WO2022239628A1 - ポリ(メタ)アクリル酸(塩)系吸水性樹脂、及び吸収体 - Google Patents
ポリ(メタ)アクリル酸(塩)系吸水性樹脂、及び吸収体 Download PDFInfo
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- WO2022239628A1 WO2022239628A1 PCT/JP2022/018668 JP2022018668W WO2022239628A1 WO 2022239628 A1 WO2022239628 A1 WO 2022239628A1 JP 2022018668 W JP2022018668 W JP 2022018668W WO 2022239628 A1 WO2022239628 A1 WO 2022239628A1
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- water
- absorbent resin
- mass
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- gel
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Images
Classifications
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- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
Definitions
- the present invention relates to water absorbent resins and absorbent bodies. More specifically, the present invention relates to a poly(meth)acrylic acid (salt)-based water absorbent resin and an absorbent body.
- water-absorbing resins are widely used as water-absorbing agents.
- water absorbent resins include hydrolysates of starch-acrylonitrile graft copolymers, neutralized starch-acrylic acid graft polymers, saponified vinyl acetate-acrylic acid ester copolymers, (meth ) Cross-linked products of partially neutralized acrylic acid polymers are known.
- the water absorbent resin poly (meth) acrylic acid (salt) based water absorbent resin using (meth) acrylic acid and / or its salt as a main component of the monomer is industrially produced most in
- Patent Literatures 1 to 5 disclose water-absorbing resins that are excellent in elasticity after absorbing water when used as a constituent material of an absorbent body.
- the water absorbent resins described in Patent Documents 1 to 5 can maintain sufficiently high elastic force even when the proportion of fibrous materials in the absorbent core in the absorbent body is low (high concentration core). Therefore, according to the techniques described in Patent Documents 1 to 5, the thickness can be reduced without impairing the absorption performance.
- the water-absorbent resin having excellent elasticity described in the prior art has a swelled state due to the water-absorbent resin that swells due to liquid absorption (water absorption), and when the absorbent article is worn, the core continues to swell, and the user feels uncomfortable. Met.
- One embodiment of the present invention has been made in view of the above problems, and its object is to provide a novel absorbent resin that can provide an absorbent article that suppresses swelling of the water absorbent portion during use in a thin absorbent article;
- An object of the present invention is to provide an absorbent body.
- the present inventors have found that poly(meth)acrylic acid (salt)-based water-absorbent material having a high compressibility of the swelling gel
- the present inventors have independently found that a flexible resin is suitable, and have completed the present invention.
- the water-absorbent resin according to one embodiment of the present invention is a poly(meth)acrylic acid (salt)-based water-absorbent resin, and the swollen gel compressibility represented by the following (formula 1) is 3% or more.
- Swollen gel compressibility [%] (D1-D2) / D1 ⁇ 100 (Formula 1)
- D1 is a measuring device equipped with a piston with a diameter of 59 mm and a cell with an inner diameter of 60 mm with a mesh bottom, and the water absorbent resin 1.0 g is sprinkled on the bottom.
- the device is placed in a petri dish containing a 0.9% by mass sodium chloride aqueous solution, and the water-absorbing resin absorbs the 0.9% by mass sodium chloride aqueous solution for 5 minutes.
- D2 is the thickness [mm] of the swollen gel layer formed, and D2 is placed on the piston so that the measuring device is installed on a sieve with an opening of 4750 ⁇ m and a load of 0.7 psi is applied to the swollen gel layer. It is the thickness [mm] of the swollen gel layer formed by the water-absorbing resin after repeating 10 times the operation of placing a weight on the cell and removing the weight after allowing the cell to stand still for 10 seconds.
- a water-absorbing resin and an absorbent body that can provide an absorbent article in which the swelling of the water-absorbing portion is suppressed during use in a thin absorbent article.
- FIG. 1 is a perspective view showing an external configuration of a swollen gel compressibility measuring device viewed from one direction;
- FIG. 2 is a cross-sectional view showing a part of a swollen gel compressibility measuring device.
- FIG. 10 is a plan view showing the process of manufacturing an absorbent sheet for evaluation manufactured in Examples.
- FIG. 2 is a cross-sectional view of an absorbent sheet for evaluation produced in Examples.
- water absorbent resin in one embodiment of the present invention refers to a water-swellable and water-insoluble polymeric gelling agent that satisfies the following physical properties: Say. That is, as “water swellability”, CRC defined by ERT441.2-02 is 5 g / g or more, and as “water insoluble”, Ext defined by ERT470.2-02 is a physical property of 50% by weight or less. It refers to a polymeric gelling agent that satisfies
- the water-absorbing resin can be appropriately designed according to its use, and is not particularly limited, but is preferably a hydrophilic cross-linked polymer obtained by cross-linking an unsaturated monomer having a carboxyl group.
- the water-absorbing resin is not limited to a form in which the total amount (100% by mass) is a polymer, and a water-absorbing resin composition containing additives etc. within the range satisfying the physical properties (CRC, Ext) may be in the form of
- the water-absorbing resin in one embodiment of the present invention is not limited to the final product, and is an intermediate in the manufacturing process of the water-absorbing resin (for example, a hydrous gel-like crosslinked polymer after polymerization (hydrous gel polymer), after drying and water absorbent resin powder before surface cross-linking, etc.). Together with the water-absorbent resin composition, all of these are collectively referred to as "water-absorbent resin”.
- the shape of the water-absorbing resin in one embodiment of the present invention includes sheet-like, fibrous, film-like, particulate, gel-like, and the like.
- the shape of the water absorbent resin in one embodiment of the present invention is preferably particulate. More preferably, the water absorbent resin in one embodiment of the present invention is a particulate poly(meth)acrylic acid (salt)-based water absorbent resin.
- EDANA European Disposables and Nonwovens Association
- ERT is an abbreviation for the European standard (almost a global standard) method for measuring water-absorbing resin (EDANA Recommended Test Methods). In the present invention, the physical properties of the water absorbent resin are measured according to the ERT original (2002 revision/publicly known document) unless otherwise specified.
- ppm means “mass ppm” unless otherwise specified.
- (meth)acrylic acid (salt)-based water absorbent resin means a water absorbent resin containing repeating units derived from (meth)acrylic acid (salt) as a main component, and is specifically used for polymerization.
- (meth)acrylic acid (salt) is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 90 to 100 mol%, particularly preferably means a water-absorbing resin containing substantially 100 mol %.
- weight and weight% are treated as synonyms.
- the water-absorbent resin is preferably in the form of particles, and specifically, irregularly crushed, spherical, or football-shaped. , aggregates, and the like.
- the water-absorbent resin is more preferably aggregate particles of spherical particles (for example, spherical particles containing a poly(meth)acrylic acid (salt)-based water-absorbent resin).
- the spherical particles of the water-absorbing resin can be called primary particles, and the aggregate-like particles of the water-absorbing resin can be called aggregate-like secondary particles formed by aggregating spherical primary particles.
- the term “spherical” includes not only true spheres but also substantially spherical ones having an aspect ratio of 1.0 to 1.2.
- CRC is an abbreviation for Centrifuge Retention Capacity, and means the water absorption capacity of a water absorbent resin under no pressure.
- the CRC of the water absorbent resin according to one embodiment of the present invention is preferably 30 g/g or more, more preferably 32 g/g or more, and even more preferably 34 g/g or more.
- the upper limit of the CRC is not particularly limited, and the higher the CRC of the water-absorbent resin is, the better. /g or less, more preferably 46 g/g or less.
- the water-absorbing resin has a sufficient absorption amount, and can be suitably used as an absorbent for absorbent articles such as paper diapers.
- the CRC is 50 g / g or less, a decrease in the rate of absorption of body fluids such as urine and / or blood in the water-absorbing resin is prevented or reduced, so the water-absorbing resin is a high water absorption rate type. Suitable for use in paper diapers, etc.
- the CRC value can be controlled by changing the type and/or amount of the internal cross-linking agent and/or the surface cross-linking agent during production of the water absorbent resin. An example of the CRC measurement method will be described in detail in Examples.
- Ext is an abbreviation for Extractables (water-soluble matter), and means the amount of soluble matter extracted from the water absorbent resin.
- the water-soluble content is measured according to the EDANA method (ERT470.2-02).
- the Ext of the water absorbent resin according to one embodiment of the present invention is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
- the lower limit of Ext is 0% by mass, but it is preferably 2% by mass or more, more preferably 4% by mass or more, from the viewpoint of the balance between other physical properties of the water absorbent resin and Ext.
- the Ext is 30% by mass or less, a decrease in the rate at which the water-absorbing resin absorbs body fluids such as urine and/or blood is prevented or reduced, so the water-absorbing resin is a high water-absorbing rate type paper diaper.
- suitable for use in The value of Ext can be controlled by changing the types and/or amounts of the polymerization initiator, internal cross-linking agent, and/or surface cross-linking agent during production of the water absorbent resin.
- the value of Ext can also be controlled by using a chain transfer agent in the polymerization process during production of the water absorbent resin.
- AAP is an abbreviation for Absorption against Pressure, and means the water absorption capacity of a water absorbent resin under pressure.
- AAP is measured according to the EDANA method (ERT442.2-02), except that the load condition is changed to 4.83 kPa (0.7 psi). Specifically, using a 0.9% by mass (mass/mass%) sodium chloride aqueous solution, 0.9 g of a water-absorbing resin was swollen for 1 hour under a pressure of 4.83 kPa, and then AAP (absorption capacity under pressure ) (unit: g/g).
- the AAP of the water absorbent resin according to one embodiment of the present invention is preferably 18 g/g or more, more preferably 20 g/g or more, and still more preferably 23 g/g or more from the viewpoint of water absorption characteristics when used in sanitary materials. is.
- the upper limit of AAP of the water absorbent resin is not particularly limited, but is preferably 40 g/g or less.
- Moisture content is measured according to the EDANA method (ERT430.2-02) except that the sample amount is changed to 1.0 g and the drying temperature is changed to 180°C. An example of a method for measuring the moisture content will be described in detail in Examples.
- the water content of the water absorbent resin according to one embodiment of the present invention is not particularly limited, but is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and still more preferably 2% by mass to 13% by mass. %, more preferably 5% by mass to 13% by mass, still more preferably 8% by mass to 13% by mass, and particularly preferably 10% by mass to 13% by mass. If the water content is 1% by mass to 20% by mass, a decrease in the absorption rate of body fluids such as urine and/or blood in the water-absorbing resin is prevented or reduced, so the water-absorbing resin has a high water absorption rate. Suitable for use with type paper diapers, etc.
- Mass average particle size (D50) "Mass-average particle diameter (D50)" is defined as "(3) Mass-Average Particle Diameter (D50) and Logarithmic Standard Deviation” described in columns 27 and 28 of US Pat. No. 7,638,570. ( ⁇ ) of Particle Diameter Distribution”. A specific measuring method will be described in detail in Examples below.
- the mass average particle diameter (D50) of the water absorbent resin according to one embodiment of the present invention is preferably 50 ⁇ m to 700 ⁇ m, more preferably 50 ⁇ m to 500 ⁇ m, still more preferably 100 ⁇ m to 400 ⁇ m.
- the ratio of particles having a mass average particle diameter of less than 45 ⁇ m in 100% by mass of the water-absorbent resin is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 10% by mass. % or less.
- the mass average particle size is 50 ⁇ m or more, the water absorbent resin has little dust and is easy to handle.
- the water absorbent resin can prevent or reduce the rate of absorption of body fluids such as urine and / or blood, so that the water absorbent resin has a high water absorption rate. Suitable for use with type paper diapers, etc.
- the number-average particle size of the primary particles (for example, spherical particles) constituting the aggregates (the aggregate-like particles) can be measured using an electron microscope.
- the number average particle diameter of the primary particles of the water absorbent resin is preferably 5 ⁇ m to 800 ⁇ m, more preferably 8 ⁇ m to 500 ⁇ m, still more preferably 10 ⁇ m to 300 ⁇ m, even more preferably 10 ⁇ m to 200 ⁇ m, particularly preferably 30 ⁇ m to 200 ⁇ m.
- the bulk density of the water absorbent resin is preferably 0.68 g/cm 3 to 1.00 g/cm 3 , preferably 0.69 g/cm 3 to 0.95 g/cm 3 , most preferably is 0.68 g/cm 3 to 0.90 g/cm 3 .
- the water absorbing resin prevents or reduces the rate at which it absorbs body fluids such as urine and/or blood.
- the resin is suitable for use in high water absorption speed type paper diapers and the like.
- liquid permeability of the water-absorbing resin in the present invention refers to the flowability of liquid passing between the particles of the swollen gel under load or under no load, and is representative A typical measurement method is GBP (Gel Bed Permeability).
- GBP Gel Bed Permeability
- “GBP” refers to the liquid permeability of a 0.9% by mass sodium chloride aqueous solution to a water absorbent resin under load or in free swelling, in accordance with the GBP test method disclosed in WO 2005/016393. measured.
- the particle size of the water-absorbing resin is measured without being classified into 300 ⁇ m or more and 600 ⁇ m or less.
- the absorbent core exhibits liquid permeability even when swelling is suppressed
- the GBP of the water absorbent resin is preferably 5 ⁇ 10 ⁇ 9 cm 2 or more, more preferably 10 ⁇ 10 ⁇ 9 cm 2 or more, and still more preferably. is 15 ⁇ 10 ⁇ 9 cm 2 or more.
- the “swollen gel compression ratio” in the present invention refers to the water absorbent resin when a load is repeatedly applied to the swollen gel of the water absorbent resin in the cell having a mesh-like bottom. It is a new physical property value that represents the thickness change (compressibility) of the swollen gel layer. "Swollen gel compressibility" is measured by the method described later. A water absorbent resin having a large “swollen gel compressibility” compresses the swollen gel layer of the water absorbent resin when a load is applied repeatedly in a thin water absorbent sheet for light incontinence, for example.
- a water absorbent resin having a high "swollen gel compressibility” is preferable because swelling of the absorbent core can be suppressed even when used for a long period of time.
