TWI351416B - The processes of high efficient of disperse the we - Google Patents

Description

6 1351416 IX. INSTRUCTIONS OF THE INVENTION '· TECHNICAL FIELD OF THE INVENTION The present invention relates to a water absorbing material which absorbs well in an aqueous solution, and the super absorbent resin is widely used in water retaining agents and building materials for agriculture or horticulture. Anti-dew beading agent and material for removing moisture from petroleum, or outer layer waterproofing agent in electric_electricity and hygienic articles such as diapers, feminine hygiene products, _ type wipes, and the like. ~ ', the above superabsorbent resin is directly in contact with the human body, so the safety of the super absorbent resin (4) is important. In general, the physical properties of the high water absorption (10) series include absorption rate, absorption, and absorption under pressure. Magnification 'low monomer residual amount and conductivity after absorption. Excellent (4) High-absorbing chokes not only need to meet the physical properties listed above, but also need to have good safety, and more importantly, must be sweat-free and energy-saving. [Prior Art]

The constituent materials of the superabsorbent resin known in the art have been hydrolyzed by powder_Pink-propylene guessing polymer (Japanese Patent Publication No. 95), Neutral Hall Powder-(4) Acid Graft Polymer (Japan) Patent Publication · Zhao Zhao 5] 0 976) Na 68) 'Saponified E-acid _ _ xiangxiang copolymer (10) patent disclosure public = 叩 977> 14, called fine matter · climbing amines common patent notice Zhao 53 (call 邸 9 ), and parts and acid removal (Japanese Patent Laid-Open Publication No. Sho 55 (1980)-84,304) and the like. In addition, because of the decomposing of the rot, the 7 71351416 method is preserved in the length of the law. Moreover, the manufacturing method is very complicated, so the current method of preparing for the high and the 生f The most water-absorbent age group obtained by cross-linking polymerization using acrylic acid and acrylate acid is also the most effective, because the proglycolate copolymer-acrylic acid can be quickly mentioned by the mall. The obtained highly water-absorptive resin has a high water absorption capacity, and has the most economical efficiency in manufacturing, and does not cause decomposition of rot, so it is the most general superabsorbent resin. The method of polymerizing acrylic acid and acrylate to form a superabsorbent resin can be obtained by a number of known methods, such as aqueous solution polymerization, reverse phase chromatography, emulsion polymerization, or spraying or coating a monomer onto a fibrous substrate. A method such as a polymerization reaction is carried out. In these methods, the 'anti-float polymerization and the depolymerization reaction must use the organic amount, but if the temperature of the anti-colon is not controlled, the organic solvent will increase the age, temperature and pressure. There is a fire phenomenon and even a hair explosion, which threatens the safety of the personnel at the operation site and causes environmental pollution problems. The finished product also has doubts about the residual organic solvent. The production of superabsorbent resins, whether in aqueous solution polymerization, reverse phase suspension polymerization, milk recording reaction or polymerization of monomers or coating on fibrous substrates, etc., will eventually pass the drying step. It is a one-time drying method that uses a surface temperature of 1 to 230 C. The technology industry has developed a number of methods to improve the physical properties of high water-absorbent resins or to increase production efficiency by increasing the surface area, such as the addition of a blowing agent, including the method of 7 8 1351416; A foaming agent such as a carbonate, a method of adding a parent-linked cross-linking structure while neutralizing (U.S. Patent No. 4,529,739, No. 4,529,739), a method of adding a carbonate to a monomer (Japanese Patent Publication No. 62-34042) , the method of microwave polymerization of a carbonate-containing monomer solution (U.S. Patent No. 4,808,637), which has a boiling point of 40 tM 5 (rc of an organic solvent, US Pat. No. 2, 154, 714, No. 5, 314, 420). A method of adding to a single shot for polymerization (U.S. Patent No. 4,7,3, No. 67), a method of adding a hydrophobic solvent to a specific pressure to carry out polymerization (U.S. Patent No. 5,328,935, No. 5,338,766) In the method for improving the physical properties of the superabsorbent resin, the foamed woven contact organic solvent is used for polymerization, heat decomposition, gas decomposition or gasification to generate gas. The pores increase the surface area when water is absorbed, but the superabsorbent resin with too many pores in the pores tends to cause an excessive increase in the amount of fine powder during the grinding process, so that the finished product is liable to cause a rubber block due to excessive fine powder when it absorbs water. If you do not properly reduce the amount of fine powder, it will greatly reduce the effectiveness of the actual application. There are still many scientists - efforts to save energy and improve the physical properties of superabsorbent resin 'If you have a monomer solution ( Direct injection of hot furnace) heating (Japanese special open 55_147512, special open Zhao 56' chat 9, special open 63-275607, special open knife 63-275_) or in the heating rotary drum (Japan _ flat drying, , to, the dry matter of water-based tree vinegar' However, these methods have the disadvantages of soluble fraction and fine powder. The reason why the industry is dry is that In addition to the pre-drying drying method, the pre-drying temperature is between machine and %. The