WO2012066888A1 - 吸水性樹脂の製造方法 - Google Patents
吸水性樹脂の製造方法 Download PDFInfo
- Publication number
- WO2012066888A1 WO2012066888A1 PCT/JP2011/073699 JP2011073699W WO2012066888A1 WO 2012066888 A1 WO2012066888 A1 WO 2012066888A1 JP 2011073699 W JP2011073699 W JP 2011073699W WO 2012066888 A1 WO2012066888 A1 WO 2012066888A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- molecular weight
- absorbent resin
- producing
- protective colloid
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Definitions
- the present invention relates to a method for producing a water absorbent resin. More specifically, the present invention relates to a method for producing a water absorbent resin having a small particle diameter and a narrow particle size distribution.
- Water-absorbing resins are widely used in various fields such as sanitary products such as paper diapers and sanitary products, agricultural and horticultural materials such as water retention agents and soil conditioners, and industrial materials such as water-stopping agents and anti-condensation agents. .
- water-absorbing resin examples include starch-acrylonitrile graft copolymer hydrolyzate, starch-acrylic acid graft copolymer neutralized product, vinyl acetate-acrylic ester copolymer saponified product, acrylic resin, and the like.
- Cross-linked products of acid partial neutralized polymers are known.
- Examples of the performance required for the water-absorbent resin include an absorption performance such as a water absorption amount and a water absorption speed, and an optimum particle size according to the application.
- sanitary materials such as disposable diapers and sanitary products are required to have a water-absorbing resin having a small particle size and a narrow particle size distribution in order to sufficiently exhibit absorption performance such as penetration rate, reversal amount, and diffusibility.
- a method for producing a water-absorbent resin a production method by an aqueous solution polymerization method, a reverse phase suspension polymerization method or the like is known.
- a surfactant is essential in the reverse phase suspension polymerization method, and as a technique focused on the surfactant, a production method using a sorbitan fatty acid ester, a sorbitol fatty acid ester or the like as the surfactant is known.
- Patent Document 1 Patent Document 1
- this method has a problem that it is difficult to stably obtain a water-absorbent resin having a small particle diameter, and that the method is strongly adhered to the wall surface of the polymerization equipment during production.
- Patent Document 2 a production method using a specific sucrose fatty acid ester as a surfactant is known (Patent Document 2). Although this method has improved productivity by preventing adhesion to the wall surface of the polymerization equipment during production, there are problems such as a large particle size of the resulting water-absorbent resin and a wide particle size distribution. There is room for improvement.
- the main object of the present invention is to provide a method for producing a water-absorbent resin by a reverse phase suspension polymerization method, which has a small particle size and a narrow particle size distribution.
- the inventors of the present application conducted reverse phase suspension polymerization in the presence of a polymer dispersant satisfying a specific range of weight average molecular weight and molecular weight distribution, It has been found that a water-absorbent resin having a small particle size and a narrow particle size distribution can be obtained.
- the present invention has been completed based on such findings, and widely includes the following aspects.
- Item 1 A method for producing a water-absorbent resin by subjecting a water-soluble ethylenically unsaturated monomer to reverse phase suspension polymerization in a petroleum hydrocarbon dispersion medium containing a surfactant and a polymer dispersant,
- the polymer dispersant is a polymer protective colloid having a weight average molecular weight (Mw) of 2000 to 15000 and a molecular weight distribution (Mw / number average molecular weight (Mn)) of 3 to 50.
- Mw weight average molecular weight
- Mn number average molecular weight
- Item 2 The water absorbing property according to Item 1, wherein the polymer protective colloid is at least one selected from the group consisting of maleic anhydride-modified polyethylene, maleic anhydride polypropylene, and maleic anhydride-modified ethylene / propylene copolymer. Manufacturing method of resin.
- Item 3 The method for producing a water absorbent resin according to Item 1 or 2, wherein the surfactant is at least one selected from the group consisting of sucrose fatty acid esters and polyglycerin fatty acid esters.
- Item 4 The production of the water-absorbent resin according to any one of Items 1 to 3, wherein the water-soluble ethylenically unsaturated monomer is at least one selected from the group consisting of (meth) acrylic acid and salts thereof. Method.
- a water-absorbing resin having a small particle size and a narrow particle size distribution can be easily produced using the reverse phase suspension polymerization method.
- the method for producing a water-absorbent resin according to the present invention comprises water-soluble ethylenically unsaturated monomers obtained by subjecting a water-soluble ethylenically unsaturated monomer to reverse phase suspension polymerization in a petroleum hydrocarbon dispersion medium containing a surfactant and a polymeric dispersant.