- the "swollen gel compressibility" is 3.0% or more, preferably 3.5% or more, more preferably 4.0% or more, still more preferably 4.5% or more, and particularly preferably 5.0% or more.
- the upper limit of the swelling gel compressibility is preferably 30% or less, 25% or less, and 20% or less in this order from the viewpoint of maintaining the absorption performance of the swelling gel layer of the water absorbent resin.
- Thickness D1 of swollen gel layer before compression In the measurement of the "swollen gel compressibility", the thickness D1 of the swollen gel layer before compression is used to prevent or reduce discomfort due to excessive swelling of the absorbent core when the water absorbent resin is used in the absorbent article. Therefore, the lower the numerical value, the better.
- the thickness D1 of the swollen gel layer before compression is preferably 20 mm or less, more preferably 15 mm or less, and even more preferably less than 15 mm.
- the lower limit of D1 is not particularly limited as long as it exceeds 0 mm, preferably 5 mm or more, more preferably 10 mm or more, and still more preferably 12 mm or more.
- Thickness D2 of swollen gel layer after compression In the measurement of the "swollen gel compressibility", the thickness D2 of the swollen gel layer after compression is used for the absorbent article, and when the water absorbent resin is used in the absorbent article and a load (body weight) is applied, the absorbent core swells and causes discomfort. From the viewpoint of prevention or reduction, a lower numerical value is preferable.
- the "thickness D2 of the swollen gel layer after compression” is preferably 18 mm or less, more preferably 15 mm or less, and even more preferably less than 15 mm.
- the lower limit of D2 is not particularly limited as long as it exceeds 0 mm, preferably 5 mm or more, more preferably 10 mm or more, and still more preferably 12 mm or more.
- FIG. 1 is a perspective view showing an external configuration of a swollen gel compressibility measuring device (measuring device) viewed from one direction.
- FIG. 2 is a cross-sectional view showing part of a swollen gel compressibility measuring device.
- the swollen gel compressibility measuring device comprises a cell 11, a piston 12, a petri dish 13 and a weight 14.
- the inner diameter of the cell 11 is 60 mm and the diameter of the piston 12 is 59 mm.
- the cell 11 has a bottom portion 15.
- the bottom portion 15 is a mesh made of stainless steel and is formed of a mesh with an opening of 36 ⁇ m (that is, 400 mesh).
- FIG. 2 The method for measuring the compressibility of the swollen gel will be explained using Figures 1 and 2.
- a water-absorbing resin 16 is sprinkled on the bottom portion 15 of the cell 11 having an inner diameter of 60 mm and having a mesh-like bottom portion 15 .
- a piston 12 with a diameter of 59 mm is put into the cell 11 from above the dispersed water absorbent resin 16 .
- the cell 11 having the piston 12 and the water absorbent resin 16 is placed in the petri dish 13 and left for 5 minutes.
- a 0.9% by mass sodium chloride aqueous solution is present in the petri dish 13 .
- this operation allows the water absorbent resin 16 in the cell 11 to absorb the 0.9% by mass sodium chloride aqueous solution for 5 minutes, thereby forming the water absorbent resin 16 into a swelling gel layer (swelling gel layer).
- a weight 14 is shown above the piston 12 inside the cell 11 placed in the Petri dish 13 .
- a weight was placed on the piston 12. 14 is not included.
- the weight 14 rests on the piston 12 in the cell 11 placed on the sieve.
- FIG. 1 the state when the weight 14 is placed on the piston 12 in the cell 11 placed on the sieve is shown for convenience using the piston 12 in the cell 11 placed in the petri dish 13. It's nothing more than
- the thickness [mm] of the swelling gel layer is measured, and this is defined as D1.
- the cell 11 having the swollen gel layer of the water absorbent resin 16 and the piston 12 is taken out from the petri dish 13 and placed on a sieve with an opening of 4750 ⁇ m.
- the thickness [mm] of the swollen gel layer formed by the water absorbent resin 16 is measured and defined as D2.
- the water absorbent resin may contain additives for the water absorbent resin to exhibit various functions.
- the additive include organic powders such as surfactants, compounds having phosphorus atoms, oxidizing agents, organic reducing agents, inorganic reducing agents, water-insoluble inorganic fine particles, chelating agents, polyvalent metal salts, and metal soaps. , deodorants, antibacterial agents, pulp and thermoplastic fibers, and the like.
- the amount of the additive used (addition amount) is appropriately set according to the use of the water absorbent resin to be obtained. It is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less.
- the lower limit is 0.001% by mass or more, preferably 0.01% by mass or more, relative to the water absorbent resin (for example, water absorbent resin powder).
- water absorbent resin for example, water absorbent resin powder.
- water-insoluble inorganic fine particles include compounds disclosed in "[5] Water-insoluble inorganic fine particles" of International Patent Publication No. 2011/040530, and the compound is suitable for one embodiment of the present invention. can be applied to Moreover, as the polyvalent metal salt, a water-soluble polyvalent metal salt is preferable, and a water-soluble aluminum salt is more preferable.
- Water-soluble aluminum salts include, for example, aluminum sulfate.
- the method for producing a water-absorbing resin according to one embodiment of the present invention uses any of aqueous solution polymerization, reverse phase suspension polymerization, gas phase droplet polymerization and other polymerization methods. may It is preferable to adopt a reversed-phase suspension polymerization method from the viewpoint that the physical properties of the water absorbent resin according to one embodiment of the present invention can be easily controlled.
- a reversed-phase suspension polymerization method will be described below as an example.
- gels obtained by reversed-phase suspension polymerization differ from typical reversed-phase suspension polymerizations, which involve an azeotropic dehydration step in a hydrophobic organic solvent after polymerization and/or a surface cross-linking step in the dispersion system.
- a manufacturing method including a separation step, a gel granulation step, a water-containing gel drying step (preferably hot air drying), and a surface cross-linking step (preferably powder surface treatment).
- the method for producing a water absorbent resin according to one embodiment of the present invention is not particularly limited, but polymerizes the monomer in a state in which droplets containing the monomer are dispersed or suspended in a hydrophobic organic solvent. It is preferable to include a polymerization step for obtaining a hydrous gel polymer.
- a method for producing a water absorbent resin for example, droplets containing a monomer are dispersed or suspended in a liquid phase made of a hydrophobic organic solvent, and the monomer is polymerized to obtain a hydrous gel weight.
- a method of obtaining a coalescence in other words a method of obtaining a water-containing gel polymer by reversed-phase suspension polymerization, is preferred.
- the method of reversed-phase suspension polymerization may be a batch system or a continuous system.
- the batch-type production method involves adding or dropping an aqueous monomer solution into a hydrophobic organic solvent in a reaction apparatus and mixing them, thereby dispersing or suspending droplets of the aqueous monomer solution in the hydrophobic organic solvent. After turbidity, the above-mentioned monomer is polymerized to obtain a hydrous gel polymer.
- an aqueous monomer solution is continuously fed to a hydrophobic organic solvent in a reactor, and droplets of the aqueous monomer solution are dispersed or suspended in the hydrophobic organic solvent.
- a preferred embodiment of the present invention is batch reverse phase suspension polymerization.
- a separation step may be provided for separating the hydrous gel polymer obtained in the polymerization step from the hydrophobic organic solvent.
- the method for producing a water absorbent resin includes, for example, any aqueous monomer solution preparation step; any dispersion step; any polymerization step; any separation step; It includes a hydrophilization process.
- a recycling process and the like can be included.
- it may further include a transportation process, a storage process, a packing process, a storage process, and the like.
- the monomer aqueous solution is an aqueous solution containing a monomer that is a raw material for the water-absorbent resin, and is dispersed or suspended in a hydrophobic organic solvent to perform reversed-phase suspension polymerization. It is a cloudy solution.
- the solvent for the aqueous monomer solution water or a mixture of water and a water-soluble organic solvent (eg, alcohol, etc.) is preferably used, and water is even more preferable.
- the solvent is a mixture of water and a water-soluble organic solvent
- the water-soluble organic solvent e.g., alcohol, etc.
- the solvent is preferably 30% by mass or less in the mixture (100% by mass), and 5% by mass or less. is more preferable.
- a water-soluble ethylenically unsaturated monomer is preferably used as the monomer.
- water-soluble ethylenically unsaturated monomers include (meth)acrylic acid, (anhydrous) maleic acid, itaconic acid, cinnamic acid, vinylsulfonic acid, allyltoluenesulfonic acid, vinyltoluenesulfonic acid, styrenesulfonic acid.
- a polymerization inhibitor may be added to the aqueous monomer solution, if necessary, in consideration of the stability of the water-soluble ethylenically unsaturated monomer.
- the acid group is neutralized.
- the salt (neutralization salt) of the acid group-containing unsaturated monomer is preferably a salt with a monovalent cation, and at least one selected from the group consisting of alkali metal salts, ammonium salts and amine salts. It is more preferably a seed, more preferably an alkali metal salt, even more preferably at least one selected from the group consisting of sodium salts, lithium salts and potassium salts, and particularly sodium salts. preferable.
- the water-soluble ethylenically unsaturated monomer is preferably an acid group-containing unsaturated monomer and/or a salt thereof, more preferably (meta ) acrylic acid (salt), (anhydrous) maleic acid (salt), itaconic acid (salt) and/or cinnamic acid (salt), more preferably (meth)acrylic acid (salt), particularly preferably Acrylic acid (salt).
- an acid group-containing unsaturated monomer is used as a monomer, from the viewpoint of the water absorption performance of the resulting water absorbent resin, the acid group-containing unsaturated monomer and a neutralized salt of the acid group-containing unsaturated monomer It is preferable to use together with.
- the number of moles of the neutralized salt (hereinafter referred to as "neutralization rate") with respect to the total number of moles (100 mol%) of the neutralized salt of the polymer is preferably 40 mol% or more, more preferably 40 mol%. to 95 mol %, more preferably 50 mol % to 90 mol %, even more preferably 55 mol % to 85 mol %, particularly preferably 60 mol % to 80 mol %.
- any one of the exemplified monomers may be used alone, and any two or more monomers may be appropriately mixed and used.
- the monomers exemplified above can be mixed with monomers other than those exemplified above.
- the monomer used for polymerization preferably contains (meth)acrylic acid (salt) as a main component.
- the ratio of (meth)acrylic acid (salt) to the total monomers (100 mol%) used for polymerization is usually 50 mol% or more, preferably 50 mol% or more, from the viewpoint of the water absorption performance of the resulting water absorbent resin. It is 70 mol % or more, more preferably 80 mol % or more, still more preferably 90 mol % or more (the upper limit is 100 mol %).
- an internal cross-linking agent can be used as necessary.
- the internal cross-linking agent include conventionally known internal cross-linking agents having two or more polymerizable unsaturated groups and/or two or more reactive groups in one molecule.
- Examples of internal cross-linking agents include N,N'-methylenebis(meth)acrylamide, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, Trimethylolpropane di(meth)acrylate, glycerin tri(meth)acrylate, glycerin acrylate methacrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri allyl cyanurate, triallyl isocyanurate, triallyl phosphate, triallylamine, poly(meth)allyloxyalkane, (poly)ethylene glycol diglycidyl ether, glycerol diglycidyl ether, ethylene glycol, polyethylene glycol, prop
- the amount of the internal cross-linking agent to be used may be appropriately determined according to the desired physical properties of the water-absorbing resin, but the amount of the internal cross-linking agent used is usually 0.0001 to 5 mol% with respect to the total monomers (100 mol%) used for polymerization. More preferably 0.001 to 3 mol %, still more preferably 0.005 to 1.5 mol %.
- substances exemplified below can also be added to the aqueous monomer solution.
- chain transfer agents such as thiols, thiolic acids, secondary alcohols, amines, and hypophosphites
- foaming agents such as carbonates, bicarbonates, azo compounds, and air bubbles
- Chelating agents such as metal salts of ethylenediaminetetraacetic acid and metal salts of diethylenetriaminepentaacetic acid; polyacrylic acid (salts) and crosslinked products thereof; starch; cellulose; starch-cellulose derivatives;
- Other substances may be used singly or in combination of two or more.
- the amount of other substances used is not particularly limited, but the total concentration of other substances is preferably 10% by mass or less, more preferably 10% by mass or less, relative to the total monomers (100% by mass) used for polymerization. is 1% by mass or less, and more preferably 0.1% by mass or less.
- the total concentrations of (a) polyacrylic acid (salt) and crosslinked products thereof, (b) starch, (c) cellulose, (d) starch-cellulose derivatives and (e) polyvinyl alcohol are not particularly limited, but , preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less relative to the total monomer (100% by mass) used for polymerization.
- the dissolved oxygen in the aqueous monomer solution may be reduced by raising the temperature or replacing it with an inert gas.
- polymerization initiator A polymerization initiator may be used in the preparation of the aqueous monomer solution. When using a polymerization initiator to prepare the aqueous monomer solution, the aqueous monomer solution may gel and/or increase in viscosity. It is preferable to perform the following (1), (2) and (3), etc.: (1) immediately before dispersing and/or suspending the aqueous monomer solution in the hydrophobic organic solvent; (2) monomer The aqueous solution is cooled and mixed with a polymerization initiator at a temperature lower than normal temperature (for example, 20° C.
- the aqueous monomer solution and the polymerization initiator are subjected to a dispersion step while being line-mixed.
- a thermal decomposition type polymerization initiator is preferably used.
- the thermal decomposition type polymerization initiator refers to a compound that decomposes by heat to generate radicals.
- the 10-hour half-life temperature is preferably 0° C. to 120° C., more preferably 30° C. to 100° C., still more preferably 50 C. to 80.degree. C. is preferably used as a polymerization initiator.
- the polymerization initiator is preferably a water-soluble polymerization initiator, and more preferably a water-soluble radical polymerization initiator.
- water-soluble radical polymerization initiators include persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate; methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, di-t-butyl peroxide, t-butyl Cumyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, peroxides such as hydrogen peroxide; 2,2'-azobis (2-amidinopropane) ) dihydrochloride, 2,2′-azobis[2-(N-phenylamidino)propane]dihydrochloride, 2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, etc.
- persulfates such as potassium persulfate, ammonium persulfate and sodium persul
- water-soluble azo compounds and the like.
