WO2015146784A1 - 吸水性樹脂架橋剤組成物 - Google Patents
吸水性樹脂架橋剤組成物 Download PDFInfo
- Publication number
- WO2015146784A1 WO2015146784A1 PCT/JP2015/058268 JP2015058268W WO2015146784A1 WO 2015146784 A1 WO2015146784 A1 WO 2015146784A1 JP 2015058268 W JP2015058268 W JP 2015058268W WO 2015146784 A1 WO2015146784 A1 WO 2015146784A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- group
- crosslinking agent
- absorbing
- absorbent resin
- Prior art date
Links
Classifications
-
- 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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
- C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/68—Superabsorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08J2300/104—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08J2300/105—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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 a water-absorbing resin crosslinking agent composition capable of producing a water-absorbing agent having a high water-absorbing ability, and a water-absorbing agent obtained by crosslinking a water-absorbing resin using the water-absorbing resin crosslinking agent composition. It is.
- Water-absorbing resins are widely used in various fields such as sanitary goods, foods, agriculture and forestry, and civil engineering.
- the water-absorbing resins are widely used in sanitary goods such as paper diapers and sanitary napkins, taking advantage of their water absorption.
- examples of the water-absorbent resin used in such sanitary products include partially neutralized salts of polyacrylic acid and polymethacrylic acid.
- a water-absorbing resin used in sanitary goods such as paper diapers is required to have a high water-absorbing capacity not only under normal pressure but also under body pressure (under pressure).
- a method of crosslinking the surface of water-absorbent resin particles with a crosslinking agent uses a cross-linking agent to cross-link the surface layer of water-absorbing resin particles having a carboxylic acid group and / or a carboxylic acid group, while suppressing the internal cross-linking of the water-absorbing resin particles to maintain the water absorbing ability.
- a water-absorbing agent having a high water absorption rate is obtained.
- crosslinking agent examples include a compound having at least two halohydrin groups in the molecule and a crosslinking agent containing a compound having a halohydrin group and a quaternary ammonium group in the molecule (see Patent Document 1).
- polyhydric alcohol compounds eg: ethylene glycol, propylene glycol, polyethylene glycol
- epoxy compounds eg: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether
- polyvalent amine compounds eg: ethylenediamine, diethylenetriamine
- poly Isocyanate compounds eg: 2,4-tolylene diisocyanate, hexamethylene diisocyanate
- polyvalent oxazoline compounds eg: 4,4 ′, 5,5′-tetrahydro-4,4,4 ′, 4′-tetramethyl- 2,2′-bisoxazole, 2,2 ′-(1,3-propanediyl) bis [4,5-dihydro-4,4-dimethyloxazole]
- alkylene carbonate compound eg, 1,3-dioxolane- 2-one, 4-methyl-1,3-di Xoxolan-2-one
- haloepoxy compounds e
- the main subject of this invention is providing the novel water absorbent resin crosslinking agent composition used in order to obtain a water absorbing agent with high water absorption capability.
- the present inventors have found that when a water absorbent resin is crosslinked using a water absorbent resin crosslinker composition containing a crosslinking agent and a water absorbent enhancer having a specific structure or functional group, the water absorbent resin is more water absorbent.
- the present invention has been completed by discovering that a highly water-absorbing agent can be obtained.
- a water absorbent resin crosslinking agent composition comprising a crosslinking agent (A) and a water absorption improver (B),
- the water absorption improver (B) has the following general formula (1):
- crosslinking agent (A) is represented by the following general formula (2):
- R 1 represents a (k + m) -valent aliphatic hydrocarbon group having 2 to 10 carbon atoms
- Z represents a chlorine atom or a bromine atom
- k and m are 1 ⁇ k ⁇ 6, 0 ⁇ m. ⁇ 4, 2 ⁇ k + m ⁇ 6 represents an integer.
- the water-absorbent resin crosslinking agent composition according to any one of the above [1] to [3] is added to a water-absorbent resin having a carboxylic acid group and / or a carboxylate group, and the mixture is heated and crosslinked. A water-absorbing agent obtained.
- a water-absorbent resin crosslinking agent composition according to any one of the above [1] to [3] is added to a water-absorbent resin having a carboxylic acid group and / or a carboxylic acid group, followed by heating and crosslinking.
- a method for producing a water-absorbing agent is also included.
- the water absorbent resin crosslinking agent composition of the present invention (hereinafter referred to as "the composition of the present invention") will be described in detail.