pre-drying interval is between 丨 minute and 3 () minutes, and then another dry H is added for secondary drying. Reduce the above fine powder to produce higher SUMMARY OF THE INVENTION The water-soluble unsaturated monomer required for producing the super absorbent resin of the present invention, in addition to propylene@夂, can also use other water-soluble monomers having an unsaturated double bond having an acidic group. Such as: methyl propionic acid, marinic acid, fumaric acid, 2-propyleneamine, 2-methylpropionic acid, maleic acid, maleic anhydride, fumaric acid, anti Butene dianhydride, etc. Monomers can be used without limitation, and can also be used in combination with monomers. It is also possible to add a monomer having an unsaturated double bond to its water source, such as: propylene. Indoleamine, methyl propylamine, acrylic acid 2_county vinegar, thioglycolic acid 2 county ethyl ester, propyl hydrazine, acrylic acid acetyl amide, diamine propylene acrylamide, gasified propylene propylene amide The base tri-ammonium is added in such a manner that the physical properties of the superabsorbent resin are not impaired. The concentration of the aqueous solution of the monomer in the free radical polymerization of the present invention is not particularly limited, but the preferred concentration is preferably controlled between 2% by weight and 55% by weight, and the appropriate wave is between 30% and 45% by weight. When the concentration is less than 2〇% by weight, the hydrogel after polymerization is too soft and sticky, which is unfavorable for mechanical processing. The added concentration is above 55wt% by weight, close to the saturation concentration, and it is difficult to mix and react too fast. The reaction heat is not easy to be 1351416. Control, the unsaturated monomer aqueous solution _ not less than 5.5, if the PH is lower than 5 l, after the polymerization, the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

The acid-containing monomer has an acid group, and the positive values of the Peng-Women and the sputum products make it neutral and acidic. As a gas oxide or carbonate compound of the anger family, such as: sodium hydroxide, potassium hydroxide, carbon _, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate or ammonia compounds; One or more of them can be used alone. The acid-containing monomer-based syrup and the oil sulphate potassium salt or the recorded salt have a neutral concentration molar percentage of 45_% to 85 md%, preferably 1% to 75 mol%. When the percentage of neutralization wave Moment is 45_% or less, the positive value of the finished product will be low. When the concentration of neutral concentration is 85_% or more, the pH value of the finished product will be high, and the pH value of the finished product is not neutral or slightly acidic. The temple is not safe if it is inadvertently in contact with the human body. Water-soluble high molecules may also be added to the aqueous monomer solution to reduce the cost before the radical polymerization. Such water-soluble polymers such as partially saponified or fully saponified ethylene glycol, polyethylene glycol, polyacrylic acid, polypropylene decylamine, temple powder or temple powder derivatives such as methyl cellulose, methyl acrylate A polymer such as cellulose or ethyl cellulose; the molecular weight of such water-soluble polymers is not particularly limited, and among them, a preferred water-soluble polymer is starch. The partially saponified or fully saponified polyvinyl alcohol or the like may be used singly or in combination. A suitable weight percentage of the superabsorbent resin containing such a water-soluble polymer is from 〇 to 20% by weight, preferably from 0 to 10% by weight, particularly preferably from 5% to 5% by weight, and more than 11 1351416 # · 20% by weight. Affecting physical properties, making physical properties worse. The free-knit reaction cross-linking agent is added to the unreacted monomer solution towel, and the free-spinning reaction cross-linking agent can be selected from compounds having two or more unsaturated double bonds, such as :N,N'_bispropenyl)amine, N,N,-decyldipropylene _, N,N'-methine bis-decyl acrylamide, propylene acrylate, ethylene glycol diacrylate Ester, polyethylene glycol diacrylate, ethylene glycol diacetate acrylate vinegar, polyethylene glycol dimercapto acrylate vinegar, glycerol triacrylate cool, glyceryl tridecyl acrylate, glycerin plus ethylene oxide Acrylate or tridecyl propylene oxime, diterpene propyl ketone plus epoxy triacetate or trimethacrylate, triterpene propyl tridecyl acrylate, triterpene propane triacrylate Ester, N, N, N_ tris(2-propenyl)amine, ethylene glycol diacrylate, polyoxyethylene glyceryl triacrylate, diethyl ethoxylate diacrylate, dipropylene triethylene glycol ester, etc. Also, a compound having two or more epoxy groups, such as sorbitol polyglycidyl ether, _ T-propylene glycol polyglycerin test, ethylene glycol diglycidyl hydrazine, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diglycerin polyglycidyl ether and the like. After the radical reaction, the superabsorbent resin can have an appropriate degree of crosslinking, and the superabsorbent resin colloid can have appropriate processability. The radical polymerization crosslinking agent may be used singly or in combination of two or more. The free radical polymerization crosslinker is suitably present in an amount of from 0.001 wt% to 5 wt% by weight based on the total solids of the reactants. More suitably, the amount by weight is between 0.Olwt% and 3 wt%, Addition of the dose after the polymerization of the weight percentage of O.OOlwt% or less is too soft and viscous. ^51416 Machining, the amount of the additive is less than 5% by weight, the water absorption is too low, and the resin property is lowered.