- the polymerization initiator one of these may be used alone, or two or more of them may be used in combination.
- persulfates and/or water-soluble azo compounds are preferred, and sodium persulfate, potassium persulfate, ammonium persulfate, and/or 2,2'-azobis(2-amidinopropane) dihydrochloride are more preferred.
- a salt more preferably sodium persulfate, is used.
- the amount of the thermal decomposition type polymerization initiator to be used is appropriately set according to the types of the monomer and the polymerization initiator, and is not particularly limited. From the viewpoint of production efficiency, the amount of the thermal decomposition type polymerization initiator used is preferably 0.001 g/mol or more, more preferably It is 0.005 g/mol or more, more preferably 0.010 g/mol or more. In addition, from the viewpoint of improving the water absorption performance of the water-absorbing resin, the amount of the thermal decomposition type polymerization initiator used is preferably 2 g/mol with respect to the total monomers (1 mol) used for polymerization. 1 g/mol or less, more preferably 1 g/mol or less.
- thermally decomposable polymerization initiator can also be used in combination with other polymerization initiators such as photodecomposable polymerization initiators, if necessary.
- specific examples of the photolytic polymerization initiator include benzoin derivatives, benzyl derivatives, acetophenone derivatives, benzophenone derivatives and the like.
- the thermal decomposition type polymerization initiator and the reducing agent can be used together to form a redox polymerization initiator.
- the thermal decomposition type polymerization initiator functions as an oxidizing agent.
- the reducing agent used is not particularly limited, but for example, sodium sulfite, sodium hydrogen sulfite and other (bi)sulfites; reducing metal salts such as ferrous salts; L-ascorbic acid (salts); amines, etc. is mentioned.
- the concentration of the monomer in the aqueous monomer solution (100% by mass) is selected depending on the selected monomer and the type of hydrophobic organic solvent.
- the lower limit of the concentration of the monomer in the aqueous monomer solution (100% by mass) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass. % or more, and the upper limit is preferably 100% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, and even more preferably 70% by mass or less.
- Additives such as an internal cross-linking agent, a surfactant, a density adjusting agent, a thickener, and a chelating agent can be added to the aqueous monomer solution as long as the object of one embodiment of the present invention is not hindered.
- the type and amount of additive to be added can be appropriately selected depending on the combination of the monomer and hydrophobic organic solvent used.
- the dispersing step is a step of dispersing or suspending droplets containing a monomer (for example, droplets of aqueous monomer solution) in a hydrophobic organic solvent.
- a monomer for example, droplets of aqueous monomer solution
- the concept includes suspension. More specifically, the aqueous monomer solution is added to a hydrophobic organic solvent and mixed and stirred to disperse droplets containing the monomer in the hydrophobic organic solvent.
- a stirring device equipped with stirring blades propeller blades, paddle blades, anchor blades, turbine blades, Faudler blades, ribbon blades, flat plate blades, etc.
- the diameter of the dispersed droplets (the diameter of the droplets of the dispersed monomer aqueous solution) can be adjusted by the type of stirring blade, the blade diameter, the number of revolutions, and the like.
- the stirrer is particularly suitable for batch reversed-phase suspension polymerization.
- a dispersion can also be obtained by the methods described in International Publication Nos. 2009/025235, 2013/018571, and the like.
- the dispersing step includes continuously supplying a monomer aqueous solution and a hydrophobic organic solvent separately to a dispersing device, and dispersing the monomer dispersed in the hydrophobic organic solvent. It is preferable to make droplets comprising
- the dispersing device used in the dispersing step includes a spray nozzle; Cylindrical nozzles; orifice plates in which a large number of holes are directly provided in a plate; centrifugal atomizers;
- Hydrophobic organic solvents include at least one organic solvent selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons. Specific examples include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, cyclooctane and decalin; benzene, toluene, xylene and the like.
- the hydrophobic organic solvent is preferably one or more selected from the group consisting of n-hexane, n-heptane and cyclohexane from the viewpoint of availability and quality stability. It is also possible to use a mixed solvent in which two or more kinds of hydrophobic organic solvents are mixed.
- a dispersing aid such as a surfactant and/or a polymer additive is optionally added to the hydrophobic organic solvent as long as the object of one embodiment of the present invention is not hindered.
- a dispersing aid is appropriately selected depending on the combination of the hydrophobic organic solvent and the monomers used, and usable dispersing aids are exemplified by the following surfactants and polymeric additives.
- the surfactant include sucrose fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, sorbitol fatty acid ester, polyoxyethylene sorbitol fatty acid ester, Polyoxyethylene Alkyl Ether, Polyoxyethylene Alkylphenyl Ether, Polyoxyethylene Castor Oil, Polyoxyethylene Hydrogenated Castor Oil, Alkyl Allyl Formaldehyde Condensed Polyoxyethylene Ether, Polyoxyethylene Polyoxypropylene Block Copolymer, Polyoxyethylene Polyoxypropyl Alkyl ethers, polyethylene glycol fatty acid esters, alkyl glucosides, N-alkyl gluconamides, polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, polyoxyethylene alkyl ether phosphates, and polyoxyethylene alkyl allyl ether phosphates
- R 1 and R 2 are each independently hydrogen, methyl or ethyl, and n is an integer of 3-20.
- sucrose fatty acid esters such as fatty acid esters are preferred, and sucrose fatty acid esters are particularly preferred.
- the HLB value of the surfactant used in one embodiment of the present invention is preferably in the range of 1-20, more preferably 1-10, and even more preferably 3-6.
- polymer additive examples include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, maleic anhydride-modified ethylene-propylene-diene terpolymer (EPDM), maleic anhydride-modified polybutadiene, maleic anhydride-ethylene copolymer, maleic anhydride-propylene copolymer, maleic anhydride-ethylene-propylene copolymer, maleic anhydride-butadiene copolymer, polyethylene, polypropylene , ethylene-propylene copolymer, oxidized polyethylene, oxidized polypropylene, oxidized ethylene-propylene copolymer, ethylene-acrylic acid copolymer, ethyl cellulose, hydroxyethyl cellulose and the like.
- one type may be used alone, or two or more types may be used in combination. Further, these polymer additives and the surfactant may be used in combination.
- the polymeric additive is used alone without a surfactant.
- the amount of the dispersing aid used is appropriately set according to the type of polymerization, the types of the aqueous monomer solution and the hydrophobic organic solvent, and the like. Specifically, the concentration of the dispersing aid in the hydrophobic organic solvent (100% by mass) is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass.
- the reactor used in the polymerization step may be the same dispersing device used in the dispersing step, or may be another device.
- the apparatus used in the dispersing step can be used as it is as a reaction apparatus, which is preferable in terms of workability.
- the reactor is a separate device from the dispersing device, the monomer dispersion liquid obtained in the dispersing step is supplied to the reactor.
- the shape of the reactor in which the polymerization reaction is carried out is not particularly limited, and a known reactor can be used. As described above, a stirring device that can be suitably used in the dispersion step can also be suitably used in the polymerization reaction.
- the shape of the reactor is preferably such that the monomer (aqueous solution) is dispersed as droplets in a hydrophobic organic solvent, which is a continuous phase formed in the reactor. It is a shape that allows polymerization reaction while moving.
- a reactor includes, for example, a reactor in which tubular reaction tubes are arranged vertically, horizontally or spirally.
- the monomer (aqueous solution) is supplied to the hydrophobic organic solvent moving in the reaction section (reaction tube), so that the droplets of the aqueous monomer solution do not stay and the hydrophobic organic Moves with solvent. Thereby, contact between monomer reactants having different polymerization rates is suppressed.
- the reactor may be provided with temperature control means (eg, heating means) so that the continuous phase inside the reactor can be heated and/or cooled from the outside, if necessary.
- temperature control means eg, heating means
- the polymerization temperature which is the reaction temperature in the polymerization step, may be appropriately set depending on the type and/or amount of the polymerization initiator used, but is preferably 20°C to 100°C, more preferably 40°C to 90°C. If the polymerization temperature is higher than 100°C, a rapid polymerization reaction will occur, which is not preferable.
- the polymerization temperature means the temperature of the hydrophobic organic solvent as the dispersion medium (hereinafter referred to as "Td").
- the temperature of the aqueous monomer solution rapidly rises due to heat transfer from the hydrophobic organic solvent.
- the thermally decomposable polymerization initiator decomposes with the temperature rise to generate radicals.
- a polymerization reaction is initiated by the generated radicals, and a water-containing gel is formed as the polymerization reaction progresses.
- the formed hydrous gel moves inside the reactor with the moving continuous phase, and is discharged from the reactor together with the hydrophobic organic solvent forming the continuous phase.
- the Td is preferably 70° C. or higher, more preferably 75° C. or higher, and still more preferably 80° C. or higher, from the viewpoint of the polymerization rate. be.
- the upper limit of Td is not particularly limited, it is appropriately selected from the viewpoint of safety within a range not exceeding the boiling point of the hydrophobic organic solvent forming the continuous phase.
- Multistage reversed-phase suspension polymerization In the production method according to one embodiment of the present invention, multistage polymerization may be performed from the viewpoint of obtaining an appropriate aggregate particle size (particle size of aggregate particles). Specifically, multi-stage polymerization can be carried out by further adding the aqueous monomer solution and carrying out a polymerization reaction after the completion of the first-stage polymerization step. In the multistage polymerization, the reaction solution may be appropriately stirred.
- inorganic fine particles In the production method according to one embodiment of the present invention, inorganic fine particles may be added to the water-containing gel polymer during and/or after polymerization from the viewpoint of obtaining an appropriate aggregated particle size.
- inorganic fine particles examples include silicon dioxide, aluminum oxide, titanium dioxide, calcium phosphate, calcium carbonate, magnesium phosphate, calcium sulfate, diatomaceous earth, bentonite, zeolite, and other metal oxides. be done. Silicon dioxide, aluminum oxide, and titanium dioxide are particularly preferable as the inorganic fine particles.
- the inorganic fine particles are added in an amount of generally 0.001 to 1 part by mass, preferably 0.001 to 0.5 part by mass, relative to the water-containing gel polymer (100 parts by mass).
- the amount of the inorganic fine particles to be added is within this range, the effect of adding the inorganic fine particles is efficiently exhibited, and the influence of the inorganic fine particles on the water absorption performance is small, which is preferable.
- the separation step is a step of separating the hydrous gel polymer obtained in the polymerization step from the hydrophobic organic solvent.
- the type and structure of the device used in the separation step are not particularly limited, but for example, known devices used for filtration, sedimentation, centrifugation, compression, etc. can be used.
- the mixture of the hydrous gel polymer and the hydrophobic organic solvent is heated under normal pressure or reduced pressure using the stirring device having the stirring blade used in the polymerization step, and the hydrogel polymer and the hydrophobic organic solvent are distilled.
- the solvent may be separated. Distillation under normal pressure or reduced pressure is preferably carried out in the batch-type reversed-phase suspension polymerization.
- Gel sizing step In the gel sizing step, the water-containing gel polymer separated from the hydrophobic organic solvent in the separation step is sized using a gel sizing device having an extrusion action part and a perforated plate. do. As a result, a granulated hydrogel polymer is obtained (hereinafter, the granulated hydrogel is referred to as a granulated gel).
- the gel sizing step is an optional step. Having the gel granulation step makes it easier to control the compressibility of the swollen gel layer of the water absorbent resin (swollen gel compressibility).
- the water-containing gel polymer to be subjected to the gel sizing step is in the form of a single particle of spherical gel or in the form of an aggregate of spherical gels.
- the lower limit of the average particle size of the hydrous gel polymer is not particularly limited, it is preferably 0.01 mm or more, more preferably 0.03 mm or more, still more preferably 0.05 mm or more, and still more preferably 0.1 mm or more.
- the upper limit is not particularly limited, it is preferably 20 mm or less, more preferably 10 mm or less.
- the average primary particle size of the water-containing gel polymer is not particularly limited, but is preferably 5 ⁇ m to 2000 ⁇ m, more preferably 5 ⁇ m to 1000 ⁇ m, from the viewpoint of suppressing the generation of fine powder in the drying process. , more preferably 5 ⁇ m to 800 ⁇ m, still more preferably 8 ⁇ m to 500 ⁇ m, even more preferably 10 ⁇ m to 300 ⁇ m, and particularly preferably 10 ⁇ m to 200 ⁇ m.
- a device having a cutter may be installed in front of the gel sizing device having the extrusion action part and the perforated plate to crush large aggregates of the hydrous gel polymer.
- the lower limit of the temperature of the hydrogel entering (throwing in) the gel sizing apparatus is not particularly limited, but from the viewpoint of granulation efficiency and suppression of damage to the hydrogel, it is preferably 80°C or higher, more preferably 90°C or higher. is. Although there is no particular upper limit for the temperature of the hydrous gel when it is put into the gel sizing apparatus, it is generally 100° C. or less.
- Gel sizing device As used herein, the term “gel sizing” refers to the process of extruding a wet mass of powder (e.g., hydrous gel) through small holes in a perforated plate into a columnar shape to obtain a substantially uniform shape and size from the wet powder raw material. It is an operation to create grains with In other words, by using a perforated plate, the hydrous gel in the form of coarse aggregates that have excessively aggregated in the previous solvent separation step is crushed, and the small-diameter single-particle hydrous gel is moderately aggregated. be done. Therefore, by the gel sizing step, it is possible to obtain a granulated hydrous gel (granule-sized gel) having a relatively uniform particle size.
- the granulated gel may contain monoparticulate hydrous gel.
- the "gel sizing apparatus having an extrusion action part and a perforated plate” used in the gel sizing step includes an extrusion action part and a perforated plate (die or screen), and the extrusion action part is usually a perforated plate. It is not particularly limited as long as it has an extruding member that extrudes and supplies the contents toward the perforated plate and can produce grains of a certain size by extruding the material from the perforated plate (for example, an extruder). Also, a plurality of the devices described above may be prepared, and the plurality of devices may be arranged in series and used.