- composition of the present invention is a water absorbent resin crosslinking agent composition
- a crosslinking agent (A) and a water absorption improver (B) The water absorption improver (B) has the following general formula (1):
- the composition of the present invention comprises a crosslinking agent (A) and a water absorption improver (B) as essential components, and in particular, a water absorption improver having a specific structure or functional group is used as the water absorption improver (B). Is the gist. Therefore, first, the water absorption improver (B) will be described among the components of the composition of the present invention.
- the water absorption improver (B) has the following general formula (1):
- X represents a chlorine atom or a bromine atom
- Y represents a hydroxyl group, a chlorine atom or a bromine atom.
- halohydrin compound (b1) examples include chlorohydrin compounds such as 3-chloro-1,2-propanediol and 1,3-dichloro-2-propanol; 3-bromo-1,2-propanediol, 1,3 And bromohydrin compounds such as dibromo-2-propanol.
- chlorohydrin compounds such as 3-chloro-1,2-propanediol and 1,3-dichloro-2-propanol
- 3-bromo-1,2-propanediol 1,3 And bromohydrin compounds such as dibromo-2-propanol.
- the halohydrin compound (b1) a commercially available reagent can be used as it is.
- the said halohydrin compound (b1) may use only 1 type, and may use 2 or more types together.
- the compound (b2) is a compound having at least one group selected from the group consisting of a carbonate group, a carbamide group, a carbamate group, and a ureido group.
- Examples of the compound having a carbonate group include aliphatic carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and ethyl methyl carbonate; aromatic carbonates such as methyl phenyl carbonate and ethyl phenyl carbonate; 1,3-dioxolane-2 And cyclic carbonates such as -one and 4-methyl-1,3-dioxolan-2-one.
- Examples of the compound having a carbamide group include lactams such as azetidin-2-one, pyrrolidin-2-one, piperidin-2-one, and 2-oxohexamethyleneimine; pyrrolidine-2,5-dione, piperidine-2 And imides such as 6-dione.
- Examples of the compound having a carbamate group include oxazolidine-2-one, 3- (2-hydroxyethyl) oxazolidine-2-one, 3- (3-hydroxypropyl) oxazolidine-2-one, and 3- (2-hydroxy Propyl) oxazolidin-2-one, 2-oxotetrahydro-1,3-oxazine and the like.
- Examples of the compound having a ureido group include imidazolidin-2-one, 1- (2-hydroxyethyl) imidazolidin-2-one, 1,3-bis (hydroxymethyl) imidazolidin-2-one, 1, 3-bis (hydroxymethyl) -4,5-dihydroxyimidazolin-2-one, 4,5-ureylene imidazolidin-2-one, imidazolidine-2,4-dione, tetrahydropyrimidin-2-one, etc. be able to.
- the water absorption improver (B) may be a combination of the halohydrin compound (b1) and the compound (b2).
- the amount of the water absorption improver (B) in the composition of the present invention can be appropriately adjusted depending on the type of the crosslinking agent (A) and the like, but is usually 1 to 30% by weight in the composition of the present invention. Preferably, it is 1.5 to 15% by weight.
- the cross-linking agent (A) is not particularly limited as long as it can cross-link the water-absorbing resin, and may include known cross-linking agents.
- known cross-linking agents include halohydrin compounds, polyhydric alcohol compounds, epoxy compounds, polyvalent amine compounds, polyisocyanate compounds, polyvalent oxazoline compounds, alkylene carbonate compounds, haloepoxy compounds, silane coupling agents, A valent metal compound etc. can be mentioned. These crosslinking agents may be used alone or in combination of two or more.
- polyhydric alcohol compound examples include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,3-propanediol, dipropylene glycol, 2,2,4-trimethyl-1, 3-pentanediol, polypropylene glycol, glycerin, polyglycerin, 2-butene-1,4-diol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol 1,2-cyclohexanedimethanol, 1,2-cyclohexanediol, trimethylolpropane, diethanolamine, triethanolamine, polyoxypropylene, oxyethylene-oxypropylene block copolymer , It may be mentioned pentaerythritol, sorbitol and the like.
- epoxy compound examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and glycidol. Etc.
- polyvalent amine compound examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine, and inorganic salts or organic salts (such as aditinium salts) of these polyvalent amine compounds. Can do.
- polyisocyanate compound examples include 2,4-tolylene diisocyanate and hexamethylene diisocyanate
- polyvalent oxazoline compound examples include 1,2-ethylenebisoxazoline
- alkylene carbonate compound examples include 1,3-dioxolan-2-one, 4-methyl-1,3-dioxolan-2-one, 4,5-dimethyl-1,3-dioxolan-2-one, , 4-Dimethyl-1,3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan-2-one, 1,3-dioxane- 2-one, 4-methyl-1,3-dioxane-2-one, 4,6-dimethyl-1,3-dioxane-2-one and the like can be mentioned.