- the weight average molecular weight (Mw) is 2000 to 15000 and the molecular weight distribution (Mw / number average molecular weight (Mn)) is 3 to 50 as the polymer dispersant. It is a method characterized by using a polymer protective colloid.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) of the above polymer protective colloid are values measured by a high temperature gel permeation chromatograph.
- the dispersion stability of the water-soluble ethylenically unsaturated monomer in the petroleum hydrocarbon dispersion medium in the reverse phase suspension polymerization method is improved.
- the protective polymer colloid satisfies the range of 2000 to 10,000.
- the weight average molecular weight is 2000 or more, the resulting water-absorbent resin is prevented from becoming fine particles, and by setting it to 15000 or less, the particle diameter of the obtained water-absorbent resin is prevented from becoming large.
- a water-absorbent resin having a narrow particle size distribution can be obtained.
- a polymer protective colloid satisfying the range of 5 to 45 is preferable.
- a water-absorbing resin having a small particle diameter can be stably obtained, and by setting the molecular weight distribution to 50 or less, the obtained water-absorbing resin can be prevented from having a wide particle size distribution. .
- a water-absorbing resin having a small particle size and a narrow particle size distribution can be produced by the reverse phase suspension polymerization method. It is.
- the polymer protective colloid used in the production method according to the present invention is not particularly limited.
- maleic anhydride-modified polyethylene maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene / propylene copolymer Copolymers, maleic anhydride modified EPDM (ethylene / propylene / diene / terpolymer), maleic anhydride modified polybutadiene, ethylene / maleic anhydride copolymer, ethylene / propylene / maleic anhydride copolymer, butadiene / maleic anhydride copolymer
- examples thereof include polymers, oxidized polyethylene, ethylene / acrylic acid copolymers, ethyl cellulose, and ethyl hydroxyethyl cellulose.
- These polymer protective colloids may be used alone or in combination of two or more.
- maleic anhydride-modified polyethylene maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene / propylene copolymer, etc. should be used as polymer protective colloids. Is preferred.
- the amount of the polymer protective colloid used is not particularly limited, but in order to obtain a dispersion effect commensurate with the amount used, while maintaining a good dispersion state of the water-soluble ethylenically unsaturated monomer in the petroleum hydrocarbon dispersion medium.
- the amount may normally be 0.05 to 5 parts by mass with respect to 100 parts by mass of the monomer.
- the amount is preferably 0.1 to 3 parts by mass.
- the water-soluble ethylenically unsaturated monomer used in the production method according to the present invention is not particularly limited.
- (meth) acrylic acid in this specification, “acrylic” and “methacrylic” are combined).
- “(Meth) acryl” its salt; 2- (meth) acrylamide-2-methylpropanesulfonic acid, its salt; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2-
- Nonionic monomers such as hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide, polyethylene glycol mono (meth) acrylate; N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meta ) Amino such as acrylate, diethylaminopropyl (meth) acrylamide Containing unsaturated monomer, the quaternary compound and the like.
- acrylic acid, acrylate, methacrylic acid, methacrylate, acrylamide, methacrylamide, N, N-dimethylacrylamide, etc. are used as water-soluble ethylenically unsaturated monomers from the viewpoint of industrial availability. It is preferable. More preferred are acrylic acid, acrylate, methacrylic acid, methacrylate and the like.
- the water-soluble ethylenically unsaturated monomer described above may be used as an aqueous solution in order to more efficiently disperse it in a petroleum hydrocarbon dispersion medium in the reverse phase suspension polymerization method.
- concentration of the monomer in such an aqueous solution is not particularly limited, but is usually 20% by mass or more and saturated concentration or less, and preferably 25 to 70% by mass. More preferably, it is 30 to 55% by mass.
- the acid group is previously neutralized with an alkaline neutralizing agent.
- an alkaline neutralizer is not particularly limited, and examples thereof include alkali metal salts such as sodium hydroxide and potassium hydroxide, and aqueous solutions such as ammonia. These alkaline neutralizing agents may be used alone or in combination of two or more.
- the degree of neutralization of all acid groups by the above-described alkaline neutralizer is not particularly limited, but the absorption capacity is increased by increasing the osmotic pressure of the resulting water-absorbent resin, and the presence of an excess alkaline neutralizer is present. From the viewpoint of preventing problems due to safety and the like due to this, it is usually in the range of 10 to 100 mol%, and more preferably in the range of 30 to 80 mol%.