The polymerization starts by the decomposition of the radical polymerization initiator to generate a radical. The free radical initiator can be selected from a thermal decomposition type initiator, and the suitable thermal decomposition initiator is a peroxide such as: Wei hydrogen, a second wire oxide, an amine peroxide or a persulfate (money) Salt, metal salt, etc., and azo compounds such as: 2 2, azobis(2-cyanopropyl) dihydrochloride, 2 2, • even double-bounded dimethyl-isobutyl) Dihydrochloride; can also make (iv) the original agent 'make a redox initiator, such as: acid sulfite, thiosalt, ascorbic acid or argon; or redox initiator and thermal decomposition type The initiator is combined, firstly, the redox initiator starts to react to produce a self-peak, and when the radical is on the monomer, the polymerization is initiated. 'Because the polymerization proceeds, a large number of slits are generated to raise the temperature. When the / degree reaches the decomposition temperature of the thermal decomposition type initiator, the decomposition of the second stage thermal decomposition type initiator is caused, and the whole bribe reaction is more complete. - The radical polymerization reaction starts _# dosage is _ swim. To coffee (10) and propylene, the weight of the salt is based on the basis), the more appropriate amount is between 0 and 5 wt%, so that the weight is less than _lwt%, the reaction is too slow, unfavorable economic benefits, the use of the percentage of weight lGwt% When the above is too fast, the reaction heat is not easy to control. The south water-absorbent resin is an insoluble hydrophilic polymer, and the interior of the resin has a 1416 step bridge in the resin county, such as increasing the absorption rate, increasing the colloid strength, "anti-caking property, (4) permeability, and the like. The surface cross-linking treatment is a multi-functional cross-linking agent capable of reacting with an acid group. Before that, the material is specifically prepared; for example, dispersing high-absorbent degreasing and cross-linking in an organic bath for surface crosslinking treatment. (疋_八_561316〇8, JKA_57_44627, JP_A_58•Gam 2, Claw sister 117222), using inorganic powder to directly mix the cross-linking agent and cross-linking agent solution into the superabsorbent resin (JP-A60-163956, jp_A_6〇_ 255814), after adding a crosslinking agent, steam treatment (JP-A-; M134 () 6) 'surface treatment of solvent, water and polyol (JP-A-1-292004, US patent gamma number) Use organic solution, water, -',: chemical substances (JP_A_2_1539()3), etc.; these surface treatment methods can increase the absorption rate and increase the water absorption rate under 5 movements, but will cause the adverse effects of excessive retention. , to reduce the performance of the actual application. _ local moon on the surface When processing a crosslinking agent capable of reacting at the same time can multiple

j such as: glycerol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol: propanol M butyl alcohol, three-chamber thiol propylamine, sorbitol, etc.; Females such as: B-European-diamine, triethylenediamine, polyethylenediamine; or compounds with two or more Wei groups can be used to convert polycondensation = alcohol = glycidyl ether, ethylene Alcohol dihydrate, diglycidyl diethylene glycol diglycidyl alcohol, alcohol diglycol diol, diglycerin polyglycidol can also be used in stone anaerobic sub-furnace gfe: 士 · ' 45• diethylene glycol carbon , 4·曱基妙二oxycyclopentan-2-one, methyl 4-yl oxime dioxane, Μ·: methyl·], 3·: oxygen heterocycle • ethyl·1, 3 dioxolane 2 - ketone,], 3 dioxin, i 13 1451416 4,6-dimethyl-1,3-dioxanone or 1,3-dioxepane-2-one and the like. The crosslinking agent may be used singly or in combination of two or more. The appropriate amount of the crosslinking agent is between 0.001% by weight and 10% by weight (based on the total solids of the reactants). A more suitable amount is between 5% and 5% by weight of the crosslinking agent. The addition dose is incapable of exhibiting an effect at a weight percentage of less than 0.001% by weight, and the amount of the crosslinking agent additive is less than the weight percentage of 〇wt°/〇, the water absorption is too low, and the resin property is lowered. The polymerization reaction can be carried out in a conventional batch reaction vessel or on a conveyor belt reactor, and the high water absorption machine can be cut into a small gel having a volume of 10 cm 3 or less. When the mincer is in the process of making the gel into a small condensate, the drying is carried out in a pre-drying manner. 