- haloepoxy compound examples include epichlorohydrin, epibromohydrin, ⁇ -methylepichlorohydrin, and polyvalent amine adducts thereof (eg, Kaimen (registered trademark) manufactured by Hercules). .
- crosslinking agents include silane coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -aminopropyltriethoxysilane, and hydroxides such as zinc, calcium, magnesium, aluminum, iron and zirconium. And polyvalent metal compounds such as chlorides can also be used.
- the crosslinking agent (A) is preferably a halohydrin compound, and is represented by the following general formula (2):
- R 1 represents a (k + m) -valent aliphatic hydrocarbon group having 2 to 10 carbon atoms
- Z represents a chlorine atom or a bromine atom
- k and m are 1 ⁇ k ⁇ 6, 0 ⁇ m. ⁇ 4, 2 ⁇ k + m ⁇ 6 represents an integer.
- the halohydrin compound (a1) can be produced by a known method, and can be synthesized, for example, according to the method described in JP-A-2002-60544.
- the content ratio of the crosslinking agent (A) and the water absorption improver (B) is usually such that the content ratio of the water absorption improver (B) to the total of the crosslinking agent (A) and the water absorption improver (B) is 1 to It is 50% by weight, preferably 1 to 30% by weight, more preferably 2.5 to 25% by weight. If the content ratio of the water absorption improver (B) is more than 50% by weight, the water absorption ability may be inferior to that when the crosslinking agent (A) is used alone, and the content ratio of the water absorption improver (B) is If it is less than 1% by weight, the water absorption improver (B) may not work effectively.
- this invention composition contains the solvent which consists of water, a hydrophilic organic solvent, or these mixtures.
- hydrophilic organic solvents include lower aliphatic alcohols such as methanol, ethanol, n-propyl alcohol and isopropyl alcohol; ketones such as acetone; ethers such as dioxane, tetrahydrofuran and methoxy (poly) ethylene glycol; Amides such as ⁇ -caprolactam and N, N-dimethylformamide; sulfoxides such as dimethyl sulfoxide; ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,3-propanediol, Examples include polyhydric alcohols such as dipropylene glycol, polypropylene glycol, glycerin, and polyglycerin. These hydrophilic organic solvents may be one kind or a mixture of two or more kinds.
- the amount of the hydrophilic organic solvent used can be appropriately adjusted depending on the type of the crosslinking agent and the like, but is usually 10 to 2000 parts by weight, preferably 50 to 1000 parts by weight with respect to 100 parts by weight of the crosslinking agent. is there.
- composition of the present invention can be disinfectant, deodorant, antibacterial agent, fragrance, various inorganic powders, foaming agent, pigment, dye, hydrophilic short fiber, fertilizer, oxidizing agent, reducing agent, if necessary. You may contain other additives, such as water and salts.
- the water-absorbing agent of the present invention Water-absorbing agent obtained with the composition of the present invention
- the water-absorbing agent of the present invention water-absorbing agent obtained with the composition of the present invention
- the water-absorbing agent of the present invention is obtained by adding the composition of the present invention to a water-absorbing resin having a carboxylic acid group and / or a carboxylic acid group, heating and crosslinking.
- the water-absorbing agent of the present invention is usually obtained by crosslinking the surface of a water-absorbing resin having a carboxylic acid group and / or a carboxylic acid group using the composition of the present invention.
- the composition can also be used for internal crosslinking of the water absorbent resin.
- a water-absorbing agent that is internally crosslinked by the composition of the present invention is also included in the present invention.
- the water-absorbing resin having a carboxylic acid group and / or a carboxylic acid group is particularly limited as long as it has a carboxylic acid group and / or a carboxylic acid group, absorbs water, swells, and forms a hydrogel.
- a known water-absorbing resin can be used. Specific examples include crosslinked polyacrylic acid partially neutralized products, self-crosslinked polyacrylic acid partially neutralized products, starch-acrylate graft copolymer crosslinked products, and starch-acrylonitrile graft copolymer crosslinked products.
- a water-absorbing resin having a high density of carboxylic acid groups and / or carboxylic acid bases is preferable because of its high water absorption capability.
- Specific examples of such a water-absorbing resin include a crosslinked product of a partially neutralized acrylic acid and a self-crosslinked polyacrylic acid partially neutralized product.