- the surfactant used in the production method according to the present invention is not particularly limited.
- sucrose fatty acid ester polyglycerin fatty acid ester or the like as the surfactant.
- the amount of the above-mentioned surfactant used is not particularly limited, but in order to maintain a good dispersion state of the water-soluble ethylenically unsaturated monomer in the petroleum hydrocarbon dispersion medium and obtain a dispersion effect commensurate with the amount used.
- the amount of the monomer is usually 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the monomer.
- the petroleum hydrocarbon dispersion medium used as the dispersion medium in the production method according to the present invention is not particularly limited, but examples thereof include aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane and ligroin, Examples thereof include alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. These petroleum hydrocarbon dispersion media may be used alone or in combination of two or more.
- n-hexane, n-heptane, cyclohexane and the like are suitably used as petroleum hydrocarbon dispersion media because they are easily available industrially, have stable quality, and are inexpensive.
- commercially available Exol heptane (ExxonMobil Corp .: containing 75 to 85% of heptane and isomer hydrocarbons) is preferably used as an example of the mixture of the above petroleum hydrocarbon dispersion medium. .
- the amount of the petroleum hydrocarbon dispersion medium described above is not particularly limited, but from the viewpoint of easily removing the heat of polymerization and controlling the reaction temperature of the reverse phase suspension polymerization method, the amount is 100 parts by mass of the monomer. Usually, it may be 50 to 600 parts by mass, and more preferably 100 to 550 parts by mass.
- water in an amount of usually 10 to 200 parts by mass may be used with respect to 100 parts by mass of the petroleum hydrocarbon dispersion medium.
- the amount is less than 10 parts by mass, the efficiency in industrial production is poor and economically undesirable.
- the amount exceeds 200 parts by mass, the dispersion state of the water-soluble ethylenically unsaturated monomer is deteriorated, and the resulting water-absorbent resin is obtained. There is a possibility that the particle diameter of the particle becomes large.
- a crosslinking agent when reverse-phase suspension polymerization of a water-soluble ethylenically unsaturated monomer, a crosslinking agent may be used as necessary.
- a crosslinking agent is not particularly limited, and a compound having two or more polymerizable unsaturated groups may be used.
- (poly) ethylene glycol in the present specification, for example, “polyethylene glycol” And “ethylene glycol” are collectively referred to as “(poly) ethylene glycol”.
- a compound having two or more other reactive functional groups may be used.
- These crosslinking agents may be used alone or in combination of two or more.
- (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, N, N′-methylenebisacrylamide, etc. Is preferably used as a crosslinking agent.
- the cross-linking agent is preferably used by adding to the above-mentioned water-soluble ethylenically unsaturated monomer in order to exhibit the effect of the cross-linking agent more efficiently.
- the amount of the above-mentioned crosslinking agent used is not particularly limited, but from the viewpoint of sufficiently enhancing the absorption performance of the resulting water-absorbent resin, it may be usually 0 to 1 mol% with respect to the total amount of the monomers used. 0.0001 to 0.5 mol% is preferable.
- crosslinking agent is optional because the water absorbing resin absorbability can also be obtained by performing crosslinking in the vicinity of the surface of the water absorbing resin in any step from the polymerization of the monomer to drying. It is because it is possible to control.
- the reaction is usually carried out by a reverse phase suspension polymerization method using a radical polymerization initiator.
- radical polymerization initiators are not particularly limited, but are, for example, persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate; methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, di-t-butyl.
- Peroxides such as peroxide, t-butylcumyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, hydrogen peroxide; 2,2′-azobis (2-Amidinopropane) dihydrochloride, 2,2′-azobis [2- (N-phenylamidino) propane] dihydrochloride, 2,2′-azobis [2- (N-allylamidino) propane] 2 hydrochloric acid Salt, 2,2′-azobis ⁇ 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane Dihydrochloride, 2,2'-azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide ⁇ , 2,2'-azobis [2-methyl-N- Azo compounds such as (2-hydroxyethyl) -propionamide] and 4,4′-azobis
- the amount of the radical polymerization initiator used is not particularly limited, but may be usually 0.005 to 1 mol% based on the total amount of the monomers used. When the amount used is less than 0.005 mol%, it takes a long time for the polymerization reaction, which is not preferable. When the amount used exceeds 1 mol%, an abrupt polymerization reaction occurs, which is not preferable.
- the radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, or L-ascorbic acid.
- a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, or L-ascorbic acid.
- the reaction temperature of the reversed-phase suspension polymerization method in the production method according to the present invention is usually 20 to 110 ° C., preferably 40 to 90 ° C., although it varies depending on the radical polymerization initiator used.