- the shape of the perforated plate (die or screen) is not particularly limited, and any shape suitable for use, such as a perfect circle, an ellipse, a polygonal shape such as a hexagon, or a triangular shape, can be selected. It is possible. From the viewpoint of sizing strength, the hole shape of the perforated plate (die or screen) is preferably circular or elliptical.
- the hole diameter of the perforated plate is also not particularly limited, but is preferably 1.5 mm or less, more preferably 1.0 mm or less, and even more preferably 0.8 mm or less.
- the pore size is preferably 0.3 mm to 1.5 mm, more preferably 0.3 mm to 0.8 mm. If the hole diameter of the perforated plate is 0.3 mm or more, the extrusion can be performed efficiently.
- the pore size is defined as follows. First, when the hole is not a perfect circle, the geometric mean value of the short diameter and long diameter of the hole is adopted as the hole diameter. When the pore diameters of the pores of the perforated plate are different, the pore diameters of all the pores are calculated, and the geometric mean value thereof is adopted as the pore diameter of the perforated plate. Furthermore, when the pore diameter of the perforated plate changes from the extrusion acting portion side of the perforated plate to the opposite side (the pore diameter changes in the thickness direction of the perforated plate), the value that gives the smallest pore diameter is adopted. .
- Additives may be added to the hydrous gel polymer in the gel sizing step.
- Additives that can be added in the gel sizing process include polymerization initiators, oxidizing agents, reducing agents, chelating agents, thickening agents, surfactants, cross-linking agents, acids, bases, foaming agents, organic or inorganic fine particles, and many other additives. and valence metal salts.
- additives capable of controlling the degree of cohesion are preferably starch, cellulose, starch-cellulose derivatives, thickeners such as polyvinyl alcohol, surfactants, water-absorbing resin fine powder, cross-linking agents, polyvalent metal salts, and the like.
- the polyvalent metal salt a water-soluble polyvalent metal salt is preferable, and a water-soluble aluminum salt is more preferable.
- Water-soluble aluminum salts include, for example, aluminum sulfate.
- the drying step is a step of drying the hydrous gel.
- a drying process is a process of drying a sizing gel.
- the method of drying in the drying step is not particularly limited.
- a drying technique azeotropic dehydration in a hydrophobic dispersing solvent used in conventional reversed-phase suspension polymerization may be employed.
- both agitation drying and static drying can preferably be employed instead of azeotropic dehydration.
- a device equipped with heating means may be used to heat the hydrous gel.
- a rotary dryer equipped with a rotary container may be used as the drying device.
- a dried polymer consisting of particles obtained in the drying process can be used as a water-absorbing resin as it is for various purposes. Moreover, when producing a water-absorbing resin in this production method, it is also possible to subject the dried polymer obtained in the drying step to the surface cross-linking step described below. In this case, the dry polymer to be subjected to the surface cross-linking step, which will be described later, is also referred to as "water absorbent resin powder" for convenience.
- additives may be added to the hydrous gel as long as the effects of one embodiment of the present invention are not inhibited.
- the additive may be added to the hydrogel during heating of the hydrogel by the heating means and/or during stirring (rotation) of the hydrogel by the rotating container.
- the additive may be added to the hydrogel before the drying step (before heating the hydrogel by the heating means and/or before stirring (rotating) the hydrogel by the rotating container).
- additives may be added to the hydrous gel in any step before the drying step. The additive can reduce excessive adhesion of the hydrous gel to each other during drying, and a water absorbent resin having an excellent water absorption rate can be obtained.
- a drying aid is an example of an additive added to the hydrous gel.
- a drying aid to the hydrogel when handling particulate hydrogel with a diameter of 1 mm or less.
- a drying aid to the hydrous gel before the drying step according to one embodiment of the present invention, a water absorbent resin having an excellent water absorption rate can be obtained. That is, a method for producing a water absorbent resin according to a preferred embodiment of the present invention has a step of adding a drying aid to a hydrous gel polymer.
- drying aid The drying aid is added for the purpose of maintaining the fluidity of the hydrous gel during stirring and drying, and examples of drying aids include surfactants and/or polymer lubricants.
- a polymer lubricant and a surfactant may be used in combination as a drying aid.
- the amount of drying aid added is appropriately set according to the moisture content of the drying aid and/or the type of gel fluidizing agent.
- the total amount of drying aid added is preferably 0.001% by mass to 0.5% by mass, more preferably 0.01% by mass to 0.3% by mass, relative to the solid content (100% by mass) of the hydrous gel. %, more preferably 0.02% by mass to 0.2% by mass.
- the hydrous gel polymer in the drying step contains less than 0.08% by mass of a drying aid relative to the solid content (100% by mass) of the hydrous gel polymer.
- the water-containing gel obtained by reversed-phase suspension polymerization using a rotary dryer as in one embodiment of the present invention, the water-containing gel is less likely to fuse and the particle size can be adjusted by crushing or the like. become easier. Therefore, when the hydrous gel is dried using a rotary dryer, the amount of drying aid used can be reduced.
- the addition of the drying aid to the hydrous gel polymer is preferably carried out in a step prior to the drying step. ) addition to the granulated gel before the drying step, (3) addition to the monomer aqueous solution in the monomer aqueous solution preparation step, and (4) addition to the hydrophobic organic solvent in the dispersion step.
- Addition of the drying aid to the hydrous gel polymer is more preferably performed in the step immediately before the drying step, and is performed after the step before the drying step (for example, the gel granulation step) to before the drying step. It is more preferable to do it in between.
- drying aid is added to the hydrous gel polymer in the pre-drying step (e.g., gel sizing step), and after the pre-drying step (e.g., gel sizing step) and before the drying step. It is also a preferred form to add a drying aid to the hydrous gel polymer during the period.
- the form of addition of the drying aid before the drying step is, for example, a form in which the hydrous gel polymer and the drying aid are put into the dryer; A form in which a drying aid is added; and the like.
- the drying aid may overlap with the surfactant and/or polymeric additive used as a dispersing aid in the dispersing step.
- surfactants used in drying aids include (1) sucrose fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, and sorbitol fatty acid esters.
- polyoxyethylene sorbitol fatty acid ester polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, alkyl allyl formaldehyde condensed polyoxyethylene ether, polyoxyethylene polyoxypropylene block Copolymers, polyoxyethylene polyoxypropyl alkyl ethers, polyethylene glycol fatty acid esters, alkyl glucosides, N-alkyl gluconamides, polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, phosphate esters of polyoxyethylene alkyl ethers, and polyoxy nonionic surfactants such as phosphate esters of ethylene alkyl allyl ether; (2) betaine alkyldialkylaminoacetates such as betaine capryldimethylaminoacetate, betaine lauryldimethylaminoacetate, betaine myristyldimethylaminoacetate, be
- anionic surfactants such as monoalkali metal acetate
- cationic surfactants such as (4) long-chain alkyldimethylaminoethyl quaternary salts.
- one type may be used alone, or two or more types may be used in combination.
- polymeric lubricants include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, and maleic anhydride-modified ethylene-propylene-diene terpolymer (EPDM).
- maleic anhydride-modified polybutadiene maleic anhydride-ethylene copolymer, maleic anhydride-propylene copolymer, maleic anhydride-ethylene-propylene copolymer, maleic anhydride-butadiene copolymer, polyethylene, polypropylene, ethylene -Propylene copolymer, oxidized polyethylene, oxidized polypropylene, oxidized ethylene-propylene copolymer, ethylene-acrylic acid copolymer, ethyl cellulose, hydroxyethyl cellulose, and polyalkylene oxides such as polyethylene glycol.
- the molecular weight (weight-average molecular weight) of these polymer lubricants is suitably selected in the range of preferably 2 million to 2 million, more preferably 4 million to 1 million. Among these, one type may be used alone, or two or more types may be used in combination.
- the ratio of particles having a particle diameter of 850 ⁇ m or more is preferably as small as possible, and the dry polymer is 100% by mass. Medium, preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less.
- the formation of coarse particles is significantly suppressed by combination with drying using an agitating dryer, so the proportion of particles with a diameter of 850 ⁇ m or more is set in the preferred range. becomes possible.
- the ratio of particles having a particle size of 1400 ⁇ m or more in 100% by mass of the dry polymer is preferably as small as possible, preferably 40% by mass or less, more preferably 35% by mass. % by mass or less, more preferably 30% by mass or less.
- the water-absorbent resin (eg, water-absorbent resin powder) obtained through the drying step (and optional subsequent steps) is preferably surface-crosslinked with a surface cross-linking agent.
- This surface cross-linking is a process of providing a portion with a high cross-linking density in the surface layer of the water-absorbent resin (e.g., water-absorbent resin powder) (a portion several tens of ⁇ m from the surface of the water-absorbent resin (e.g., water-absorbent resin powder) to the center).
- Various water absorbing properties of the water absorbent resin can be improved by performing the surface cross-linking treatment.
- by appropriately adjusting the cross-linking density of the water absorbent resin it is possible to obtain particularly excellent absorbency against pressure.
- surface cross-linking in a state dispersed in a hydrophobic organic solvent which is performed in conventional reversed-phase suspension polymerization, and to powder in a dry state, which is generally performed in aqueous solution polymerization.
- Known surface cross-linking techniques are appropriately applied, including the surface cross-linking of .
- the surface cross-linking agent used in the surface cross-linking step is also indicated as a “post-crosslinking agent” in the known art in order to distinguish it from the internal cross-linking agent used in the aqueous monomer solution preparation step.
- the surface cross-linking step may be performed after the drying step or during the drying step.
- a surface cross-linking agent is generally mixed with a hydrous gel polymer (e.g., hydrous gel cross-linked polymer) or a dry polymer (e.g., cross-linked polymer) of the dried product thereof, and the mixture is heated. cross-linking reaction.
- these steps may be provided separately after the drying step, or a surface cross-linking agent may be added to the hydrous gel polymer in the drying step to simultaneously carry out the surface cross-linking reaction and drying of the polymer.
- a surface-crosslinked water-absorbing resin for example, water-absorbing resin particles
- a surface-crosslinked water-absorbing resin can be obtained by adding a surface-crosslinking agent to the water-containing gel polymer during the separation process.
- the method for producing a water-absorbing resin according to an embodiment of the present invention includes, in addition to the above-described steps, a cooling step, a pulverizing step, a water-containing (re-moistening) step, and other steps as necessary. can include an additive addition step, a classification step, a granule sizing step, and a fine powder recycling step.
- the method for producing a water absorbent resin according to an embodiment of the present invention may further include a transportation step, a storage step, a packing step, a storage step, and the like.
- the particulate dry polymer obtained in the drying step is cooled using a known cooling means to obtain a particulate dry polymer cooled to a desired temperature. be able to.
- the method for producing a water absorbent resin according to an embodiment of the present invention preferably includes a pulverization step of pulverizing the particulate dry polymer obtained in the drying step (and any subsequent cooling step).
- a water absorbent resin for example, water absorbent resin powder
- a controlled particle size or particle size distribution By performing the pulverization step, it is possible to obtain a water absorbent resin (for example, water absorbent resin powder) having a controlled particle size or particle size distribution.
- pulverization means for example, high-speed rotary pulverizers such as roll mills, hammer mills, screw mills, and pin mills; vibration mills; knuckle-type pulverizers; cylindrical mixers;
- the water-absorbing resin for example, water-absorbing resin particles
- the water-absorbing resin is treated with a polyvalent metal salt, a cationic polymer, a chelating agent, an inorganic reducing agent and an ⁇ -hydroxycarboxylic acid. It is a step of adding at least one additive selected from the group consisting of acid compounds.
- a polyvalent metal salt a water-soluble polyvalent metal salt is preferable, and a water-soluble aluminum salt is more preferable.
- Water-soluble aluminum salts include, for example, aluminum sulfate.
- the additive is preferably added to the water absorbent resin (for example, water absorbent resin particles) in the form of an aqueous solution or dispersion (slurry).
- the additive may be added to the water absorbent resin and mixed with the water absorbent resin at the same time as the surface cross-linking agent solution described above.
- Specific examples of the re-wetting step include the method described in International Patent Publication No. 2015/053372 "(2-7) Re-wetting step", and the method is also applied to one embodiment of the present invention. can be
- additives other than the additives described above can be added to the water absorbent resin to add various functions.
- additives include surfactants, compounds having phosphorus atoms, oxidizing agents, organic reducing agents, water-insoluble inorganic fine particles, organic powders such as metal soaps, deodorants, antibacterial agents, pulp and thermoplastics. A fiber etc. are mentioned.
- water-insoluble inorganic fine particles compounds disclosed in "[5] Water-insoluble inorganic fine particles" of International Patent Publication No. 2011/040530 can be mentioned, and the compound is applied to one embodiment of the present invention.
- additives from the group consisting of polyvalent metal salts, cationic polymers, and inorganic fine particles, which preferably improve the liquid permeability so that the water-absorbing resin does not impair the water-absorbing properties especially when the swollen gel layer is compressed. It is preferable to add one or more selected types to the water absorbent resin.
- a water-soluble polyvalent metal salt is preferable, and a water-soluble aluminum salt is more preferable.
- Water-soluble aluminum salts include, for example, aluminum sulfate.
- the “granule regulating step” means a step of loosening loosely agglomerated water absorbent resin (for example, water absorbent resin powder) through the surface cross-linking step to adjust the particle size.
- this granule regulating step includes a fine powder removing step and a classifying step after the surface cross-linking step.
- the granule regulating step is preferably carried out from the viewpoint of regulating the particle size of the water absorbent resin and obtaining stable water absorbing properties.
- the “fine powder recycling step” means a step of supplying fine powder of water-containing gel or water-absorbent resin generated by sieving and the like in each step as it is or after granulating the fine powder to any step. From the viewpoint of reducing the production loss of the water-absorbing resin, the fine powder recycling step is preferably carried out in one embodiment of the present invention.
- the water absorbent resin and the absorbent body according to one embodiment of the present invention can provide a thin absorbent article in which swelling of the water absorbent portion is suppressed during use. More specifically, the water absorbent resin and absorbent body according to one embodiment of the present invention can be used for a long time because the gel layer of the absorbent core is compressed due to repeated load (body weight) being applied during use in a thin absorbent article. It is possible to provide an absorbent article in which swelling of the core is suppressed even during use.