- examples of the carboxylate include a sodium salt, a potassium salt, and an ammonium salt, and a sodium salt is particularly preferable.
- the production method and shape of the water-absorbing resin having a carboxylic acid group and / or a carboxylic acid group are not particularly limited.
- the reversed-phase suspension polymerization method, the pearl-like water-absorbing resin particles obtained thereby examples thereof include a water-absorbent resin having a scaly shape, a lump shape, a rock shape, a granule shape, and an amorphous shape obtained by pulverizing a dried product after polymerization.
- a water-absorbent resin having a scaly shape, a lump shape, a rock shape, a granule shape, and an amorphous shape obtained by pulverizing a dried product after polymerization.
- what granulated these water absorbing resin particles can be mentioned.
- the composition of the present invention is used for 100 parts by weight of the water-absorbent resin, depending on the type and degree of crosslinking of the water-absorbent resin and the desired degree of surface crosslinking.
- the amount of the crosslinking agent (A) in the inventive composition is usually from 0.01 to 20 parts by weight, preferably from 0.05 to 10 parts by weight.
- the content of the crosslinking agent in the composition of the present invention to be used is within the above range relative to 100 parts by weight of the water absorbent resin, not only can the water absorbent resin be effectively crosslinked, but the crosslinking density becomes too high. It can prevent that the water absorption capacity and water absorption speed of the water-absorbing agent to be obtained are reduced.
- composition of the present invention and the water-absorbent resin include, for example, spraying an aqueous solution of a crosslinking agent onto the water-absorbent resin, and then cylindrical mixer, V-shaped mixer, ribbon-type mixer, screw-type mixer, double-arm type It is appropriate to mix by a known method using a mixer, a pulverizing kneader or the like. At this time, a surfactant can be added as necessary.
- water, a hydrophilic organic solvent, or a solvent composed of a mixture thereof may be added as necessary.
- this hydrophilic organic solvent the hydrophilic organic solvent similar to what is added to this invention composition can be mentioned, for example.
- These hydrophilic organic solvents may be one kind or a mixed solvent of two or more kinds.
- the composition of the present invention is added to and mixed with a water-absorbing resin having a carboxylic acid group and / or a carboxylic acid group, and then surface crosslinking is performed by heating.
- the heating temperature at the time of surface cross-linking may be appropriately changed according to the type of the water-absorbent resin, but is usually 40 ° C to 250 ° C.
- the heating temperature is within the above range, the surface of the water-absorbent resin particles is uniformly crosslinked without deterioration of the water-absorbent resin particles, and has an excellent balance between the water absorption ratio under normal pressure and the water absorption ratio under pressure. A water-absorbing agent with high ability can be obtained.
- the heating temperature is preferably 60 ° C. to 200 ° C., more preferably 70 ° C. to 200 ° C.
- the heating time may be appropriately adjusted depending on the type of the water-absorbent resin, but is usually 0.2 hours to 3 hours.
- the water-absorbing agent of the present invention is provided with a disinfectant, a deodorant, an antibacterial agent, a fragrance, various inorganic powders, a foaming agent, a pigment, a dye, a hydrophilic short fiber, a fertilizer, and an oxidizing agent for the purpose of imparting various functions.
- Other additives such as a reducing agent, water, and salts may be contained. The addition amount of these other additives is appropriately selected by those skilled in the art.
- these other additives may be mixed with the water-absorbent resin after being added to the composition of the present invention, or may be added separately from the composition of the present invention.
- the water-absorbing performance under pressure of the water-absorbing agent produced by crosslinking the water-absorbing resin with the composition of the present invention was evaluated as follows.
- a crucible type glass filter (inner diameter 40 mm, height 70 mm) was set up vertically, and 1 g of the water-absorbing agent was uniformly put therein.
- a PET film (thickness: 100 ⁇ m) was placed on this water-absorbing agent, and the initial weight Wa (g) was measured. Further, a weight with an outer diameter of 38 mm was placed thereon so as to obtain a load of 50 g / cm 2 .
- Synthesis of cross-linking agent (A) Synthesis example 1 A 500 mL separable flask was charged with 100 g (0.55 mol) of sorbitol and dissolved at an internal temperature of 110 ° C. to 115 ° C., and then 0.4 g of tin tetrachloride was charged as a catalyst. While maintaining the internal temperature at 95 ° C. to 100 ° C., 124 g (1.3 mol) of epichlorohydrin was added dropwise thereto. At the end of the addition, the reaction system was a homogeneous solution.