- the reaction temperature is lower than 20 ° C., the polymerization rate is slow and the polymerization time becomes long, which is not economically preferable.
- the reaction temperature is higher than 110 ° C., it becomes difficult to remove the heat of polymerization, so that it is difficult to carry out the reaction smoothly.
- the reaction time is usually 0.1 to 4 hours.
- moisture and dispersion medium are removed, and the water content of the obtained water-absorbent resin is appropriately adjusted by subjecting it to a step such as drying. Further, depending on the purpose, a lubricant, a deodorant An additive such as an antibacterial agent may be added.
- the uniformity of the particle size distribution of the water-absorbent resin obtained by the above-described production method according to the present invention is usually 1.0 to 2.3, preferably 1.0 to 2.1.
- a water-absorbing resin as an absorber
- the absorber is partially hardened when the absorber is compressed.
- the particles easily move in the absorber and the dispersion uniformity of the water-absorbent resin in the absorber is impaired. Therefore, it is preferable that the water-absorbent resin used for the absorber has a narrow particle size distribution, in other words, a smaller uniformity of the particle size distribution.
- the above-mentioned uniformity can be measured by the method shown in the following examples.
- the physiological saline water-absorbing ability, median particle size, and uniformity of particle size distribution of the water-absorbing resins obtained in each Example and Comparative Example were evaluated by the following methods.
- ⁇ Saline water absorption capacity> In a 500 mL beaker, 500 g of 0.9% by mass sodium chloride aqueous solution (physiological saline) was weighed, and 2.0 g of the water absorbent resin was dispersed so as not to generate mako. The mixture was allowed to stand for 60 minutes in a stirred state to sufficiently swell the water absorbent resin. Thereafter, the weight Wa (g) of the 75 ⁇ m JIS standard sieve is measured in advance, and the content of the beaker is filtered using this, so that the sieve has an inclination angle of about 30 degrees with respect to the horizontal. Excess water was filtered off by standing for 30 minutes in an inclined state.
- a water-absorbing resin for measurement was prepared by mixing 0.25 g of amorphous silica (Degussa Japan Co., Ltd., Sipernat 200) as a lubricant with 50 g of the water-absorbing resin. Combine the JIS standard sieve from the top in the order of 500 ⁇ m, 250 ⁇ m, 180 ⁇ m, 150 ⁇ m, 106 ⁇ m, 75 ⁇ m, 38 ⁇ m, and tray in order of the mesh, put the water absorbent resin for measurement in the top sieve, and use a low-tap shaker And shaken for 20 minutes.
- amorphous silica Degussa Japan Co., Ltd., Sipernat 200
- the mass of the water-absorbent resin remaining on each sieve is calculated as a percentage by mass with respect to the total mass, and the sieve openings and the water-absorbent remaining on the sieve are accumulated in order from the larger particle size.
- the relationship between the resin mass percentage and the integrated value was plotted on a logarithmic probability paper. By connecting the plots on the probability paper with a straight line, the particle diameter corresponding to an integrated mass percentage of 50 mass% was defined as the median particle diameter.
- ⁇ Device HLC-8121GPC / HT (detector: RI) Column: TSKgel GMHHR-H (20) HT + G2000HHR (20) HT ⁇ 2 (7.8 mm ID ⁇ 30 cm, manufactured by Tosoh Corporation) Eluent: HPLC grade 1,2,4, -trichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.), dibutylhydroxytoluene (100 parts by mass of 1,2,4, -trichlorobenzene as stabilizer) .05 parts by mass).
- ⁇ Flow rate 1.0 mL / min -Detection condition: polarity (-) ⁇ Injection volume: 0.3 mL -Column temperature: 140 ° C ⁇ System temperature: 40 °C
- Example 1 A 2 L round bottom cylindrical separable flask equipped with a stirrer, a two-stage paddle blade, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube was prepared. 286 g of n-heptane was taken into this flask, 0.92 g of sucrose stearate ester of HLB3 (Mitsubishi Chemical Foods Co., Ltd., Ryoto Sugar Ester S-370), polymer protective colloid A (manufactured by Mitsui Chemicals, High Wax 2203A). 0.092 g) was added, the temperature was raised to 80 ° C. while stirring to dissolve the surfactant and the polymer protective colloid A, and then cooled to 50 ° C.