'Reducing that the heat transfer effect is not good leads to the high residual monomer of the finished product. ,point. The pre-drying drying temperature can be from 耽 to 2 thieves, but it is better to dry from 5叱 to 200t, and the pre-drying time is preferably between 分钟 white (four) minutes. The pre-baked small gel is then flooded and supplied between 50 and 25 CTC. 5 (Under TC, unless it is known to be limited, the secret temperature is above 25Gt, and the effect of prolonging the drying effect will be caused by overheating, and the fineness of the day will be adjusted. 30. After drying for 4 to 240 minutes, pulverize and screen the particle size and then carry out surface crosslinking and coating treatment. 416 When the surface crosslinking agent is applied, the sound is added to the _ county surface crosslink (four) type ' Silk surface cross-axis addition, (4) loyalty product hexapeptide or surface crosslinking agent aqueous solution machine 1..., field-agent hydrophilic organic solvent aqueous solution. Hydrophilic organic solvents such as methanol, ethanol, propanol, special restrictions , can form a solution, (a) to:,:,, (10), etc. without 684966S ^ ^ ^ ^, medium to methanol, ethanol is better (US patent in the end, ^ 丨 Yang time high-yield resin towel can add 'New profit machine Salt dynasty: help solution dispersion 'inert inorganic salt powder can be sulphuric acid, or: oxidized or milky, or oxidized material mixture is better. Inert inorganic salt powder _ a secret 佶 use # ” Use or combine two or more mixed inorganic salt powders In the weight percentage, please know 5. Among them, _ to 4% is better. After entering the 嶋, (10) 叱 υ匕 υ匕 υ匕 υ匕 父 父 父 父 父 父 父 父 父 父 父 父 父 父 父 父 父 父 父 父 父 以上 以上 以上 以上 以上 以上 以上 以上 以上Pit - Bay ",, k between 30 minutes to 15 minutes ===: effect to do heat treatment temperature adjustment, heat treatment temperature coffee, heat treatment temperature is low, the occupation temperature is long. This day dryer Or the heating furnace can complete the heat treatment step, suitable for == Lifan set includes: accompanying type mixing dryer, rotating drum to work 6 dry 0, knocking bed dryer, airflow drying, and infrared drying 1351416 Etc. After the heat treatment of the surface parent joint, adding water-insoluble fine powder to the super absorbent resin, the anti-caking treatment of the lamp is aimed at increasing the difficulty between the superabsorbent resin surface, so that the superabsorbent resin still has high flow in the absorption test. The water is not added by the way of adding directly, and then the water-insoluble micropowder is adhered to the surface of the superabsorbent resin by using an adhesive; the water micro-powder includes aluminum sulfate, magnesium sulfate, aluminum oxide, magnesium oxide, zinc oxide, and the like. Phosphoric acid , Wei Wei, Shi Xizao soil, soft soil, clay, talcum powder, stagnation stone, kaolin, bentonite, activated carbon, dioxide, inorganic salt powder of titanium dioxide, and such as cellulose powder, polyester, polyethylene, Organic powder of polystyrene and polystyrene. The above-mentioned water is not miscible, and the effect of adding inorganic salt powder is the best. The use of inorganic salt powder can be used alone or in combination with two kinds of additions. The percentage _lwt% to 1 〇._%, wherein 〇() lwt% to 4 Gwt% is preferred. The water-insoluble fine powder preferably has a particle size of not more than 1 〇, and a more appropriate size _ is 0.6 mm or less. The adhesive may be a polyhydric alcohol such as glycerin, polyethylene glycol, sorbitol or the like, or a polyethyleneimine may be used. The adhesive may be used singly or in combination of two or more. The appropriate amount of the additive of the adhesive is between 0.001 wt%/〇 to i〇wt% (based on the total solids of the reactants), and more suitably between 0.005 wt% and 5 wt%, the amount of the adhesive additive. When the weight percentage is less than 0.001% by weight, the inert inorganic salt powder cannot be completely adhered to the surface of the superabsorbent resin, and when the amount of the adhesive additive is more than 1% by weight by weight, the water absorption is too low, and the resin property is lowered. 1351416