- Applications of the water-absorbing resin according to one embodiment of the present invention are not particularly limited, but preferably include absorbent articles such as disposable diapers (for infants and adults), sanitary napkins, and incontinence pads. .
- the water-absorbent resin according to one embodiment of the present invention can be suitably used as an absorber for thin high-concentration paper diapers, in which swelling of the absorbent core due to swelling gel after liquid absorption has been a problem.
- absorbent articles include soil water retention agents, sheets for raising seedlings, seed coating materials, dew condensation prevention sheets, drip absorption materials, freshness retention materials, disposable body warmers, cooling bandanas, refrigerants, and solidification of medical waste liquids.
- waste soil solidification agent water damage prevention waste liquid gelling agent, water absorbing sandbag, emergency toilet, poultice material, thickener for cosmetics, water stop material for electrical and electronic materials communication cables, gasket packing, slow release agent for fertilizer , various sustained-release agents (space disinfectants, air fresheners, etc.), pet sheets, cat litter, wound protection dressings, dew condensation prevention construction materials, oil-based moisture removers, paints, adhesives, anti-blocking agents, light Diffusing agents, matting agents, additives for decorative boards, additives for artificial marble, additives for resins such as additives for toner, and the like.
- an absorbent material such as pulp fiber can be used together with the water absorbent resin.
- the content (core concentration) of the water absorbent resin in 100% by mass of the absorbent body is preferably 30% by mass to 100% by mass, more preferably 40% by mass to 100% by mass, and still more preferably 50% by mass. to 100% by weight, even more preferably 60% to 100% by weight, particularly preferably 70% to 100% by weight, most preferably 75% to 95% by weight.
- the absorbent article can be kept white with a clean feeling. Furthermore, since an absorber having a core concentration within the above range is excellent in diffusibility of body fluids such as urine and/or blood, it is expected that the absorption amount will be improved by efficient liquid distribution.
- the absorbent body described above may be an absorbent body that contains the water absorbent resin according to one embodiment of the present invention and does not contain hydrophilic fibers.
- the absorbent body described above contains a water absorbent resin and hydrophilic fibers according to an embodiment of the present invention, and the weight of the water absorbent resin is 100% by weight in total of the water absorbent resin and hydrophilic fibers,
- the absorber may be 50% by mass or more.
- the weight of the water absorbent resin is preferably 50% of the total 100% by weight of the water absorbent resin and hydrophilic fibers. % by mass or more and less than 100% by mass, more preferably 60% by mass or more and less than 100% by mass, more preferably 70% by mass or more and less than 100% by mass, more preferably 80% by mass or more and less than 100% by mass, still more preferably 90% by mass More than 100% by mass, particularly preferably 90% to 95% by mass.
- the mass of the water-absorbing resin in the absorbent is within the above range, (1) when the absorbent is used in the upper layer of the absorbent article, the absorbent article can be kept white with a clean feeling. and/or (2) the absorber has excellent diffusibility for body fluids such as urine and/or blood, so that efficient liquid distribution can be performed, and the advantage that the absorption amount can be expected to be improved. .
- the hydrophilic fiber is not particularly limited, and examples thereof include pulp fiber, cotton linter crosslinked cellulose fiber, rayon, cotton, wool, acetate and vinylon.
- the present invention can also be configured as follows.
- the device is placed in a petri dish containing a 0.9% by mass sodium chloride aqueous solution, and the water-absorbing resin absorbs the 0.9% by mass sodium chloride aqueous solution for 5 minutes.
- D2 is the thickness [mm] of the swollen gel layer formed, and D2 is placed on the piston so that the measuring device is installed on a sieve with an opening of 4750 ⁇ m and a load of 0.7 psi is applied to the swollen gel layer. It is the thickness [mm] of the swollen gel layer formed by the water-absorbing resin after repeating 10 times the operation of placing a weight on the cell and removing the weight after allowing the cell to stand still for 10 seconds.
- [9] Contains the water absorbent resin according to any one of [1] to [8], and (1) does not contain hydrophilic fibers, or (2) contains hydrophilic fibers, An absorbent body in which the mass of the water absorbent resin is 50% by mass or more in the total 100% by mass of the water absorbent resin and the hydrophilic fibers.
- the aluminum cup (aluminum cup containing water absorbent resin or water absorbent resin powder) was taken out from the oven, and the total mass W2 (g) was accurately weighed.
- M the mass of the sample (water-absorbent resin or water-absorbent resin powder) subjected to the main measurement
- the water content (% by mass) of the sample is obtained according to the following (formula 2).
- Moisture content (% by mass) ⁇ (W1-W2)/M ⁇ x 100 (Formula 2).
- CRC centrifuge retention capacity
- AAP absorbency under pressure
- the bulk density The bulk density of the water absorbent resin was measured according to the EDANA method (T460.2-02).
- the water absorbent resin 16 was swollen to form a swollen gel layer. After that, the thickness (D1 [mm]) of the swollen gel layer formed by the swollen water absorbent resin 16 was measured. Subsequently, the cell 11 is placed on a JIS standard sieve with an opening of 4750 ⁇ m with the piston 12 mounted, and a weight of 1283 g is placed on the piston so that a load of 0.7 psi is applied to the swollen gel. An operation of placing the weight 14 on the cell and allowing the cell to stand still for 10 seconds and then removing the weight 14 was repeated 10 times. Immediately after removing the weight 14, a load was applied for the next 10 seconds.
- FIG. 3 is a plan view showing the manufacturing process of the absorbent sheet for evaluation 20 manufactured in Examples.
- FIG. 3 shows the sprayed area of the water absorbent resin 16 (that is, the water absorbent resin sprayed area 22) on the adhesive surface of the adhesive tape 21.
- FIG. 4 is a cross-sectional view of the evaluation absorbent sheet 20 produced in Examples.
- FIG. 4 shows the internal structure of the obtained evaluation absorbent sheet 20 .
- 3 and 4 can also be said to be drawings showing a method for manufacturing an absorbent body according to an embodiment of the present invention.
- the inner area ie, 1.0 g of water-absorbing resin 16 is evenly spread over the central 8 cm x 8 cm region of the adhesive tape (water-absorbing resin spraying region 22), and a 10 cm x 10 cm non-woven fabric 23 (air laid A nonwoven fabric having a basis weight of 46.6 g/m 2 is placed, and the nonwoven fabric 23 and the adhesive surfaces of the four sides of the adhesive tape 21 are adhered to form a laminated structure (adhesive tape 21, water absorbent resin 16, nonwoven fabric 23 were laminated in this order).
- the evaluation absorbent sheet 20 can also be said to be an absorbent body containing the water absorbent resin 16 and not containing hydrophilic fibers.
- D1' is written as "thickness of absorbent sheet before compression” and D2' is written as "thickness of absorbent sheet after compression”.
- Example 1 800 g of n-heptane was placed in a 2000 ml four-necked separable flask equipped with a stirrer, reflux condenser, thermometer, nitrogen gas inlet tube and dropping funnel, and maleic anhydride-modified ethylene-propylene copolymer was used as a dispersing aid.
- aqueous monomer solution (1) was prepared from 215 g of exchanged water, and dissolved oxygen dissolved in the aqueous monomer solution (1) was expelled by blowing nitrogen gas into the aqueous monomer solution (1).
- the hydrous gel polymer (1) (gel temperature: 90° C.) is put into a gel sizing device having a screw and a perforated plate with a hole diameter of 0.8 mm, and the sizing gel is discharged from the gel sizing device. (1) was obtained.
- the granulated gel (1) was dried using a cylindrical container rotary dryer. Specifically, in an atmosphere at a temperature of 200° C., the rotary container provided in the cylindrical container rotary dryer is rotated at 75 rpm, and the sizing gel (1) after heating is supplied to the cylindrical container rotary dryer. Drying was carried out using a vacuum cleaner to obtain a dry polymer (1).
- the moisture content of dry polymer (1) was 10% by mass.
- the dry polymer (1) is supplied to a roll mill (pulverizer) and pulverized to adjust the particle size, and further classified using a sieve with an opening particle size of 150 ⁇ m to obtain a water absorbent resin powder (1). Obtained.
- the mass average particle size of the water absorbent resin powder (1) was 380 ⁇ m.
- the obtained mixture was introduced into a heat treatment machine adjusted to an ambient temperature of 195 ° C. ⁇ 2 ° C., and after heat treatment for 30 minutes, the powder temperature was forcibly cooled to 60 ° C. to surface-crosslink water absorption.
- a flexible resin powder (1) was obtained.
- the obtained water absorbent resin (1) was in the form of particles, more specifically, aggregate particles of spherical particles.
- Tables 1 to 3 show the physical properties of the obtained water absorbent resin (1).
- DK Ester registered trademark
- F- 50/Daiichi Kogyo Seiyaku Co., Ltd., HLB 6
- a monomer consisting of 141 g of sodium acrylate, 36 g of acrylic acid, 0.022 g of N,N'-methylenebisacrylamide, 0.71 g of hydroxyethyl cellulose as a thickening agent, and 327.65 g of deionized water was added.
- An aqueous solution (2) was prepared, and dissolved oxygen dissolved in the aqueous monomer solution (2) was expelled by blowing nitrogen gas into the aqueous monomer solution (2).
- the hydrous gel polymer (2) (gel temperature: 90° C.) is put into a gel sizing device having a screw and a perforated plate with a hole diameter of 0.8 mm, and discharged from the gel sizing device to produce a sizing gel ( 2) was obtained.
- the granulated gel (2) was dried using a cylindrical container rotary dryer. Specifically, in an atmosphere at a temperature of 200° C., the rotary container provided in the cylindrical container rotary dryer is rotated at 75 rpm, and the sizing gel (2) after heating is supplied to the cylindrical container rotary dryer. Drying was carried out using a vacuum cleaner to obtain a dry polymer (2). The moisture content of dry polymer (2) was 8% by mass.
- the dry polymer (2) is supplied to a roll mill (pulverizer) and pulverized to adjust the particle size, and further classified using a sieve with an opening particle size of 150 ⁇ m to obtain the water absorbent resin powder (2). Obtained.
- the mass average particle size of the water absorbent resin powder (2) was 110 ⁇ m.
- a surface cross-linking agent solution consisting of 0.1 parts by mass of ethylene glycol diglycidyl ether, 1.0 parts by mass of isopropyl alcohol and 3.0 parts by mass of deionized water is added to 100 parts by mass of the water absorbent resin powder (2). was sprayed and uniformly mixed using a high speed continuous mixer.
- the obtained mixture was introduced into a heat treatment machine adjusted to an ambient temperature of 100°C, and after heat treatment for 40 minutes, the powder temperature was forcibly cooled to 60°C to surface-crosslink the water-absorbing resin powder. (2) was obtained.
- the obtained water absorbent resin (2) was particulate, more specifically, spherical particles. Tables 1 to 3 show the physical properties of the obtained water absorbent resin (2).
- a 500 mL Erlenmeyer flask was charged with 73.6 g of acrylic acid, and while externally cooling this, 102.2 g of a 30 mass% (mass/mass%) sodium hydroxide aqueous solution was added dropwise to the Erlenmeyer flask. , neutralized 75 mol % of the acrylic acid. Furthermore, 0.71 g of hydroxyethyl cellulose, 68.6 g of ion-exchanged water, 0.11 g of potassium persulfate, and 0.0092 g of ethylene glycol diglycidyl ether as thickeners were added to an Erlenmeyer flask, and the monomers for the first stage polymerization were added. A body solution (3A) was prepared.
- the entire amount of the monomer aqueous solution (3A) for the first-stage polymerization is added to the five-necked cylindrical round-bottomed flask under stirring at a rotation speed of 450 rpm with a stirrer to form the monomer aqueous solution (3A). was dispersed in a heptane solution. Then, after the inside of the system was sufficiently replaced with nitrogen, the temperature was raised, and the bath temperature in which the round-bottomed flask was immersed was kept at 70° C., and the polymerization reaction was carried out for 1 hour. cooled to
- the system was sufficiently replaced with nitrogen, and then the bath temperature was raised to 70° C. to polymerize. After the reaction was started and the polymerization reaction was carried out for 2 hours, the polymerization was stopped, the residue was separated by suction filtration, and the residue was air-dried overnight to obtain a hydrous gel polymer (3).
- the primary particle size of the hydrous gel polymer (3) was 70 ⁇ m.
- the hydrous gel polymer (3) (gel temperature: 90° C.) is put into a gel sizing device having a screw and a perforated plate with a hole diameter of 0.8 mm, and discharged from the gel sizing device to produce a sizing gel ( 3) was obtained.
- the granulated gel (3) was dried using a cylindrical container rotary dryer. Specifically, in an atmosphere at a temperature of 200° C., the rotary container provided in the cylindrical container rotary dryer is rotated at 75 rpm, and the sizing gel (3) after heating is supplied to the cylindrical container rotary dryer. Drying was then carried out to obtain a dry polymer (3).
- the moisture content of dry polymer (3) was 7% by mass.
- the dry polymer (3) is supplied to a roll mill (pulverizer) and pulverized to adjust the particle size, and further classified using a sieve with an opening particle size of 150 ⁇ m to obtain the water absorbent resin powder (3). Obtained.
- the mass average particle size of the water absorbent resin powder (3) was 400 ⁇ m.
- a surface cross-linking agent solution consisting of 0.18 parts by mass of ethylene glycol diglycidyl ether, 1.5 parts by mass of propylene glycol and 5.0 parts by mass of ion-exchanged water is added to 100 parts by mass of the water absorbent resin powder (3). was sprayed and uniformly mixed using a high speed continuous mixer.
- the obtained mixture was introduced into a heat treatment machine adjusted to an ambient temperature of 100°C, and after heat treatment for 40 minutes, the powder temperature was forcibly cooled to 60°C to surface-crosslink the water-absorbing resin powder. (3) was obtained.
- the obtained water absorbent resin (3) was in the form of particles, more specifically, aggregate particles of spherical particles.
- Tables 1 to 3 show the physical properties of the obtained water absorbent resin (3).