- HLB3 Mitsubishi Chemical Foods Co., Ltd., Ryoto Sugar Ester S-370
- polymer protective colloid A manufactured by Mitsui Chemicals, High Wax 2203A
- Example 2 The same operation as in Example 1 was carried out except that the polymer protective colloid A was changed to the polymer protective colloid B (manufactured by Honeywall, A-C575A) in Example 1, to obtain 95.6 g of a water absorbent resin. Table 2 shows the measurement results of each performance.
- Example 1 is the same as Example 1 except that the polymer protective colloid A is changed to polymer protective colloid C (manufactured by Sanyo Chemical Co., Ltd., Sun Wax E310) and the amount of the polymer protective colloid used is changed to 0.28 g. Operation was performed to obtain 95.2 g of a water absorbent resin. Table 2 shows the measurement results of each performance.
- Example 1 The same operation as in Example 3 was performed except that the polymer protective colloid C was changed to the polymer protective colloid D (manufactured by Mitsui Chemicals, high wax 110P) in Example 3, to obtain 96.0 g of a water absorbent resin. .
- Table 2 shows the measurement results of each performance.
- Example 2 The same operation as in Example 3 was performed except that the polymer protective colloid C was changed to the polymer protective colloid E (manufactured by Clariant, Licowax PED522) in Example 3, and 95.5 g of the water-absorbing resin was obtained. Obtained. Table 2 shows the measurement results of each performance.
- Example 3 In Example 3, except that the polymer protective colloid C was changed to the polymer protective colloid F (manufactured by Sanyo Chemical Co., Ltd., Umex 2000), the same operation as in Example 3 was performed to obtain 95.7 g of a water absorbent resin. Table 2 shows the measurement results of each performance.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
500mL容のビーカーに、0.9質量%塩化ナトリウム水溶液(生理食塩水)500gを量り取り、吸水性樹脂2.0gを、ママコが発生しないように分散させた。撹拌させた状態で60分間放置し、吸水性樹脂を十分に膨潤させた。その後、あらかじめ目開き75μmJIS標準篩の重量Wa(g)を測定しておき、これを用いて、前記ビーカーの内容物をろ過し、篩いを水平に対して約30度の傾斜角となるように傾けた状態で、30分間放置することにより余剰の水分をろ別した。吸水ゲルの入った篩いの質量Wb(g)を測定し、以下の式により、生理食塩水吸水能を求めた。
生理食塩水吸水能(g/g)=[Wb-Wa](g)/吸水性樹脂の質量(g)
吸水性樹脂50gに、滑剤として、0.25gの非晶質シリカ(デグサジャパン(株)、Sipernat200)を混合し測定用吸水性樹脂とした。JIS標準篩いを上から、目開き500μm、250μm、180μm、150μm、106μm、75μm、38μm、受け皿の順に組み合わせて、前記測定用吸水性樹脂を最上の篩いに入れ、ロータップ式振とう機を用いて、20分間振とうさせた。
前記中位粒子径測定において、積算質量百分率が15.9質量%に相当する粒子径(X1)および84.1質量%の相当する粒子径(X2)を求め、下記式により均一度を求めた。
均一度=X1/X2
すなわち、粒子径分布が狭い場合、均一度は1に近づき、粒子径分布が広くなれば、均一度が1より大きくなる。
実施例及び比較例に用いた、高分子保護コロイドの重量平均分子量(Mw)、数平均分子量(Mn)を測定し、分子量分布(Mw/Mn)を算出した。なお、測定には、高温ゲル浸透クロマトグラフを用いて、以下の条件で測定した。結果を表1に示す。
・装置:HLC-8121GPC/HT(検出器:RI)
・カラム:TSKgel GMHHR-H(20)HT+G2000HHR(20)HT×2本(7.8mmID×30cm、東ソー(株)製)
・溶離液:HPLC級1,2,4,-トリクロロベンゼン(和光純薬工業(株)製)に、安定剤としてジブチルヒドロキシトルエン(1,2,4,-トリクロロベンゼン100質量部に対して0.05質量部)を添加したもの。
・流量:1.0mL/min
・検出条件:polarity(-)
・注入量:0.3mL
・カラム温度:140℃
・システム温度:40℃
攪拌機、2段パドル翼、還流冷却器、滴下ロートおよび窒素ガス導入管を備えた2L容の丸底円筒型セパラブルフラスコを準備した。このフラスコにn-ヘプタン286gをとり、HLB3のショ糖ステアリン酸エステル(三菱化学フーズ(株)、リョートーシュガーエステルS-370)0.92g、高分子保護コロイドA(三井化学製、ハイワックス2203A)を0.092g添加し、撹拌しつつ80℃まで昇温して界面活性剤及び高分子保護コロイドAを溶解した後、50℃まで冷却した。