I » [Embodiment] The object of the present invention is to provide a powdery, water-insoluble, water-absorbing liquid or urine and blood, which has high retention, low residual unreacted monomers, and is still under high pressure. A high-performance superabsorbent resin having a high absorption ratio characteristic, which comprises at least: (a) a neutralization ratio in the range of 45 to 85 mol%, and an φ wave of an unsaturated monomer aqueous solution in the range of 20 to 55 (b) The superabsorbent resin hydrogel formed by polymerization after neutralization is first cut into large pieces of hydrogel by twisting; (c) the bulk hydrogel block is made by mincing Small particle gel; (d) pre-dried and completely dried, pulverized, and screened. (e) surface cross-linking agent coating; and (f) heating surface modification treatment at a temperature of 90t to 230〇C. When Lu produces a water-absorbent resin, it will produce a superabsorbent resin with a particle size of not more than 106μιη (mesh 14〇mesh) during the pulverization, grinding and screening process, which is called fine powder, and the amount of fine powder. It has a great relationship with the rate, degree and manner of drying the superabsorbent resin surface. When the superabsorbent resin is rapidly dried at a high temperature, the water inside the water-absorbent resin tends to escape due to the inability to escape, and the inside is swollen to form a blister, and the more the voids are, the squeezing and cutting during the pulverization and grinding, The easier it is to form air/envelope/breaking with the surrounding south water-absorbent resin to form fine powder, which increases the amount of superabsorbent resin dust; the amount of fine powder produces the same amount of material for the environment and the organism to the lungs Produce _... spit her (4) when the suction channel enters the lungs, the more the amount, the chance of the It suction path lesion, and when the fine powder is less: back (four) Bu, the size of the sputum is suitable for the amount of superabsorbent resin used in the dragon The more you read, the lower the rate of births and the higher the cost.

Monomer 2 depends on the (four) job of the powder, can be re-examined. First, σ was added to the catalyst to obtain a superabsorbent resin hydrogel, which was granulated by a machine (manufactured by Meridian Co., model No. SCN_2s type), and its pore diameter was ^ and 8 mm. In the process of drum granulation, pre-drying is carried out at a low temperature of 8 〇t, and the miscellaneous dryer (product of Qian Ruiyi 11 company, model DV7G type; or the product of Meridian 司司) is a type of _ Ying _28 type) is completely flooded with 13〇〇c, the high water absorption after drying is turned into a grinding mill, and the sifting out and calculating the distribution of each grain _, the system does not dry the ship, The effect of the complete drying temperature on the amount of fine powder produced and compared to observe its effect. The present invention uses a JIS standard sieve to examine the amount of fine powder produced. According to the method described in EDANA test method No. WSP22〇2(〇5); the screen with a flat plate at the bottom is placed in the vibrator, the order of the screen is that the mesh is small, and the vibrator is activated. After 1.0 mm, the vibrator was stopped after 10 minutes. _Select the superabsorbent resin of different particle sizes and weigh it' and calculate the distribution ratio of each particle size by the following equation. The particle size distribution is better than copper = * qing /. 1351416 The invention is inspected for the evaluation of the heterogeneous energy scale, and the super absorbent resin towel is coarser than l〇6um (JIS standard sieve is 140mesh^ is a fine powder, and the influence of the drying temperature on the fine powder is judged by the increase or decrease of the occupied powder. In order to demonstrate the water absorption capacity under pressure of the super absorbent resin of the present invention, the pressure absorption _ force load: 2 _ ^ and 49 fine 2) to determine the pressure absorption amount according to the European Patent 〇 339461 A specification seventh page The method described in the method is as follows; the initial weight of the super absorbent resin is placed in a cylinder according to the bottom of the screen to 'pure pure 2GgW and 49g/em2_ force for the powder, and then the cylinder is placed in a demanding position. On the top of the superabsorbent resin, α9% of sodium chloride: liquid-hours, and then the measured water-absorbent weight is divided by the weight of the superabsorbent resin. The retention force (CRC) of the present invention is determined by the tea bag test method, and the highest value and the most healthy value are taken after five times