- Synthesis example 2 A 1 L separable flask was charged with 200 g (2.2 mol) of glycerin and 0.9 g of tin tetrachloride as a catalyst, and heated and stirred. While maintaining the internal temperature at 70 ° C. to 75 ° C., 221 g of epichlorohydrin ( 2.4 mol) was added dropwise. At the end of the addition, the reaction system was a homogeneous solution. After completion of the dropwise addition, the internal temperature was raised to 90 ° C. to 95 ° C., and stirring was continued in the same temperature range, and the disappearance of epichlorohydrin was confirmed based on the quantification of the epoxy group by titration to complete the reaction. .
- Example 1 The crosslinking agent (A) was diluted with 0.5 g of water by diluting 0.1 g of the sorbitol chlorohydrin compound of Synthesis Example 1 (in terms of solid content) and 0.01 g of oxazolidin-2-one as the water absorption improver (B).
- An inventive composition was prepared (crosslinking agent composition solution 1).
- the cross-linking agent (A) was diluted with 1.0 g of water by diluting 0.2 g (in terms of solid content) of the sorbitol chlorohydrin compound of Synthesis Example 1 and 0.02 g of oxazolidin-2-one as the water absorption improver (B).
- crosslinking agent composition solution 2 An inventive composition was prepared (crosslinking agent composition solution 2).
- the crosslinker composition solution 1 was sprayed onto 10 g of the polyacrylate water-absorbing resin and mixed well (1% / water-absorbing resin particles).
- the crosslinker composition solution 2 was sprayed onto 10 g of the polyacrylate water-absorbing resin and mixed well (2% / water-absorbing resin particles).
- the water-absorbing resin thus treated was heated at 150 ° C. for 60 minutes to obtain the water-absorbing agent of the present invention that was surface-crosslinked with the composition of the present invention.
- the performance of this water-absorbing agent is shown in Table 1.
- Example 2 A water-absorbing agent of the present invention was obtained in the same manner as in Example 1 except that 0.01 g and 0.02 g of imidazolidin-2-one were used as the water absorption improver (B) in Example 1. The performance is shown in Table 1.
- Example 3 the water-absorbing agent of the present invention was obtained in the same manner as in Example 1 except that 0.01 g and 0.02 g of dimethyl carbonate were used as the water absorption improver (B). The performance is shown in Table 1.
- Example 4 The water-absorbing agent of the present invention was obtained in the same manner as in Example 1 except that 0.01 g and 0.02 g of 3-chloro-1,2-propanediol were used as the water absorption improver (B) in Example 1. It was. The performance is shown in Table 1.
- Example 5 A water-absorbing agent of the present invention was obtained in the same manner as in Example 1 except that 0.01 g and 0.02 g of 1,3-dichloro-2-propanol were used as the water absorption improver (B) in Example 1. .
- the performance is shown in Table 1.
- Example 6 As a crosslinking agent (A), 0.1 g of the glycerin chlorohydrin compound of Synthesis Example 2 (in terms of solid content) and 0.01 g of oxazolidin-2-one as a water absorption improver (B) were diluted with 0.5 g of water. An inventive composition was prepared (crosslinking agent composition solution 3). As a crosslinking agent (A), 0.2 g (in terms of solid content) of the glycerin chlorohydrin compound of Synthesis Example 2 and 0.02 g of oxazolidin-2-one as a water absorption improver (B) were diluted with 1.0 g of water. An inventive composition was prepared (crosslinking agent composition solution 4).
- the crosslinker composition solution 3 was sprayed onto 10 g of the polyacrylate water-absorbing resin and mixed well (1% / water-absorbing resin particles). Further, the crosslinker composition solution 4 was sprayed on 10 g of the polyacrylate water-absorbing resin and mixed well (2% / water-absorbing resin particles).
- the water-absorbing resin thus treated was heated at 150 ° C. for 60 minutes to obtain the water-absorbing agent of the present invention that was surface-crosslinked with the composition of the present invention.
- the performance of this water-absorbing agent is shown in Table 1.
- Example 7 A water-absorbing agent of the present invention was obtained in the same manner as in Example 6 except that 0.01 g and 0.02 g of imidazolidin-2-one were used as the water absorption improver (B) in Example 6. The performance is shown in Table 1.
- Example 8 In Example 6, the water-absorbing agent of the present invention was obtained in the same manner as in Example 6 except that 0.01 g and 0.02 g of dimethyl carbonate were used as the water absorption improver (B). The performance is shown in Table 1.
- Example 9 A water-absorbing agent of the present invention was obtained in the same manner as in Example 6 except that 0.01 g and 0.02 g of imidazolidine-2,4-dione were used as the water-absorbing agent (B) in Example 6. The performance is shown in Table 1.