実施例1において、高分子保護コロイドAを高分子保護コロイドB(Honeywll製、A-C575A)に変更した以外は、実施例1と同様の操作を行い、吸水性樹脂95.6gを得た。各性能の測定結果を表2に示す。
実施例1において、高分子保護コロイドAを高分子保護コロイドC(三洋化成製、サンワックスE310)に、高分子保護コロイドの使用量を0.28gに変更した以外は、実施例1と同様の操作を行い、吸水性樹脂95.2gを得た。各性能の測定結果を表2に示す。
実施例3において、高分子保護コロイドCを高分子保護コロイドD(三井化学製、ハイワックス110P)に変更した以外は、実施例3と同様の操作を行い、吸水性樹脂96.0gを得た。各性能の測定結果を表2に示す。
実施例3において、高分子保護コロイドCを高分子保護コロイドF(三洋化成製、ユーメックス2000)に変更した以外は、実施例3と同様の操作を行い、吸水性樹脂95.7gを得た。各性能の測定結果を表2に示す。
Claims (4)
- 水溶性エチレン性不飽和単量体を、界面活性剤および高分子系分散剤を含む石油系炭化水素分散媒中で逆相懸濁重合させて吸水性樹脂を製造する方法であって、該高分子系分散剤が、重量平均分子量(Mw)が2000~15000であり、且つ分子量分布(Mw/数平均分子量(Mn))が3~50である高分子保護コロイドであることを特徴とする吸水性樹脂の製造方法。
- 高分子保護コロイドが、無水マレイン酸変性ポリエチレン、無水マレイン酸ポリプロピレン、及び無水マレイン酸変性エチレン・プロピレン共重合体からなる群より選ばれた少なくとも1種である請求項1に記載の吸水性樹脂の製造方法。
- 界面活性剤が、ショ糖脂肪酸エステル及びポリグリセリン脂肪酸エステルからなる群より選ばれた少なくとも1種である請求項1又は2に記載の吸水性樹脂の製造方法。
- 水溶性エチレン性不飽和単量体が、(メタ)アクリル酸、及びその塩からなる群より選ばれた少なくとも1種である請求項1~3いずれか1項に記載の吸水性樹脂の製造方法。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012544159A JP5855012B2 (ja) | 2010-11-15 | 2011-10-14 | 吸水性樹脂の製造方法 |
BR112013011953A BR112013011953A2 (pt) | 2010-11-15 | 2011-10-14 | método para produzir resina absorvente de água |
CN201180054940.3A CN103209999B (zh) | 2010-11-15 | 2011-10-14 | 制造吸水性树脂的方法 |
EP11842161.9A EP2641920A4 (en) | 2010-11-15 | 2011-10-14 | METHOD FOR PRODUCING A WATER ABSORBENT RESIN |
SG2013030242A SG189955A1 (en) | 2010-11-15 | 2011-10-14 | Method for producing water-absorbent resin |
US13/882,314 US9273156B2 (en) | 2010-11-15 | 2011-10-14 | Method for producing water-absorbent resin |
KR1020137013903A KR101785442B1 (ko) | 2010-11-15 | 2011-10-14 | 흡수성 수지의 제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010254363 | 2010-11-15 | ||
JP2010-254363 | 2010-11-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012066888A1 true WO2012066888A1 (ja) | 2012-05-24 |
Family
ID=46083828
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/073699 WO2012066888A1 (ja) | 2010-11-15 | 2011-10-14 | 吸水性樹脂の製造方法 |
Country Status (9)
Country | Link |
---|---|
US (1) | US9273156B2 (ja) |
EP (1) | EP2641920A4 (ja) |
JP (1) | JP5855012B2 (ja) |
KR (1) | KR101785442B1 (ja) |
CN (1) | CN103209999B (ja) |
BR (1) | BR112013011953A2 (ja) |
SG (1) | SG189955A1 (ja) |
TW (1) | TWI511984B (ja) |
WO (1) | WO2012066888A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015016075A1 (ja) * | 2013-07-29 | 2015-02-05 | 住友精化株式会社 | 吸水性樹脂粒子の製造方法 |
EP3391961A1 (en) | 2017-04-19 | 2018-10-24 | The Procter & Gamble Company | Agglomerated superabsorbent polymer particles having a specific size ratio |
EP3391963A1 (en) | 2017-04-19 | 2018-10-24 | The Procter & Gamble Company | Agglomerated superabsorbent polymer particles comprising clay platelets with edge modification and/or surface modification |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR112013014730B1 (pt) * | 2011-02-08 | 2021-05-04 | Sumitomo Seika Chemicals Co., Ltd | método de produção de resina absorvente de água |
KR102086805B1 (ko) | 2013-11-19 | 2020-03-09 | 엘지디스플레이 주식회사 | 유기전계발광표시장치 |
KR102501011B1 (ko) * | 2017-03-29 | 2023-02-17 | 스미토모 세이카 가부시키가이샤 | 흡수성 수지 |
US11053370B2 (en) | 2017-04-19 | 2021-07-06 | The Procter & Gamble Company | Agglomerated superabsorbent polymer particles having a specific size ratio |