of measurement results, and the average value is taken; the Q2g super absorbent resin is tested and left in the sputum. .9% of the hydrazine aqueous solution 2 () minutes, but only this / again, the bag after the bag is centrifuged (diameter 23 (10), rotation speed ( 4 (8) -) knives | The value obtained is first subtracted from the blank group which is not filled with the superabsorbent resin, and the weight is obtained by dividing the weight of the blank (by the step jsj step) and dividing by the polymer weight. The determination of low residual monomers was carried out by liquid chromatography (HPLC). First, take o.5〇〇g to the water-absorbent resin in the 〇5〇cc conical flask to add a ruler; a solution of 100g of grain and 2cm of stir-mixer, stir at $(8) rpm for one hour. 201351416 « Add 5g of 20% A12(S〇4)3 aqueous solution, filter it with 2qing filter paper, put the filtrate into liquid chromatograph and analyze it, compare the obtained signal with the calibration curve to get the residual order. Volume. EXAMPLES The present invention is illustrated by the following examples; however, the patents and technical scope of the present invention are not limited by the examples. Embodiment 1:

1) Take 8〇2g of 48% sodium hydroxide solution and 1〇69% of water in 4〇〇 plus c conical flask, add 330g of acrylic acid and keep the temperature of the neutralization reaction system below 40C. The water-soluble unsaturated monomer after neutralization has a positive value of 6. After standing for 5 minutes, the water-soluble unsaturated monomer after partial neutralization of _g acrylic acid was neutralized, and the pH of the water-soluble unsaturated monomer after complete neutralization of ruthenium was 5.6. At this time, a water-soluble unsaturated monomer concentration aqueous solution of Irvine flag was obtained, in which 7 〇m〇l% (mole ratio) of the acrylic acid was partially neutralized with sodium acrylate. 2) Add L518 g of lysine--decyl bis acrylamide to the water-soluble unsaturated monomer solution and maintain the temperature at about 2 Torr. 3) Add 0.528 g of hydrogen peroxide' 6.62 g of sodium hydrogen sulfite and 6 62 g of persulfate to initiate the reaction. 4) The gel formed after the reaction was chopped by a cutter mill, and pre-dried in a granulation drum for about 5 minutes with a hot air of 8 (). 20 1351416 5) Dry at 130 ° C for 2 hours. 5以上。 Please, after the grinding, using a JIS standard sieve (mesh of 140, a particle size of 1 〇 6μιη), the proportion of the amount of fine powder obtained by the screening of the time of 10 minutes is 1. 52% (please Refer to Table 1). 7) The residual monomer test by HPLC was 2 〇ppm. The holding power (crq is 29.6 g/g, the water absorption ratio under pressure of 20 g/cm2 (〇·3ΑΑΡ) is 26 7 g/g, and the water absorption ratio (ojaaP) under pressure of 49 g/cm 2 is 16.3 g/g (please refer to Table-) Example 2: 1) Repeat steps 1) to 4) of Example 1, but the chopped gel is pre-dried with 12 (r hot air for about 5 minutes. 2) Repeat Example 1 Step 5. )~7) 'The retention force, the water absorption ratio under the pressure of 20g/cm2, the water absorption ratio under the pressure of 49g/cm2, the test value of the residual monomer of HPLC, and the amount of fine powder obtained by screening with JIS standard sieve, as shown in Table 1. Show. Example 3: 1) Repeated application - step 1) ~ 4) 'But the chopped gel is not pre-dried in the granulation drum, taken to the dryer, pre-dried with 8 (rc hot air) 2) 2) Repeated Example - Step 5) ~ 7), its retention force, water absorption ratio under 2 () 2 pressure, water absorption ratio under pressure of 49 gW and the residual test of HPLC seem to use JIS standard sieve screen The amount of fine powder obtained is shown in Table 1. 1351416 # * Example 4: 1) Repeat Example - Steps D to 4), but the chopped gel, preheated with α-step hot air for about 15 minutes. 2) Repeated remuneration - step 5) ~ 7), its simple force, water absorption ratio under 2〇gW pressure, residual measurement of water absorption doubled HPLC under 49-2 pressure, and the use of JIS standard_screening The amount of powder is shown in Table 1. Example 5: 1) Repeat Example - Step 1M), but chopped the condensate, pre-dried with a hot air of 12 Torr for about 15 minutes. 2 halls are actually supplemented - steps 5) to 7), their holding power, (4) m2 submersible water absorption ratio 49g/Cm [the underwater absorption ratio and the residual value of the surviving monomer and the fine powder obtained by JIS standard _ screening The amount is shown in Table 1.