- Example 10 A water-absorbing agent of the present invention was obtained in the same manner as in Example 6 except that 0.01 g and 0.02 g of pyrrolidine-2,5-dione were used as the water absorption improver (B) in Example 6. The performance is shown in Table 1.
- Comparative Example 1 As a crosslinking agent, 0.1 g of the sorbitol chlorohydrin compound of Synthesis Example 1 (in terms of solid content) was diluted with 0.5 g of water to prepare an aqueous crosslinking agent solution (crosslinking agent composition solution 5). As a crosslinking agent, 0.2 g of the sorbitol chlorohydrin compound of Synthesis Example 1 (in terms of solid content) was diluted with 1.0 g of water to prepare an aqueous crosslinking agent solution (crosslinking agent composition solution 6). The crosslinker composition solution 5 was sprayed onto 10 g of the polyacrylate water-absorbing resin and mixed well (1% / water-absorbing resin particles).
- the cross-linking agent composition solution 6 was sprayed on 10 g of the polyacrylate water-absorbing resin and sufficiently mixed (2% / water-absorbing resin particles).
- the water absorbent resin thus treated was heated at 150 ° C. for 60 minutes to obtain a surface-crosslinked water absorbent.
- the performance of this water-absorbing agent is shown in Table 1.
- the water-absorbing agent of the present invention obtained by using the composition of the present invention is higher than the water-absorbing agent obtained by using the water-absorbing resin cross-linking agent aqueous solution that does not contain the water-absorbing agent (B). It is clear that the water absorption ratio is shown.
- Example 11 Dilution of 0.1 g (solid content) of the glycerin chlorohydrin compound of Synthesis Example 3 as the crosslinking agent (A) and 0.005 g of imidazolidine-2,4-dione as the water absorption improver (B) with 0.5 g of water
- the composition of the present invention was prepared (crosslinking agent composition solution 7).
- the crosslinker composition solution 7 was sprayed on 10 g of the polyacrylate water-absorbing resin and mixed well (1% / water-absorbing resin particles).
- the water-absorbing resin thus treated was heated at 150 ° C. for 60 minutes to obtain the water-absorbing agent of the present invention that was surface-crosslinked with the composition of the present invention.
- Table 2 shows the performance of this water-absorbing agent.
- Example 12 A water-absorbing agent of the present invention was obtained in the same manner as in Example 11 except that 0.01 g of imidazolidine-2,4-dione was used as the water-absorbing agent (B). The performance is shown in Table 2.
- Example 13 The water-absorbing agent of the present invention was obtained in the same manner as in Example 11 except that 0.02 g of imidazolidine-2,4-dione was used as the water-absorbing agent (B). The performance is shown in Table 2.
- Example 14 The water-absorbing agent of the present invention was obtained in the same manner as in Example 11 except that 0.03 g of imidazolidine-2,4-dione was used as the water-absorbing agent (B). The performance is shown in Table 2.
- Example 15 A water-absorbing agent of the present invention was obtained in the same manner as in Example 11 except that 0.04 g of imidazolidine-2,4-dione was used as the water-absorbing agent (B). The performance is shown in Table 2.
- the water-absorbing agent of the present invention obtained using the composition of the present invention has a content ratio of the water-absorbing agent (B) to the sum of the crosslinking agent (A) and the water-absorbing agent (B). It can be seen that up to about 25% by weight, the water absorption ratio improves as the content ratio increases.