US10767029B2 (en) | 2017-04-19 | 2020-09-08 | The Procter & Gamble Company | Agglomerated superabsorbent polymer particles comprising clay platelets with edge modification and/or surface modification |
JP7144284B2 (ja) * | 2018-11-09 | 2022-09-29 | Joyson Safety Systems Japan株式会社 | 動力伝達部材、プリテンショナ、リトラクタ及び動力伝達部材の製造方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56131608A (en) | 1980-03-19 | 1981-10-15 | Seitetsu Kagaku Co Ltd | Production of acrylic acid polymer having excellent absorptive capacity for saline water |
JPS5721405A (en) * | 1980-07-14 | 1982-02-04 | Kao Corp | Production of bead polymer from water-soluble ethylenically unsaturated monomer |
JPS6187702A (ja) | 1984-10-05 | 1986-05-06 | Seitetsu Kagaku Co Ltd | 吸水性樹脂の製造方法 |
JPH01168703A (ja) * | 1987-02-06 | 1989-07-04 | Lion Corp | 逆相懸濁重合用分散剤 |
JPH0559107A (ja) * | 1991-09-04 | 1993-03-09 | Kao Corp | 逆相懸濁重合用分散剤 |
WO2007126003A1 (ja) * | 2006-04-27 | 2007-11-08 | Sumitomo Seika Chemicals Co., Ltd. | 吸水性樹脂の製造方法 |
WO2009025235A1 (ja) * | 2007-08-23 | 2009-02-26 | Sumitomo Seika Chemicals Co., Ltd. | 衛生材用途に適した吸水性樹脂 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2938920B2 (ja) * | 1990-01-31 | 1999-08-25 | 住友精化株式会社 | 吸水性樹脂の製造方法 |
GB2418669B (en) * | 2003-06-23 | 2008-05-21 | Mitsui Chemicals Inc | Polyethylene wax, lost wax composition for precision casting containing same, and method for forming model for precision casting |
JP2006143766A (ja) | 2004-11-16 | 2006-06-08 | Dainippon Ink & Chem Inc | 吸水性樹脂の製造方法 |
DE602007003397D1 (de) | 2006-03-29 | 2010-01-07 | Nippon Catalytic Chem Ind | Verfahren zur Herstellung von wasserabsorbierendem Polyacrylsäure (Salz)-Harz |
WO2007123188A1 (ja) * | 2006-04-24 | 2007-11-01 | Sumitomo Seika Chemicals Co., Ltd. | 吸水性樹脂粒子の製造方法、およびそれにより得られる吸水性樹脂粒子 |
-
2011
- 2011-10-14 CN CN201180054940.3A patent/CN103209999B/zh active Active
- 2011-10-14 JP JP2012544159A patent/JP5855012B2/ja active Active
- 2011-10-14 KR KR1020137013903A patent/KR101785442B1/ko active IP Right Grant
- 2011-10-14 US US13/882,314 patent/US9273156B2/en not_active Expired - Fee Related
- 2011-10-14 EP EP11842161.9A patent/EP2641920A4/en not_active Withdrawn
- 2011-10-14 BR BR112013011953A patent/BR112013011953A2/pt not_active Application Discontinuation
- 2011-10-14 WO PCT/JP2011/073699 patent/WO2012066888A1/ja active Application Filing
- 2011-10-14 SG SG2013030242A patent/SG189955A1/en unknown
- 2011-10-27 TW TW100139108A patent/TWI511984B/zh not_active IP Right Cessation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56131608A (en) | 1980-03-19 | 1981-10-15 | Seitetsu Kagaku Co Ltd | Production of acrylic acid polymer having excellent absorptive capacity for saline water |
JPS5721405A (en) * | 1980-07-14 | 1982-02-04 | Kao Corp | Production of bead polymer from water-soluble ethylenically unsaturated monomer |
JPS6187702A (ja) | 1984-10-05 | 1986-05-06 | Seitetsu Kagaku Co Ltd | 吸水性樹脂の製造方法 |
JPH01168703A (ja) * | 1987-02-06 | 1989-07-04 | Lion Corp | 逆相懸濁重合用分散剤 |
JPH0559107A (ja) * | 1991-09-04 | 1993-03-09 | Kao Corp | 逆相懸濁重合用分散剤 |
WO2007126003A1 (ja) * | 2006-04-27 | 2007-11-08 | Sumitomo Seika Chemicals Co., Ltd. | 吸水性樹脂の製造方法 |