- a water absorbent resin was obtained by aqueous solution polymerization. That is, in a polypropylene container having a capacity of 1 L, 296 g of 48.5% by mass sodium hydroxide aqueous solution, 354 g of acrylic acid, 1.00 g of polyethylene glycol diacrylate (average number of ethylene oxide units: 9), 0.1% by mass of diethylenetriamine 5 21.66 g of acetic acid-pentasodium aqueous solution and 319 g of ion-exchanged water were charged, and the charged raw materials were stirred to prepare a comparative monomer aqueous solution (1) composed of these raw materials.
- the stirring of the comparative monomer aqueous solution (1) was continued, and the comparative monomer aqueous solution (1) was heated.
- the liquid temperature of the comparative monomer aqueous solution (1) reached 78° C.
- 15.8 g of a 3.8% by weight sodium persulfate aqueous solution was added to the comparative monomer aqueous solution (1) to obtain a mixed solution.
- the stainless steel vat-type reactor was previously set to have a surface temperature of 50° C. using a hot plate (NEO HOT PLATE HI-1000/manufactured by Iuchi Seieido Co., Ltd.).
- the polymerization reaction proceeded by expanding and foaming in all directions upward in the vat-type reactor while generating steam, and then contracted to a size slightly larger than the bottom of the reactor.
- the polymer obtained by this operation was used as a comparative hydrous gel polymer (1).
- the polymerization reaction expansion/shrinkage
- the comparative water-containing gel polymer (1) was held in the reactor for 3 minutes thereafter. A series of these operations were performed in an open-air system.
- the resulting comparative hydrous gel polymer (1) was pulverized using a meat chopper (No. 32 type/manufactured by Hiraga Seisakusho Co., Ltd.) equipped with a die having a die hole diameter of 9.5 mm.
- a meat chopper No. 32 type/manufactured by Hiraga Seisakusho Co., Ltd.
- 5.0 (kg / h) of steam are mixed with the screw shaft rotation speed of the meat chopper at 130 rpm. I did it by putting it in a chopper.
- the comparative hydrous gel polymer (1) was dried using a hot air dryer to obtain a comparative dry polymer (1).
- the drying was carried out by placing the comparative hydrous gel polymer (1) pulverized with a meat chopper on a stainless steel wire mesh with an opening of 850 ⁇ m and blowing hot air at 180° C. for 30 minutes.
- Comparative dried polymer (1) was pulverized using a roll mill (WML type roll pulverizer/manufactured by Inokuchi Giken Co., Ltd.), and then classified using JIS standard sieves with mesh openings of 850 ⁇ m and 150 ⁇ m, and irregular crushed shapes were compared.
- a water absorbent resin powder (1) was obtained.
- the mass average particle size of the comparative water absorbent resin powder (1) was 340 ⁇ m.
- Comparative water absorbent resin powder (1) 100 parts by mass, 0.024 parts by mass of ethylene glycol diglycidyl ether, 0.308 parts by mass of ethylene carbonate, 0.515 parts by mass of propylene glycol and 2.08 parts by mass of deionized water and the surface cross-linking agent solution were uniformly mixed.
- the obtained mixture was introduced into a heat treatment machine adjusted to an atmospheric temperature of 190 ° C. ⁇ 2 ° C., and after heat treatment for 30 minutes, the powder temperature was forcibly cooled to 60 ° C., thereby surface-crosslinked comparative water absorption.
- a flexible resin powder (1) was obtained.
- a solution consisting of 0.022 parts by mass of 45% by mass diethylenetriaminepentaacetic acid-3 sodium salt and 1 part by mass of ion-exchanged water was uniformly mixed with 100 parts by mass of the surface-crosslinked comparative water absorbent resin powder (1), and the comparison was performed. Water absorbent resin particles (1) were obtained.
- Tables 1 to 3 show the following.
- the water absorbent resins (1) to (3) of Examples 1 to 3 have a swollen gel compressibility of 3% or more, and can provide thin absorbent articles in which swelling of the water absorbing portion is suppressed during use. It can be said that it is a water absorbent resin.
- the comparative water absorbent resin (1) of Comparative Example 1 although the absolute values of D1 and D2, which are the thicknesses of the swollen gel, are small, the swollen gel compressibility (%) is negative, and the thickness D1 before loading is smaller. The thickness D2 after loading is rather large. Further, as shown in Table 3, when the comparative water absorbent resin (1) of Comparative Example 1 is used in an absorbent sheet, the absorbent sheet after loading is thicker than those of Examples 1 to 3.
- the water-absorbent resin and absorbent body according to one embodiment of the present invention can provide a thin absorbent article in which swelling of the water-absorbing portion is suppressed during use. Therefore, the water-absorbing resin and absorbent according to one embodiment of the present invention can be suitably used for absorbent articles such as disposable diapers (for infants and adults), sanitary napkins, and incontinence pads. .
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Abstract
Description
膨潤ゲル圧縮率[%]=(D1-D2)/D1×100 (式1)
(ここで、D1は、直径59mmのピストンと、メッシュ状の底部を備えた内径60mmのセルと、を備えた測定装置であり、該底部に前記吸水性樹脂1.0gが散布された前記測定装置を、0.9質量%塩化ナトリウム水溶液を入れたシャーレ内に載置して、該吸水性樹脂に該0.9質量%塩化ナトリウム水溶液を5分間吸収させたときの、該吸水性樹脂が成す膨潤ゲル層の厚み[mm]であり、D2は、該測定装置を目開き4750μmの篩上に設置して、該膨潤ゲル層に0.7psiの荷重が掛かるように、該ピストンの上に錘を載せて該セルを10秒間静置後に該錘を取り外す操作を10回繰り返した後の、該吸水性樹脂が成す該膨潤ゲル層の厚み[mm]である。)。
〔1-1〕吸水性樹脂
本発明の一実施形態における「吸水性樹脂」とは、水膨潤性及び水不溶性の高分子ゲル化剤を指し、以下の物性を満たすものをいう。即ち、「水膨潤性」として、ERT441.2-02で規定されるCRCが5g/g以上、かつ、「水不溶性」として、ERT470.2-02で規定されるExtが50重量%以下の物性を満たす高分子ゲル化剤を指す。
「EDANA」は、欧州不織布工業会(European Disposables and Nonwovens Associations)の略称である。「ERT」は、欧州標準(ほぼ世界標準)の吸水性樹脂の測定法(EDANA Recommended Test Methods)の略称である。本発明では、特に断りのない限り、ERT原本(2002年改定/公知文献)に準拠して、吸水性樹脂の物性を測定する。
本明細書において、範囲を示す「X~Y」は「X以上、Y以下」を意味する。
〔2-1〕吸水性樹脂の形状
本発明の一実施形態において、吸水性樹脂は、好ましくは粒子状であり、具体的には、不定形破砕状、球状、フットボール状、凝集体状等であることが好ましい。中でも吸水性樹脂の粒子形状が球状であること、特に凝集体状であることで高いゲル圧縮率が得られる。そのため、吸水性樹脂は、球状粒子(例えば、ポリ(メタ)アクリル酸(塩)系吸水性樹脂を含む球状粒子)の凝集体状粒子であることがより好ましい。なお、吸水性樹脂の球状粒子は一次粒子ともいえ、吸水性樹脂の凝集体状粒子は、球状の一次粒子が凝集して成る、凝集体状の二次粒子ともいえる。ここで、「球状」とは、真球だけでなく、アスペクト比が1.0~1.2である略球状のものも含む。
「CRC」は、Centrifuge Retention Capacity(遠心分離機保持容量)の略称であり、吸水性樹脂の無加圧下での吸水倍率を意味する。
「Ext」は、Extractables(水可溶分)の略称であり、吸水性樹脂から抽出される可溶分量を意味する。水可溶分は、EDANA法(ERT470.2-02)に準拠して測定される。
「AAP」は、Absorption Against Pressureの略称であり、吸水性樹脂の加圧下における吸水倍率を意味する。本発明においてAAPは、荷重条件を4.83kPa(0.7psi)に変更する以外は、EDANA法(ERT442.2-02)に準拠して測定される。具体的には、0.9質量%(質量/質量%)塩化ナトリウム水溶液を用い、吸水性樹脂0.9gを1時間、4.83kPaの加圧下で膨潤させた後、AAP(加圧下吸収倍率)(単位:g/g)を測定する。
「含水率」は、試料量を1.0g、乾燥温度を180℃にそれぞれ変更する以外は、EDANA法(ERT430.2-02)に準拠して測定される。含水率の測定方法については、その一例を実施例にて詳述する。
「質量平均粒子径(D50)」は、米国特許第7638570号のカラム27及び28に記載された「(3)Mass-Average Particle Diameter (D50) and Logarithmic Standard Deviation
