced superabsorbent resin aging (aging) time control)
[158]
And to put water in the water-absorbent resin and prevent the long time that has passed between particle aggregation occurs and the experiment was to increase the temperature of the water absorbent resin added with water. After the second porous insert the super-absorbent resin fine particles treated with a hydrophobic airgel of 600 ppm in the oven tailored to about 60 ℃, put in a stirrer and maintained at 70 ℃ the water-absorbent resin was added 2.5% by weight of water. Since under the conditions of room temperature using a simple stirrer such as a kitchen-aid it gave aging (aging) time 0 to 45 minutes. The results, aging (aging) in Figure 4 is a particle size distribution with time, the aging (aging) time according to the flowability and apparent density is shown in Table 1 to. According to Fig aging (aging) time from the results of Table 1 and 4 was confirmed to particle size distribution, there is no significant change flowability and apparent density. Compared with Example 2 of the results look to high when the input of water at high temperature of the water absorbent resin reduced the required aging (aging) time significantly to reduce the aggregation between particles than when added to water at room temperature under the same conditions It could be confirmed.
[159]
TABLE 1
[160]
Example 4: out Mars is prepared 4 (water temperature control) of the enhanced superabsorbent resin
[161]
By raising only the temperature of the water to be added in Example 1 it was performed under the same conditions the experiment. And then put into a water temperature rising of water and 70 ℃ of room temperature grain size comparison of the distribution, it was confirmed that even when put into a water temperature increase, such as 5 having a particle size distribution as the original of the superabsorbent resin (PD). The aggregation of the particles when the increase from the above results, it was confirmed that the temperature of the water that are resistant.
[162]
Example 5: out Mars is improved and the production of water-absorbent resin 5 (temperature and aging (aging) time control)
[163]
Based on lab experiments conducted a pilot test. After a second porous hydrophobic fine particles of super-absorbent resin of the airgel it is treated with 600 ppm tailored 60 ℃, In the continuous input of the agitator with 40 kg / h and the progress was a function of 2.5% by weight. After the stirrer at room temperature for 0 ~ 50 bun gives the aging (aging) time confirmed the aggregation degree of the particles. As a result, similarly to the results held in lab 0, 5, 10, 20, 30, 40, if all of the 50 minutes it was confirmed that caking does not occur. In addition to the caking it was more than 48 hours to determine the test time 1 hour eseo aggregation of the particles does not occur even.
[164]
Example 6: out Mars is improved and the production of water-absorbent resin 6 ( aging (aging) temperature and time control)
[165]
600 ppm of the hydrophobic porous ultra fine particles of an airgel is introduced in a continuous stirrer and treated with a water-absorbent resin Loading of 40 kg / h at room temperature and progress was a function of 2.5% by weight. Since in accordance with binary agitator 50 ℃ for 0 ~ 50 bun gives the aging (aging) time confirmed the aggregation degree of the particles. As a result, it was confirmed that Example, like that with the experimental results in five at 0, 5, 10, 20, 30, 40, 50 In all cases the bun caking occurred.
[166]
In addition to the caking it was more than 48 hours to determine the test time 1 hour eseo aggregation of the particles does not occur even.
[167]
Therefore, according to the present invention by controlling the temperature or aging (aging) time when the water is added to the high-absorbent resin and can prevent the aggregation phenomena of the water-absorbent resin particles in advance, the high absorbent resin through such variable control It was introduced into a water and then can be expected to prevent the aggregation between the particles of the superabsorbent polymer in the final product in storage or transported to.

Claims
[Claim 1]
a) adding to said particles (100 parts by weight of 0.0001 to 15.0 parts by weight of the addition of the super-absorbent resin (A) to B) having the following properties i) and ii) a water absorbent resin (A); And b) such that the step a) the tough, super-absorbent resin (A) and add the particles (and the water (C) to B) the water absorbent resin (A) and the particles (B) 0.1 based on 100 parts by weight to 20.0 parts by weight in the heat treatment and aging (aging) time control processing of the at least one out by the processing Mars improved superabsorbent polymer comprising: preparing a; way to put Mars improved superabsorbent polymer comprises a prepared: i) 300 to 1500 m 2 / g BET specific surface area (specific surface area) of, ii) more than 50% porosity (porosity).
[Claim 2]
The method according to claim 1, wherein the heat treatment in step b) the superabsorbent resin (A) and particles (B); agitator; And that at least any one or more temperatures selected from the group consisting of water, characterized in that heating to 26 ~ 95 ℃, Mars out the improved method of producing a superabsorbent resin.
[Claim 3]
The method according to claim 1, the aging (aging) time adjustment process of the step b) for input of water (C) to the superabsorbent resin (A) and particles in the 15 ~ 25 ℃ (B) from 1 to 120 minutes 26 ~ 95 and stirred at a temperature of 5 ~ 1500rpm ℃ characterized in that aging (aging), out chemical conversion and improved method of producing water-absorbent resin.
[[4]
The method according to claim 1, and the aging heat treatment (aging) time adjustment process in step b) is a super-absorbent resin (A) and the particles (B); agitator; And water, and heating at least one or more temperatures selected from the group with 26 ~ 95 ℃ made, by stirring with 5 ~ 1500 rpm for 1 to 120 minutes at a temperature of 15 ~ 25 ℃ aging characterized in that (aging), Mars out the improved method of producing a superabsorbent resin.
[Claim 5]
The method according to claim 1, wherein the particles (B) is characterized in that the high-contained 100 parts by weight of 0.001 to 2.0 parts by weight based on the water-absorbent resin (A), out chemical conversion and an improved method of producing water-absorbent resin.
[6.]