- the composition of the present invention can efficiently crosslink a water-absorbent resin as compared with a conventional cross-linking agent that does not contain a water-absorbing agent. Therefore, the water-absorbing agent obtained by using the composition of the present invention (the water-absorbing agent of the present invention) has a high water-absorbing ability and is useful in the field of sanitary products such as paper diapers.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
紙オムツ等の衛生用品で用いられる吸水性樹脂は、常圧下はもちろんのこと、体圧がかかった状態(圧力下)でも、高い吸水能力が求められる。
該架橋剤として、例えば、分子中にハロヒドリン基を少なくとも2つ有する化合物や、分子中にハロヒドリン基及び第四級アンモニウム基を有する化合物を含む架橋剤を挙げることができる(特許文献1参照)。また、多価アルコール化合物(例:エチレングリコール、プロピレングリコール、ポリエチレングリコール)、エポキシ化合物(例:エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル)、多価アミン化合物(例:エチレンジアミン、ジエチレントリアミン)、ポリイソシアネート化合物(例:2,4-トリレンジイソシアネート、ヘキサメチレンジイソシアネート)、多価オキサゾリン化合物(例:4,4’,5,5’-テトラヒドロ-4,4,4’,4’-テトラメチル-2,2’-ビスオキサゾール、2,2’-(1,3-プロパンジイル)ビス[4,5-ジヒドロ-4,4-ジメチルオキサゾール])、アルキレンカーボネート化合物(例:1,3-ジオキソラン-2-オン、4-メチル-1,3-ジオキソラン-2-オン)、ハロエポキシ化合物(例:エピクロロヒドリン、エピブロモヒドリン)、シランカップリング剤(例:γ-グリシドキシプロピルトリメトキシシラン)、多価金属化合物(例:亜鉛、カルシウム等の水酸化物や塩化物)等も挙げることができる(例えば、特許文献2~6参照)。
[1]架橋剤(A)と吸水性向上剤(B)とを含む吸水性樹脂架橋剤組成物であって、
吸水性向上剤(B)が、次の一般式(1):
で表されるハロヒドリン化合物(b1)
又は、
カーボネート基、カルバミド基、カルバメート基及びウレイド基からなる群より選択される少なくとも1つの基を有する化合物(b2)であることを特徴とする吸水性樹脂架橋剤組成物。
で表されるハロヒドリン化合物(a1)である、上記[1]に記載の吸水性樹脂架橋剤組成物。
まず、本発明の吸水性樹脂架橋剤組成物(以下、「本発明組成物」という)について詳述する。
吸水性向上剤(B)が、次の一般式(1):
で表されるハロヒドリン化合物(b1)
又は
カーボネート基、カルバミド基、カルバメート基及びウレイド基からなる群より選択される少なくとも1つの基を有する化合物(b2)
であることを特徴とする吸水性樹脂架橋剤組成物である。
で表されるハロヒドリン化合物(b1)
又は
カーボネート基、カルバミド基、カルバメート基及びウレイド基からなる群より選択される少なくとも1つの基を有する化合物(b2)
である。
で表されるハロヒドリン化合物(a1)であることがより好ましい。
次に、本発明組成物で得られる吸水剤(以下、「本発明吸水剤」という)について詳述する。
まず、カルボン酸基及び/又はカルボン酸塩基を有する吸水性樹脂の表面を本発明組成物により架橋する場合について説明する。
本発明組成物による吸水性樹脂の架橋によって製造した吸水剤(本発明吸水剤)の加圧下の吸水性能は以下のようにして評価した。
るつぼ型ガラスフィルター(内径40mm、高さ70mm)を鉛直に立て、この中に吸水剤1gを均一に入れた。この吸水剤の上にPETフィルム(厚さ100μm)をのせ、初期重量Wa(g)を測定した。更にこの上に50g/cm2荷重となるように外径38mmの分銅をのせた。次に、生理食塩水(濃度0.9%)約630gを入れたバット(縦210mm、横170mm)の中に、前記吸水剤を入れたるつぼ型ガラスフィルターを底部を下側にして30分間浸漬した後、引き上げて吸水後の重量Wb(g)を測定した。これらWa、Wbから、次式に従って加圧下の吸水倍率を算出した。
加圧下の吸収倍率=(Wb(g)-Wa(g))/吸水剤の重量(g)
合成例1