Example 6: 1) Repeat the application - steps 1) to 4), but the chopped gel is not subjected to the pre-filament in the granulation drum. u 2=Overlapping Example-Step 5)~7) 'The holding force, the water absorption ratio under the pressure of (10)2, the water absorption ratio under the waste force of 49g/cm and the residual monomer of HpLc, and the standard of the claw The amount of fine powder is shown in Table-. Example 7: 22 23 1351416 1) Repeat Example - Step 1) ~ 5) ' But in step 5) the drying temperature was changed to Wc, and the drying time was about 60 minutes. 2) Repetitive Example - Step 6M), retention force, water absorption ratio under pressure of 20 g/cm2, water absorption ratio at 49 gW waste force, and test value of residual monomer of HpLC and amount of fine powder obtained by screening using JIS standard sieve As shown in Table 1. Example 8: • ^ Repeat Example 1 Steps D to 4), but the chopped gel was pre-dried with a hot air of 12 Torr for about 5 minutes. 2) Repeat Example - Step 5M), but the drying temperature in step 5) is changed to boots, the drying time is about 60 minutes, the holding force, the water absorption ratio under the pressure of 2〇g/cm2, the water absorption ratio under the pressure of 49gW and HpL ( The test value of the residual monomer and the fine powder amount obtained by screening using the JIS standard sieve are shown in Table 1. Φ Example 9: 1) Repeat Example - Step 1) to 4), but chopped coagulation The colloid is not in the granulation drum for the thief drying, and it is pre-dried with hot air for about 5 minutes. Fantasy re-solidification _-师) ~7), but in step 5) dry the temperature is OK, dry no time about 60 minutes, its retention force, 2 〇 _2 Li Li under the suction rate, under the force of absorbent HPLC_Monitoring position and utilization

23 24 1351416 No JIS standard __ selected fine powder amount, as shown in Table 1 Example 10: 1) Repeat Example 1 Step 1) a Wind pre-dry for about 15 minutes. ~ After _’(10). Example C of hot face - step 5) ~ 7), but the drying temperature in step 5) is changed to duty, dry secret room about 6 〇 minutes 'its retention force, 2 〇 gW pressure under water absorption rate, 49 g / cm (four) The amount of fine powder obtained from the material and the residual monomer of HpLc is shown in Table 1. Example 11: 1) The Example 1 step / Π / ) 4) was repeated, but the chopped gel was pre-dried with hot air for about 15 minutes. 2) Repeat Example - Step 5), but the drying temperature in Step 5) is changed to ·. C, dry _ about 6G minutes, its retention, · & moving water absorption rate, J two: T rich and new ^ 赫 赫 单体 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及As shown in Table 1. Example 12: 1) 2 Examples - Steps D to 4), but the chopped gel was not pre-dried in the granulation drum, and was taken to dryness, and pre-dried by hot air for about 玷 minutes. 24 1351416 2) Repeat step 1M) of the first embodiment, but the drying temperature of the step is changed to 160 ° C, the drying time is about 6 〇 minutes, the holding force, the water absorption ratio under the pressure of 2 〇 gW, and the material under the pressure of 49 g/cm. The amount of fine powder and the amount of fine powder obtained by screening with JIS standard sieve are shown in Table 1. Comparative Example 1: D repeats the example - step υ ~ 4), but the pre-drying temperature is changed to 2 thieves to dry. 2) Repeat the examples - steps 5) ~ 7). The tilting force, the water absorption ratio under the pressure of 2GgW, the water absorption ratio under the pressure of 49 faces and 2, the test value of the residual monomer of Hpu: and the fine powder amount obtained by the JIS standard net screening are shown in Table 1. Comparative Example 2: Overprinting - Step υ~5) The hot air of the U-stage was pre-dried in the remaining drum, but the pre-drying time was changed to 40 minutes. 2): Repeat the example - step 6) ~ 7). Its holding force, water absorption times under the pressure of 2〇_2 ^ 49g / em [the under pressure of the absorbent material and the muscle [the test value of the monomer and M JIS standard sieve _ obtained fine powder amount, as shown in Table 1). Comparative Example 3. Reset Example Step 1; Μ), but the chopped gel was pre-dried in a granulation drum for about 5 minutes with a number of 2 winds. ... 2) Repeat the example - step 5) ~ 7). Its holding force, the weight of the piano under pressure - 25 1351416 rate, the weight of the money and the weight of the squad under the pressure of the squad, the use of the amount of fine powder, as shown in the table - as shown. And Comparative Example 4: 1) Repeat the first step 乂, . However, the chopped gel is dried without the step 4). 2) = column one step 5) ~ 7). Its retention, 2. _2 Pressure Secret (4) The test of the residual monomer of HPLC seems to use the amount of fine powder obtained by JIS standard __, as shown in Table 1. Comparative Example 5: υRepeat Example - Step Correction), pre-drying in the granulation drum by hot air of the boot, and the pre-drying time was changed to 4 〇 minutes. 2 halls are really fresh _ 6) ~ 7). The retention force, the adsorption/pressure under water pressure, the pressure drop of HPLC at 49 gW, the apologetic test value, and the amount of fine powder obtained by screening using a JIS standard sieve are shown in Table 1.