(σζ) of Particle Diameter Distribution」に準拠して測定される。具体的な測定方法は、後述の実施例にて詳説する。
吸水性樹脂が凝集体状粒子(二次粒子)である場合、凝集体(該凝集体状粒子)を構成する一次粒子(例えば球状粒子)の数平均粒子径は電子顕微鏡を用いて測定することができる。吸水性樹脂の一次粒子の数平均粒子径は、好ましくは5μm~800μmであり、より好ましくは8μm~500μm、さらに好ましくは10μm~300μmであり、さらに一層好ましくは10μm~200μm、特に好ましくは30μm~200μmである。数平均粒子径の測定方法については、その一例を実施例にて詳述する。
「嵩密度」は、EDANA法(ERT460.2-02)に準拠して測定される。
本発明における吸水性樹脂の「通液性」とは、荷重下又は無荷重下での膨潤ゲルの粒子間を通過する液の流れ性のことをいい、代表的な測定方法として、GBP(Gel Bed Permeability/ゲル床透過性)がある。「GBP」とは、荷重下又は自由膨潤での吸水性樹脂に対する0.9質量%塩化ナトリウム水溶液の通液性をいい、国際公開第2005/016393号に開示されるGBP試験方法に準拠して測定される。ただし、本発明においては、吸水性樹脂の粒度は300μm以上600μm以下に分級せずに測定される。吸収コアの膨らみが抑えられた状態でも通液性を示すことが好ましく、吸水性樹脂のGBPは好ましくは5×10-9cm2以上、より好ましくは10×10-9cm2以上、さらに好ましくは15×10-9cm2以上である。
本発明における「膨潤ゲル圧縮率」とは、メッシュ状の底部を備えたセル内の吸水性樹脂の膨潤ゲルに対して荷重を繰り返し加えたときの吸水性樹脂の膨潤ゲル層の厚み変化(圧縮率)を表わす新規な物性値である。「膨潤ゲル圧縮率」は、後述する方法により測定される。「膨潤ゲル圧縮率」が大きい吸水性樹脂は、例えば軽失禁用等の薄型の吸水シートにおいて、繰り返し荷重がかかった際に吸水性樹脂の膨潤ゲル層が圧縮される。それ故、「膨潤ゲル圧縮率」が大きい吸水性樹脂は、長時間使用においても吸収コアの膨らみが抑えられるため好ましい。「膨潤ゲル圧縮率」は、3.0%以上、好ましくは3.5%以上、より好ましくは4.0%以上、さらに好ましくは4.5%以上、特に好ましくは5.0%以上である。膨潤ゲル圧縮率の上限は、吸水性樹脂の膨潤ゲル層の吸収性能を維持する観点から、30%以下、25%以下、20%以下の順で好ましい。
上記「膨潤ゲル圧縮率」の測定において、圧縮前の膨潤ゲル層の厚みD1は、吸水性樹脂が吸収性物品に使用された際に吸収コアの過度な膨らみによる不快感を防止または低減する観点から、数値が低い方が好ましい。圧縮前の膨潤ゲル層の厚みD1は、好ましくは20mm以下、より好ましくは15mm以下、更に好ましくは15mm未満である。D1の下限は特に制限されないが、0mmを超えていれば良く、好ましくは5mm以上、より好ましくは10mm以上、更に好ましくは12mm以上である。
上記「膨潤ゲル圧縮率」の測定において、圧縮後の膨潤ゲル層の厚みD2は、吸水性樹脂が吸収性物品に使用され、荷重(体重)がかかった場合に吸収コアの膨らみによる不快感を防止または低減する観点から、数値が低い方が好ましい。「圧縮後の膨潤ゲル層の厚みD2」は、好ましくは18mm以下、より好ましくは15mm以下、更に好ましくは15mm未満である。D2の下限は特に制限されないが、0mmを超えていれば良く、好ましくは5mm以上、より好ましくは10mm以上、更に好ましくは12mm以上である。
膨潤ゲル圧縮率[%]=(D1-D2)/D1×100 (式1)。
本発明の一実施形態においては、吸水性樹脂(吸水性樹脂組成物)は、吸水性樹脂が種々の機能を発現するための添加剤を含むこともできる。該添加剤として、具体的には、界面活性剤、リン原子を有する化合物、酸化剤、有機還元剤、無機還元剤、水不溶性無機微粒子、キレート剤、多価金属塩、金属石鹸等の有機粉末、消臭剤、抗菌剤、パルプ及び熱可塑性繊維等が挙げられる。前記添加剤の使用量(添加量)は、得られる吸水性樹脂の用途に応じて適宜設定されるが、吸水性樹脂(例えば、吸水性樹脂粉末、粉末状の吸水性樹脂組成物など)100質量%中5質量%以下、好ましくは3質量%以下、より好ましくは1質量%以下である。下限は、吸水性樹脂(例えば、吸水性樹脂粉末)に対して0.001質量%以上、好ましくは0.01質量%以上である。なお、前記水不溶性無機微粒子としては、国際特許公開第2011/040530号の「〔5〕水不溶性無機微粒子」に開示された化合物を挙げることができ、当該化合物が本発明の一実施形態に好適に適用され得る。また、前記多価金属塩としては、水溶性多価金属塩が好ましく、水溶性アルミニウム塩がより好ましい。水溶性アルミニウム塩としては、例えば、硫酸アルミニウムが挙げられる。
本発明の一実施形態に係る吸水性樹脂の製造方法は水溶液重合、逆相懸濁重合、気相液滴重合及びその他の重合方法等のうち、何れを用いてもよい。本発明の一実施形態に係る吸水性樹脂の物性を制御しやすい点から、逆相懸濁重合法を採用することが好ましい。本発明の一実施形態に係る吸水性樹脂の製造方法として、以下、逆相懸濁重合法を一例として説明する。特に、重合後の疎水性有機溶媒中での共沸脱水工程及び/又は分散系での表面架橋工程を含む一般的な逆相懸濁重合とは異なり、逆相懸濁重合で得られたゲルの分離工程、ゲル整粒工程、含水ゲルの乾燥工程(好ましくは熱風乾燥)、及び表面架橋工程(好ましくは粉体表面処理)を含む製法を一例として、本発明の一実施形態に係る吸水性樹脂の製造方法の好ましい態様を説明する。
単量体水溶液は、吸水性樹脂の原料となる単量体を含む水溶液であり、逆相懸濁重合を行うため、疎水性有機溶媒に分散又は懸濁させる溶液である。
前記単量体水溶液の調製において、重合開始剤を用いてもよい。なお、単量体水溶液の調製に重合開始剤を使用する場合は、単量体水溶液のゲル化及び/又は粘度増大が起こる虞があるため、単量体水溶液への重合開始剤の添加は、次の(1)、(2)及び(3)等を行うことが好ましい:(1)単量体水溶液を疎水性有機溶媒に分散及び/又は懸濁させる直前に行う;(2)単量体水溶液を冷却し常温より低温(例えば20℃以下、好ましくは0℃付近)で重合開始剤と混合する;(3)単量体水溶液と重合開始剤とをラインミキシングしながら分散工程に供する。重合開始剤としては、熱分解型重合開始剤が好ましく用いられる。該熱分解型重合開始剤は、熱によって分解しラジカルを発生する化合物を指す。熱分解型重合開始剤の貯蔵安定性及び/又は吸水性樹脂の生産効率の観点から、10時間半減期温度が好ましくは0℃~120℃、より好ましくは30℃~100℃、さらに好ましくは50℃~80℃である水溶性の化合物が重合開始剤として好ましく用いられる。
本発明の一実施形態において、単量体水溶液(100質量%)中の単量体の濃度は、選択された単量体及び疎水性有機溶媒の種類等に応じて選択される。生産効率上、単量体水溶液(100質量%)中の単量体の濃度は、下限は、好ましくは10質量%以上であり、より好ましくは20質量%以上であり、さらにより好ましくは30質量%以上であり、また、上限は、好ましくは100質量%以下であり、より好ましくは90質量%以下であり、さらに好ましくは80質量%以下であり、さらにより好ましくは70質量%以下である。
分散工程は、疎水性有機溶媒に単量体を含む液滴(例えば、単量体水溶液の液滴)を分散又は懸濁する工程である。なお、以下、単に「分散」と記載した場合には、懸濁も含む概念とする。より具体的には、前記単量体水溶液を、疎水性有機溶媒に添加して混合及び攪拌することにより、疎水性有機溶媒中に単量体を含む液滴を分散させる。分散工程では、例えば、攪拌翼(プロペラ翼、パドル翼、アンカー翼、タービン翼、ファウドラー翼、リボン翼、平板翼等)を備えた攪拌装置を用いてもよい。このような攪拌翼を有する攪拌装置を用いる場合、分散液滴径(分散された単量体水溶液の液滴径)は、攪拌翼の種類、翼径、回転数等により調節することができる。バッチ式逆相懸濁重合を行う場合に、該攪拌装置を特に好適に使用できる。また国際公開第2009/025235号、第2013/018571号等に記載された方法で分散液を得ることもできる。連続式逆相懸濁重合を行う場合には、分散工程は、単量体水溶液及び疎水性有機溶媒を、分散装置に別々に連続的に供給し、疎水性有機溶媒中に分散する単量体を含む液滴を作製することが好ましい。
好ましい疎水性有機溶媒としては、脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素及びハロゲン化炭化水素からなる群から選ばれる少なくとも1種類の有機溶媒が挙げられる。具体例には、n-ペンタン、n-ヘキサン、n-ヘプタン、n-オクタン等の脂肪族炭化水素;シクロヘキサン、メチルシクロヘキサン、シクロオクタン、デカリン等の脂環式炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素;クロルベンゼン、ブロムベンゼン、四塩化炭素、1,2-ジクロロエタン等のハロゲン化炭化水素が例示される。これらの中でも、入手容易性及び品質安定性の観点から、疎水性有機溶媒は、n-ヘキサン、n-ヘプタン及びシクロヘキサンからなる群から選ばれる1種以上であることが好ましい。2種以上の疎水性有機溶媒を混合した混合溶媒として用いることも可能である。
重合工程は、前記分散工程において得られた単量体を含む液滴中の単量体を重合して、含水ゲル重合体(以下、単に含水ゲルとも称する)を得る工程である。
重合工程で用いられる反応装置は、前記分散工程で用いられた分散装置をそのまま用いてもよいし、別の装置であってもよい。バッチ式逆相懸濁重合の場合、分散工程で用いた装置をそのまま反応装置として用いることができ、作業性の面で好適である。反応装置が分散装置と別の装置である場合、分散工程で得られた単量体の分散液が反応装置に供給される。
重合工程における反応温度である重合温度としては、使用する重合開始剤の種類及び/又は量によって適宜設定すればよいが、好ましくは20℃~100℃、より好ましくは40℃~90℃である。重合温度が100℃より高い場合は急激な重合反応が起こるため好ましくない。なお重合温度とは、分散媒である疎水性有機溶媒の温度(以下、「Td」と称する)を意味する。
本発明の一実施形態に係る製造方法において、適度な凝集粒径(凝集体状粒子の粒径)を得る観点から、多段重合を行ってもよい。具体的には、一段目の重合工程の終了後に、さらに前記単量体水溶液を添加し重合反応を行う等により、多段重合を行うことができる。多段重合において、反応液を適宜攪拌してもよい。
本発明の一実施形態に係る製造方法において、重合中、及び/又は、重合終了後の含水ゲル重合体に対して、適度な凝集粒径を得る観点から無機微粒子を添加してもよい。
分離工程は、前記重合工程において得られた含水ゲル重合体と疎水性有機溶媒とを分離する工程である。分離工程で用いる装置の種類及び構造については特に限定されないが、例えば、ろ過、沈降、遠心分離、圧搾等に用いられる公知の装置を利用することができる。また、重合工程で用いた攪拌翼を有する攪拌装置を用いて常圧又は減圧下で含水ゲル重合体と疎水性有機溶媒との混合物を加熱し、蒸留することにより含水ゲル重合体と疎水性有機溶媒とを分離してもよい。バッチ式逆相懸濁重合においては常圧又は減圧下での蒸留が好適に行われる。
ゲル整粒工程では、前記分離工程で疎水性有機溶媒から分離された含水ゲル重合体を、押出作用部及び多孔板を有するゲル整粒装置を用いて整粒する。これにより、整粒された含水ゲル重合体(以後、ゲル整粒後の含水ゲルを整粒ゲルと表す)が得られる。ゲル整粒工程は任意の工程である。ゲル整粒工程を有することで、吸水性樹脂の膨潤ゲル層の圧縮率(膨潤ゲル圧縮率)を制御しやすくなる。
ゲル整粒装置に入る(投入する)含水ゲルの温度の下限は特に制限はないが、造粒効率及び含水ゲルへのダメージの抑制の観点から、好ましくは80℃以上、より好ましくは90℃以上である。ゲル整粒装置投入時の含水ゲル温度の上限は特に制限はないが、一般的に100℃以下である。
本明細書において、「ゲル整粒」とは、粉体の湿塊(例えば含水ゲル)を多孔板の小孔から円柱状に押し出すことにより、湿粉状の原料からほぼ均一な形状及びサイズを有する粒を作製する操作である。つまり、多孔板を用いることにより、前工程の溶媒分離工程で過度に凝集した粗大凝集物の形状になっている含水ゲルは解砕され、小粒径の単粒子状の含水ゲルは適度に凝集される。したがって、ゲル整粒工程によって、比較的粒子径の均一な造粒形状の含水ゲル(整粒ゲル)を得ることができる。なお、整粒ゲルは単粒子状の含水ゲルを含んでいてもよい。
乾燥工程は、含水ゲルを乾燥する工程である。ゲル整粒工程を実施する場合、乾燥工程は、整粒ゲルを乾燥する工程である。本発明の一実施形態において、乾燥工程における乾燥の手法としては、特に限定されない。乾燥の手法としては、従来の逆相懸濁重合で使用される疎水性分散溶媒中の共沸脱水を採用してもよい。本発明の一実施形態に係る吸水性樹脂を逆相懸濁重合で得る、より好適な手法として、共沸脱水に替えて、好ましくは攪拌乾燥と静置乾燥とのいずれも採用できる。上記ゲル整粒工程で制御したゲルの粒子径を維持するため、本発明の一実施形態では、乾燥工程として、攪拌乾燥を採用することがさらに好ましい。乾燥工程では、含水ゲルを加熱するために加熱手段を備えた装置を使用してもよい。また、攪拌乾燥を採用する場合、乾燥装置として、回転容器を備える回転型乾燥機を使用してもよい。
本発明の一実施形態の効果が阻害されない限り、含水ゲルに添加剤を添加してもよい。添加剤は、加熱手段による含水ゲルの加熱中及び/又は前記回転容器による含水ゲルの撹拌(回転)中に該含水ゲルに添加してもよい。添加剤は、乾燥工程前(加熱手段による含水ゲルの加熱前及び/又は前記回転容器による含水ゲルの撹拌(回転)前)に該含水ゲルに添加してもよい。さらには、乾燥工程以前の任意の工程で含水ゲルに添加剤を添加してもよい。添加剤によって乾燥時の含水ゲル同士の過度の付着が低減でき、吸水速度に優れた吸水性樹脂を得ることができる。
乾燥助剤は、攪拌乾燥時に含水ゲルの流動性を保つことを目的として添加されるものであり、乾燥助剤としては界面活性剤及び/又は高分子滑剤が挙げられる。乾燥助剤として、高分子滑剤と界面活性剤とを併用してもよい。
前記乾燥工程で得られた乾燥重合体の粒度分布として、粒子径850μm以上の割合(目開き粒子径850μmの篩を通過しなかった粒子の割合)は、少ないほど好ましく、乾燥重合体100質量%中、好ましくは50質量%以下、より好ましくは45質量%以下、更に好ましくは40質量%以下である。本発明の一実施形態の方法によれば、攪拌型乾燥機を用いた乾燥と組み合わせることにより、粗大粒子の形成が有意に抑制されるために、粒子径850μm以上の割合を前記好ましい範囲とすることが可能となる。また、乾燥重合体100質量%中の粒子径1400μm以上の割合(目開き粒子径1400μmの篩を通過しなかった粒子の割合)は、少ないほど好ましく、好ましくは40質量%以下、より好ましくは35質量%以下、更に好ましくは30質量%以下である。
前記乾燥工程(及びその後の任意の工程)を経て得られる吸水性樹脂(例えば吸水性樹脂粉末)は、表面架橋剤によって表面架橋されることが好ましい。この表面架橋は、吸水性樹脂(例えば吸水性樹脂粉末)の表面層(吸水性樹脂(例えば吸水性樹脂粉末)の表面から中心へ数10μmの部分)に架橋密度の高い部分を設ける処理である。表面架橋処理を行うことで吸水性樹脂の各種吸水特性を向上させることができる。ここで、吸水性樹脂の架橋密度を適宜調整することで、特に、優れた加圧下吸収倍率を得ることができる。