The method according to claim 1, wherein the particles (B) is characterized in that the high-absorbent resin contained (A) 100 parts by weight of 0.05 to 0.15 parts by weight based on the, out chemical conversion and an improved method of producing water-absorbent resin.
[7.]
The method according to claim 1, the method for producing the water (C) is a super-absorbent resin (A) and the particles (B) 1.0 based on 100 parts by weight to characterized in that included 10.0 parts by weight, out Mars improved superabsorbent polymer .
[8.]
The method according to claim 1, the method for producing the water (C) is a super-absorbent resin (A) and the particles (B) 2.5 based on 100 parts by weight to characterized in that comprises 7.5 parts by weight, out Mars improved superabsorbent polymer .
[9.]
The method according to claim 1, wherein the particles (B) is a method of 2 ~ 50 ㎛ ㎚ characterized in that having a particle size, the Mars out enhanced production of the superabsorbent resin.
[10.]
The method according to claim 1, wherein the particles (B) is characterized in that the contact angle with water having at least 125 ° superhydrophobic, Mars out the improved method of producing a superabsorbent resin.
[11.]
The method according to claim 1, wherein the particles (B) is 2 ~ 50 ㎚ ㎛ of particle size and the contact angle with water of more than 125 ° characterized by having a second hydrophobic, Mars out the improved method of producing a superabsorbent resin.
[12.]
The method according to claim 1, wherein the particles (B) is 500 to 1500 m 2 / g of BET specific surface area (specific surface area) and characterized in that having, Mars out the improved method of producing a superabsorbent resin.
[13.]
The method according to claim 1, wherein the particles (B) is 600 to 1500 m 2 / g of BET specific surface area (specific surface area) and characterized in that having, Mars out the improved method of producing a superabsorbent resin.
[14.]
The method according to claim 10, wherein the particles (B) is characterized in that the contact angle with water having at least 135 ° superhydrophobic, Mars out the improved method of producing a superabsorbent resin.
[15.]
The method according to claim 10, wherein the particles (B) has a contact angle for water, characterized in that more than 140 ° with a second hydrophobic, Mars out the improved method of producing a superabsorbent resin.
[16.]
The method according to claim 1, wherein the particles (B) of the method, characterized in that having at least 90% porosity (porosity), the high-absorbent resin produced out Mars improved.
[17.]
The method according to claim 1, wherein the particles (B) is silica (SiO 2 ), alumina, carbon (Carbon) and titania (TiO 2 characterized in that the at least one selected from the group consisting of a), out Mars improved superabsorbent polymer method of manufacturing.
[18.]
The method according to claim 1, after said step b), c) out of the prepared chemical conversion superabsorbent resin solidifying test (caking test) to put identifying a chemical conversion; method of producing out Mars improved superabsorbent polymer comprising a .
[19.]
The method according to claim 1, wherein the super-absorbent resin (A) is a) to the monomer composition including a water-soluble ethylenically unsaturated monomer and a polymerization initiator, a thermal polymerization or photo polymerization step to prepare the function gel polymer; b) drying the function gel polymer comprising; c) to obtain a superabsorbent resin particles by crushing the dried gel polymer functions; And d) the superabsorbent resin by the addition of the surface cross-linking agent, characterized in that the particles to be produced, including the step of the surface cross-linking reaction proceeds, out Mars improved method of producing a superabsorbent resin.
[20.]
The method according to claim 19, wherein the water-soluble ethylenically unsaturated monomers, characterized in that any one or more selected from the group consisting of anionic monomers and their salts, non-ionic hydrophilic-containing monomers, and amino group-containing unsaturated monomers and their quaternary cargo, Mars out the improved method of producing a superabsorbent resin.
[21.]
The method according to claim 19, the manufacture of the polymerization initiator is a persulfate-based initiators, azo initiators, hydrogen peroxide and ascorbic acid characterized in that any one or more selected from the group, consisting of a pay Mars improved superabsorbent resin for the thermal polymerization Way.
[22.]
Claim 19, a polymerization initiator for the photopolymerization are benzoin ethers (benzoin ether), dialkyl acetophenones (dialkyl acetophenone), hydroxyl alkyl ketones (hydroxyl alkylketone), phenyl glyoxylic rate (phenyl glyoxylate), benzyl dimethyl ketal (Benzyl Dimethyl Ketal), acylphosphine (acyl phosphine) and alpha-amino ketone (α-aminoketone) to be selected from the group consisting of any one or more characterized in that, out Mars improved super-absorbent resin in the production process.
[23.]
The method according to claim 19, wherein the step b) of the method of drying is 150 to 250 ℃ ℃ characterized in that proceeding from the temperature, out of the manufacturing Improved superabsorbent resin Mars.
[24.]
The method according to claim 19, wherein step c) is obtained after grinding and particle size range of the water-absorbent resin particles prepared in the method 150 to the 850㎛ characterized in that, out of Mars improved superabsorbent polymer.
[25.]
The method according to claim 19, wherein the surface cross-linking agent is a polyhydric alcohol compound; Epoxy compounds; Polyamine compounds; Halo epoxy compounds; Halo-epoxy compounds of the condensation products; Oxazoline compounds; Mono-, di- or poly-oxazolidinone compounds; Fantasy urea compounds; Polyvalent metal salt; And alkyl of one or more is selected from the group consisting of vinylene carbonate compounds, Mars out the improved method of producing a superabsorbent resin.
[26.]
The method according to claim 1, made out by the method for producing the chemical conversion is enhanced superabsorbent resin chamber water content (Moisture content) The method of producing a 0.1% by weight or more, characterized in that, out Mars improved superabsorbent polymer.