26 CS 271351416 CRC 0. 3AAP 0.7AAP Fine powder residuals Example 1 29. 6g / g 26. 7g / g 16. 3g / g 1.52% 120ppm Example 2 28. 4g / g 27. 2s / g 16. 5g/g 2. 33% 140ppm Example 3 27. 3s/g 25. 9s/g 14. 9g/g 3. 74% 265ppm Example 4 30. 5g/g 27. 5g/g 17. 6g/g 1.25 % 95ppm Example 5 29. 5g / g 27. Os / g 17. 6s / g 2. 46% 125ppm Example 6 28. 6r / r 26. lg / g 16. 5g / g 3. 55% 220ppm Example七31.2g/g 28.7g/s 17.4s/s 3. 42% 230ppm Example VIII 30. 7g/g 29.2g/g 18.lg/s 4. 52% 285ppm Example IX 29. 9s/s 27. 5g/g 16. 6.12% 380ppm Example 10 32. 7g/g 29.4g/g 19.2s/g 2. 98% 200ppm Example 10 31. 5s/s 28.6g/g 18.6g/g 3. 97% 280ppm Example 10 30. 8s/g 27.9s/s 17. 9s/g 5. 89% 355ppm Comparative Example 1 25.4 g/g 23. 9 g/s 14. 2r/s 9. 52% 455 ppm Comparative Example 2 23.6 g/ g 21.7g/g 13. 6g/g 10. 68% 515ppm Comparative Example 3 26. ls/s 23. 5g/g 12. 4g/g 12. 03% 600ppm Comparative Example 4 22. 8s/g 19. 8g/ g 11.7g/g 13. 15% 595ppm Comparative Example 5 24.lg/g 22.lg/g 12.5g/g 14. 98% 530ppm 27 1351416 The main elements] [Description of Symbols]

Claims (1)

29 X. Patent application scope: A method for producing a super absorbent resin by using an aqueous solution of an unsaturated monomer, which is characterized in that: (a) the neutralization ratio is in the range of 45 to 85 mol%, and the unsaturated single The trace of the aqueous solution is in the range of 20 to 55 parts by weight; (b) the superabsorbent resin hydrogel formed by the neutralization polymerization is cut into small pieces; (C) the second time after pre-drying and then drying completely Dryer. 2' The method for producing a super absorbent resin according to claim 1, wherein the superabsorbent resin hydrogel has a pre-drying temperature range of 80. (: between 120 ° C and the pre-drying time is between 1 and 15 minutes. 3. The method for producing the super absorbent resin according to item j of the patent patent gas circumference, the pre-drying coagulation The secondary drying temperature range of the colloid is from 〖3叱 to the squid drying, and the drying time is in the range of 60~120 minutes. 4. - The method for preparing the high water absorption tree by using the non-face monomer aqueous solution, The method comprises: (a) a neutralization ratio in the range of 45 to 85 mol%, and a concentration of the aqueous solution of the unsaturated monomer in the range of 20 to 55 parts by weight; (b) high water absorption by neutralization polymerization The hydrogel is first cut into small particles of less than 1 〇 coffee 3; (c) after, 'dry dry, then completely dried, pulverized, screened; (d) surface crosslinker coating;