WO2009025235A1 (ja) * | 2007-08-23 | 2009-02-26 | Sumitomo Seika Chemicals Co., Ltd. | 衛生材用途に適した吸水性樹脂 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2641920A4 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015016075A1 (ja) * | 2013-07-29 | 2015-02-05 | 住友精化株式会社 | 吸水性樹脂粒子の製造方法 |
JPWO2015016075A1 (ja) * | 2013-07-29 | 2017-03-02 | 住友精化株式会社 | 吸水性樹脂粒子の製造方法 |
EP3391961A1 (en) | 2017-04-19 | 2018-10-24 | The Procter & Gamble Company | Agglomerated superabsorbent polymer particles having a specific size ratio |
EP3391963A1 (en) | 2017-04-19 | 2018-10-24 | The Procter & Gamble Company | Agglomerated superabsorbent polymer particles comprising clay platelets with edge modification and/or surface modification |
WO2018194780A1 (en) | 2017-04-19 | 2018-10-25 | The Procter & Gamble Company | Agglomerated superabsorbent polymer particles comprising clay platelets with edge modification and/or surface modification |
WO2018194782A1 (en) | 2017-04-19 | 2018-10-25 | The Procter & Gamble Company | Agglomerated superabsorbent polymer particles having a specific size ratio |
Also Published As
Publication number | Publication date |
---|---|
EP2641920A4 (en) | 2014-03-19 |
JPWO2012066888A1 (ja) | 2014-05-12 |
US9273156B2 (en) | 2016-03-01 |
KR101785442B1 (ko) | 2017-10-16 |
EP2641920A1 (en) | 2013-09-25 |
JP5855012B2 (ja) | 2016-02-09 |
US20130217846A1 (en) | 2013-08-22 |
TWI511984B (zh) | 2015-12-11 |
BR112013011953A2 (pt) | 2016-08-30 |
TW201223971A (en) | 2012-06-16 |
CN103209999A (zh) | 2013-07-17 |
KR20130140756A (ko) | 2013-12-24 |
CN103209999B (zh) | 2015-09-16 |
SG189955A1 (en) | 2013-06-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5855012B2 (ja) | 吸水性樹脂の製造方法 | |
JP3967358B2 (ja) | 吸水性樹脂の製造方法 | |
JP5219804B2 (ja) | 吸水性樹脂粒子の製造方法、およびそれにより得られる吸水性樹脂粒子 | |
EP0751159B1 (en) | Method of preparing water-absorbing resin | |
JP5027414B2 (ja) | 吸水性樹脂粒子の製造方法 | |
JP2938920B2 (ja) | 吸水性樹脂の製造方法 | |
US9074022B2 (en) | Process for production of water-absorbent resin | |
JP5927289B2 (ja) | 吸水性樹脂粒子の製造方法 | |
JP3363000B2 (ja) | 吸水性樹脂の製造方法 | |
JP5896990B2 (ja) | 吸水性樹脂の製造方法 | |
TWI530506B (zh) | 吸水性樹脂的製造方法 | |
TW201641609A (zh) | 吸水性樹脂及吸水劑 | |
US20130273351A1 (en) | Method for producing water-absorbent resin | |
JPH11130968A (ja) | 吸水性樹脂及びその製造方法 | |
JP2002105125A (ja) | 吸水性樹脂の製造方法 | |
US10835887B2 (en) | Process for producing water-absorbing resin particles | |
JP6368211B2 (ja) | 新規架橋体組成物およびその製造方法 | |
JP4583080B2 (ja) | 吸水性樹脂の製造方法 | |
CN113906056A (zh) | 吸水性树脂和阻水材料 | |
CA3135359A1 (en) | Water-absorbing resin and water-blocking material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11842161 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2012544159 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13882314 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011842161 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137013903 Country of ref document: KR Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112013011953 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112013011953 Country of ref document: BR Kind code of ref document: A2 Effective date: 20130514 |