本発明の一実施形態に係る吸水性樹脂の製造方法は、上述した各工程以外に、必要に応じて、冷却工程、粉砕工程、含水(再湿潤)工程、その他の添加剤添加工程、分級工程、整粒工程、及び微粉再利用工程を含むことができる。また、本発明の一実施形態に係る吸水性樹脂の製造方法は、輸送工程、貯蔵工程、梱包工程、保管工程等をさらに含んでもよい。
任意に実施される冷却工程では、乾燥工程において得られた粒子状の乾燥重合体を、公知の冷却手段を用いて冷却することにより、所望の温度まで冷却された粒子状の乾燥重合体を得ることができる。
本発明の一実施形態に係る吸水性樹脂の製造方法は、前記乾燥工程(及びその後の任意の冷却工程)で得られた粒子状の乾燥重合体を粉砕する粉砕工程を含むことが好ましい。粉砕工程を実施することによって、粒子径又は粒度分布が制御された吸水性樹脂(例えば吸水性樹脂粉末)を得ることができる。
任意に実施される再湿潤工程は、前記表面架橋工程で得られた吸水性樹脂(例えば吸水性樹脂粒子)に、多価金属塩、カチオン性ポリマー、キレート剤、無機還元剤及びα-ヒドロキシカルボン酸化合物からなる群から選ばれる少なくとも1種の添加剤を添加する工程である。前記多価金属塩としては、水溶性多価金属塩が好ましく、水溶性アルミニウム塩がより好ましい。水溶性アルミニウム塩としては、例えば、硫酸アルミニウムが挙げられる。
本発明の一実施形態においては、上述した添加剤以外の添加剤を、吸水性樹脂に種々の機能を付加させるため添加することもできる。該添加剤として、具体的には、界面活性剤、リン原子を有する化合物、酸化剤、有機還元剤、水不溶性無機微粒子、金属石鹸等の有機粉末、消臭剤、抗菌剤、パルプ及び熱可塑性繊維等が挙げられる。なお、前記水不溶性無機微粒子としては、国際特許公開第2011/040530号の「〔5〕水不溶性無機微粒子」に開示された化合物を挙げることができ、当該化合物が本発明の一実施形態に適用され得る。これら添加剤のうち、特に膨潤ゲル層が圧縮された際に吸水性樹脂が吸水物性を損なわないよう、好ましくは通液性を向上させる多価金属塩、カチオン性ポリマー及び無機微粒子からなる群から選択される1種以上を吸水性樹脂に添加することが好ましい。前記多価金属塩としては、水溶性多価金属塩が好ましく、水溶性アルミニウム塩がより好ましい。水溶性アルミニウム塩としては、例えば、硫酸アルミニウムが挙げられる。
「整粒工程」とは、前記表面架橋工程を経て緩く凝集した吸水性樹脂(例えば吸水性樹脂粉末)をほぐして粒子径を整える工程を意味する。なお、この整粒工程は、表面架橋工程以降の微粉除去工程及び分級工程を含むものとする。整粒工程は吸水性樹脂の粒子径を整え、安定した吸水物性を得る観点から、本発明の一実施形態では整粒工程が実施されることが好ましい。
「微粉再利用工程」とは、前記各工程で篩分級等により発生した含水ゲルまたは吸水性樹脂の微粉をそのまま、又は微粉を造粒した後にいずれかの工程に供給する工程を意味する。微粉再利用工程は吸水性樹脂の生産ロスを低減する観点から、本発明の一実施形態では微粉再利用工程が実施されることが好ましい。
本発明の一実施形態に係る吸水性樹脂および吸収体は、薄型吸収性物品において使用時に吸水部の膨らみが抑えられる吸収性物品を提供し得る。より具体的に、本発明の一実施形態に係る吸水性樹脂および吸収体は、薄型吸収性物品において使用時に繰り返し荷重(体重)がかかることで吸収コアのゲル層が圧縮されるので、長時間使用においてもコアの膨らみが抑制される吸収性物品を提供することができる。本発明の一実施形態に係る吸水性樹脂の用途は、特に限定されないが、好ましくは紙オムツ(幼児用、成人用)、生理用ナプキン、失禁パッド等の吸収性物品の吸収体用途が挙げられる。本発明の一実施形態に係る吸水性樹脂は、特に、吸液後の膨潤ゲルによる吸収コアの膨らみが問題となっていた薄型の高濃度紙オムツの吸収体として好適に使用することができる。その他の吸収性物品の一例としては、例えば、土壌保水剤、育苗用シート、種子コーティング材、結露防止シート、ドリップ吸収材、鮮度保持材、使い捨てカイロ、冷却用バンダナ、保冷剤、医療用廃液固化剤、残土固化材、水損防止廃液ゲル化剤、吸水土のう、災害用簡易トイレ、湿布材、化粧品用増粘剤、電気及び電子材料通信ケーブル用止水材、ガスケットパッキング、肥料用徐放剤、各種徐放剤(空間除菌剤、芳香剤等)、ペットシート、ネコ砂、創傷保護用ドレッシング材、結露防止用建築資材、油中水分除去剤、塗料、接着剤、アンチブロッキング剤、光拡散剤、艶消し剤、化粧板用添加剤、人工大理石用添加剤、トナー用添加剤等の樹脂用添加剤などが挙げられる。
膨潤ゲル圧縮率[%]=(D1-D2)/D1×100 (式1)
(ここで、D1は、直径59mmのピストンと、メッシュ状の底部を備えた内径60mmのセルと、を備えた測定装置であり、該底部に前記吸水性樹脂1.0gが散布された前記測定装置を、0.9質量%塩化ナトリウム水溶液を入れたシャーレ内に載置して、該吸水性樹脂に該0.9質量%塩化ナトリウム水溶液を5分間吸収させたときの、該吸水性樹脂が成す膨潤ゲル層の厚み[mm]であり、D2は、該測定装置を目開き4750μmの篩上に設置して、該膨潤ゲル層に0.7psiの荷重が掛かるように、該ピストンの上に錘を載せて該セルを10秒間静置後に該錘を取り外す操作を10回繰り返した後の、該吸水性樹脂が成す該膨潤ゲル層の厚み[mm]である。)。
〔数平均粒子径〕
吸水性樹脂又は吸水性樹脂粉末の走査型電子顕微鏡写真(SEM)を撮影した。写真の中から凝集体状粒子(二次粒子)の正面にある50個の一次粒子を無作為に選択し、各一次粒子について長径と短径とを測定し、該測定値の積を平均化した値(測定値の相乗平均値)を一次粒子径とした。50個の各一次粒子の一次粒子径を算出し、得られた値の平均値を当該吸水性樹脂の平均一次粒子径とした。
含水率をEDANA法(ERT430.2-02)に準拠して測定した。なお、測定に際し、試料(吸水性樹脂又は吸水性樹脂粉末)の質量を1.0gに、乾燥温度を180℃に、乾燥時間を3時間にそれぞれ変更した。具体的には、底面の直径が50mmのアルミカップに試料(吸水性樹脂又は吸水性樹脂粉末)1.0gを投入した後、該アルミカップ(吸水性樹脂又は吸水性樹脂粉末を含むアルミカップ)の総質量W1(g)を正確に秤量した。次に、前記アルミカップ(吸水性樹脂又は吸水性樹脂粉末を含むアルミカップ)を、雰囲気温度180℃に設定されたオーブン内に静置した。3時間経過後、該アルミカップ(吸水性樹脂又は吸水性樹脂粉末を含むアルミカップ)を前記オーブンから取り出し、総質量W2(g)を正確に秤量した。本測定に供された試料(吸水性樹脂又は吸水性樹脂粉末)の質量をM(1.0g)としたときに、下記(式2)にしたがって、該試料の含水率(質量%)を求めた。
含水率(質量%)={(W1-W2)/M}×100 (式2)。
質量平均粒子径(D50)は、米国特許第7638570号のカラム27、28に記載された「(3)Mass-Average Particle Diameter(D50) and Logarithmic Standard Deviation(σζ) of Particle Diameter Distribution」に記載の方法に従って測定した。具体的には、吸水性樹脂10.0gを、室温(20~25℃)、湿度50RH%の条件下で、目開き850μm、710μm、600μm、500μm、425μm、300μm、212μm、150μm、45μmのJIS標準篩(THE IIDA TESTING SIEVE:径8cm)に仕込み、振動分級器(IIDA SIEVE SHAKER、TYPE:ES-65型、SER.No.0501)により、5分間、分級を行った。その後、各篩上の残留百分率Rを対数確率紙にプロットした。これにより、R=50質量%に相当する粒径を質量平均粒子径(D50)として読み取った。
CRC(遠心分離機保持容量)は、EDANA法(ERT441.2-02)に準拠して測定した。具体的には、吸水性樹脂0.2gを不織布製の袋に入れた後、該不織布製を大過剰の0.9質量%塩化ナトリウム水溶液中に30分間浸漬して吸水性樹脂を自由膨潤させ、その後、吸水性樹脂を遠心分離機(250G)で3分間、水切りした後の吸水倍率(単位;g/g)を求めた。
AAP(加圧下吸収倍率)は、EDANA法(ERT442.2-02)に準拠して測定した。なお、荷重条件を4.83kPa(0.7psi)に変更した。
本実施例及び比較例の吸水性樹脂のExt(水可溶分)は、EDANA法(ERT470.2-02)に準拠して測定した。
吸水性樹脂の嵩密度は、EDANA法(T460.2-02)に準拠して測定した。
吸水性樹脂の膨潤ゲル圧縮率は、下記に示す手順にて測定した。なお、膨潤ゲル圧縮率の測定に用いた測定装置については、図1および2を参照して説明する。
膨潤ゲル圧縮率[%]=(D1-D2)/D1×100 (式1)。
(1)吸収シート(吸収体)の作製
図3および4を使用して、吸収シート(吸収体)の厚み圧縮率の測定に使用した吸収シート(吸収体)20の作製方法を説明する。図3は、実施例において作製した評価用吸収シート20の作製過程での平面図である。図3では、粘着テープ21の粘着面における、吸水性樹脂16の散布領域(すなわち吸水性樹脂散布領域22)を示している。図4は、実施例において作製した評価用吸収シート20の断面図である。図4では、得られた評価用吸収シート20の内部構成を示している。図3および4は、本発明の一実施形態に係る吸収体の製造方法を示す図面ともいえる。
平面な台上で、アクリル板(10cm×23cm、厚さ0.3cm)上に評価用吸収シート20(吸収体)を載置し、20℃の0.9質量%塩化ナトリウム水溶液25mLを2分間かけて評価用吸収シート20に添加し、評価用吸収シート20内の吸水性樹脂16を膨潤させた。該0.9質量%塩化ナトリウム水溶液の添加が終了してから3分後、評価用吸収シート20の厚み(D1’[mm])を測定した。続いて、該評価用吸収シート20の上に別のアクリル板(10cm×23cm、厚さ0.3cm)を載せた。さらに、アクリル板上に重量1.0kgの錘を載せて10秒間静置し錘を取り外す操作を10回繰り返した。なお、錘を取り外した後は直ちに次の10秒間の荷重を掛けた。その後、評価用吸収シート20上のアクリル板を取り除き評価用吸収シート20の厚み(D2’[mm])を計測し、下記(式3)より評価用吸収シート20(吸収体)の厚み圧縮率を算出した。厚み圧縮率[%]=(D1’-D2’)/D1’×100 (式3)。
攪拌機、還流冷却器、温度計、窒素ガス導入管及び滴下ろうとを備えた2000mlの四つ口セパラブルフラスコにn-へプタン800gを取り、分散助剤として無水マレイン酸変性エチレン-プロピレン共重合体(ハイワックス(登録商標)HW2203A/三井化学株式会社製)0.88gを加え、無水マレイン酸変性エチレン-プロピレン共重合体をn-ヘプタンに溶解させ、ヘプタン溶液を得た。次いで、得られたヘプタン溶液中に窒素ガスを吹き込んでヘプタン溶液中の溶存酸素を追い出した。
攪拌機、還流冷却器、温度計、窒素ガス導入管及び滴下ろうとを備えた2000mlの四つ口セパラブルフラスコにシクロヘキサン800gを取り、分散助剤としてショ糖脂肪酸エステル(DKエステル(登録商標)F-50/第一工業製薬株式会社製、HLB=6)を0.6g加え、ショ糖脂肪酸エステルをシクロヘキサンに溶解させ、シクロヘキサン溶液を得た。次いで、得られたシクロヘキサン溶液中に窒素ガスを吹き込んでシクロヘキサン溶液中の溶存酸素を追い出した。
次いで、このフラスコ内の単量体水溶液(2)に過硫酸ナトリウムの15%水溶液0.95gを加えた後、得られた溶液の全量を前記セパラブルフラスコに加えて、該セパラブルフラスコ内の混合液を370rpmで攪拌することにより、単量体水溶液(2)をシクロヘキサン溶液中に分散させた。その後、セパラブルフラスコを浸している浴温を60℃に昇温して重合反応を開始させ、2時間この浴温60℃を保持した後、重合を止め、吸引濾過により濾別し、残渣を一晩風乾させることで含水ゲル重合体(2)を得た。含水ゲル重合体(2)の平均一次粒子径は195μmであった。
撹拌機、還流冷却器、滴下ロート、温度計及び窒素ガス導入管を備えた2000mLの五つ口円筒型丸底フラスコにn-ヘプタン500gを取り、分散助剤としてショ糖脂肪酸エステル(S-370/三菱ケミカル株式会社製、HLB=3)を0.92g加え分散、昇温して、ショ糖脂肪酸エステルをn-ヘプタンに溶解させ、ヘプタン溶液を得た。その後、得られたヘプタン溶液を55℃まで冷却した。
水溶液重合にて吸水性樹脂を得た。即ち、容量1Lのポリプロピレン製容器に、48.5質量%の水酸化ナトリウム水溶液296g、アクリル酸354g、ポリエチレングリコールジアクリレート(平均エチレンオキサイドユニット数9)1.00g、0.1質量%のジエチレントリアミン5酢酸-5ナトリウム水溶液21.66g、及びイオン交換水319gを投入し、投入した原料を攪拌し、これらの原料からなる比較単量体水溶液(1)を調製した。
11 :セル
12 :ピストン
13 :シャーレ
14 :錘
15 :底部
16 :吸水性樹脂
20 :評価用吸収シート
21 :粘着テープ
22 :吸水性樹脂散布領域
23 :不織布
Claims (9)
- 粒子状のポリ(メタ)アクリル酸(塩)系吸水性樹脂であって、下記(式1)で表される膨潤ゲル圧縮率が3%以上である、吸水性樹脂:
膨潤ゲル圧縮率[%]=(D1-D2)/D1×100 (式1)
(ここで、D1は、直径59mmのピストンと、メッシュ状の底部を備えた内径60mmのセルと、を備えた測定装置であり、該底部に前記吸水性樹脂1.0gが散布された前記測定装置を、0.9質量%塩化ナトリウム水溶液を入れたシャーレ内に載置して、該吸水性樹脂に該0.9質量%塩化ナトリウム水溶液を5分間吸収させたときの、該吸水性樹脂が成す膨潤ゲル層の厚み[mm]であり、D2は、該測定装置を目開き4750μmの篩上に設置して、該膨潤ゲル層に0.7psiの荷重が掛かるように、該ピストンの上に錘を載せて該セルを10秒間静置後に該錘を取り外す操作を10回繰り返した後の、該吸水性樹脂が成す該膨潤ゲル層の厚み[mm]である。)。 - 前記吸水性樹脂は、球状粒子の凝集体状粒子である、請求項1に記載の吸水性樹脂。
- 質量平均粒子径(D50)が50~700μmである、請求項1又は2に記載の吸水性樹脂。
- 前記吸水性樹脂は、前記D2が15mm未満である、請求項1~3のいずれか1項に記載の吸水性樹脂。
- 前記吸水性樹脂は、前記D1が15mm未満である、請求項1~4のいずれか1項に記載の吸水性樹脂。
- 加圧下における吸水倍率(AAP)が18g/g以上である、請求項1~5のいずれか1項に記載の吸水性樹脂。
- 疎水性有機溶媒中で逆相懸濁重合することによって得られる、請求項1~6のいずれか1項に記載の吸水性樹脂。
- 球状粒子を、多孔板を有する押出機によって押し出すことにより得られる、請求項1~7のいずれか1項に記載の吸水性樹脂。
- 請求項1~8のいずれか1項に記載の吸水性樹脂を含有し、かつ、(1)親水性繊維を含有しない、又は、(2)親水性繊維を含有し、前記吸水性樹脂の質量が該吸水性樹脂と親水性繊維との合計100質量%中、50質量%以上である、吸収体。
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