500mL容量セパラブルフラスコにソルビトール100g(0.55モル)を仕込み、内温110℃~115℃で溶解させた後、触媒として四塩化すず0.4gを仕込んだ。内温を95℃~100℃に保ちながら、これにエピクロロヒドリン124g(1.3モル)を滴下した。滴下終了時、反応系は均一な溶液であった。滴下終了後、同温度範囲で撹拌を続け、滴定によるエポキシ基の定量に基づいてエピクロロヒドリンの消失を確認して、反応を終了させた。反応終了後、同温度範囲でイオン交換水125g、48.5%水酸化ナトリウム水溶液1.6gを加え、減圧濃縮により溶媒を留去し、ソルビトールクロロヒドリン化合物を得た。
1L容量セパラブルフラスコにグリセリン200g(2.2モル)、触媒として四塩化すず0.9gを仕込み、加熱攪拌し、内温を70℃~75℃に保ちながら、これにエピクロロヒドリン221g(2.4モル)を滴下した。滴下終了時、反応系は均一な溶液であった。滴下終了後、内温を90℃~95℃に加温し、同温度範囲で撹拌を続け、滴定によるエポキシ基の定量に基づいてエピクロロヒドリンの消失を確認して、反応を終了させた。反応終了後、同温度範囲でイオン交換水280g、48.7%水酸化ナトリウム水溶液0.3gを加え、減圧濃縮により溶媒を留去した。濃縮残渣にイソプロピルアルコール281gを加え、ろ過を行い、グリセリンクロロヒドリン化合物を得た。
実施例1
架橋剤(A)として合成例1のソルビトールクロロヒドリン化合物0.1g(固形分換算)、吸水性向上剤(B)としてオキサゾリジン-2-オン0.01gを水0.5gで希釈して本発明組成物を調製した(架橋剤組成物溶液1)。架橋剤(A)として合成例1のソルビトールクロロヒドリン化合物0.2g(固形分換算)、吸水性向上剤(B)としてオキサゾリジン-2-オン0.02gを水1.0gで希釈して本発明組成物を調製した(架橋剤組成物溶液2)。
架橋剤組成物溶液1をポリアクリル酸塩系吸水性樹脂10gに噴霧し、十分に混合した(1%/吸水性樹脂粒子)。また、架橋剤組成物溶液2をポリアクリル酸塩系吸水性樹脂10gに噴霧し、十分に混合した(2%/吸水性樹脂粒子)。このように処理した吸水性樹脂を150℃で60分間、加熱して、本発明組成物により表面架橋した本発明吸水剤を得た。この吸水剤の性能を表1に示す。
実施例1において、吸水性向上剤(B)としてイミダゾリジン-2-オン0.01g、0.02gをそれぞれ用いた以外は、実施例1と同様にして本発明吸水剤を得た。その性能を表1に示す。
実施例1において、吸水性向上剤(B)としてジメチルカーボネート0.01g、0.02gをそれぞれ用いた以外は、実施例1と同様にして本発明吸水剤を得た。その性能を表1に示す。
実施例1において、吸水性向上剤(B)として3-クロロ-1,2-プロパンジオール0.01g、0.02gをそれぞれ用いた以外は、実施例1と同様にして本発明吸水剤を得た。その性能を表1に示す。
実施例1において、吸水性向上剤(B)として1,3-ジクロロ-2-プロパノール0.01g、0.02gをそれぞれ用いた以外は、実施例1と同様にして本発明吸水剤を得た。その性能を表1に示す。
架橋剤(A)として合成例2のグリセリンクロロヒドリン化合物0.1g(固形分換算)、吸水性向上剤(B)としてオキサゾリジン-2-オン0.01gを水0.5gで希釈して本発明組成物を調製した(架橋剤組成物溶液3)。架橋剤(A)として合成例2のグリセリンクロロヒドリン化合物0.2g(固形分換算)、吸水性向上剤(B)としてオキサゾリジン-2-オン0.02gを水1.0gで希釈して本発明組成物を調製した(架橋剤組成物溶液4)。
架橋剤組成物溶液3をポリアクリル酸塩系吸水性樹脂10gに噴霧し、十分に混合した(1%/吸水性樹脂粒子)。また、架橋剤組成物溶液4をポリアクリル酸塩系吸水性樹脂10gに噴霧し、十分に混合した(2%/吸水性樹脂粒子)。このように処理した吸水性樹脂を150℃で60分間、加熱して、本発明組成物により表面架橋した本発明吸水剤を得た。この吸水剤の性能を表1に示す。
実施例6において、吸水性向上剤(B)としてイミダゾリジン-2-オン0.01g、0.02gをそれぞれ用いた以外は、実施例6と同様にして本発明吸水剤を得た。その性能を表1に示す。
実施例6において、吸水性向上剤(B)としてジメチルカーボネート0.01g、0.02gをそれぞれ用いた以外は、実施例6と同様にして本発明吸水剤を得た。その性能を表1に示す。
実施例6において、吸水性向上剤(B)としてイミダゾリジン-2,4-ジオン0.01g、0.02gをそれぞれ用いた以外は、実施例6と同様にして本発明吸水剤を得た。その性能を表1に示す。
実施例6において、吸水性向上剤(B)としてピロリジン-2,5-ジオン0.01g、0.02gをそれぞれ用いた以外は、実施例6と同様にして本発明吸水剤を得た。その性能を表1に示す。
架橋剤として合成例1のソルビトールクロロヒドリン化合物0.1g(固形分換算)を水0.5gで希釈して架橋剤水溶液を調製した(架橋剤組成物溶液5)。架橋剤として合成例1のソルビトールクロロヒドリン化合物0.2g(固形分換算)を水1.0gで希釈して架橋剤水溶液を調製した(架橋剤組成物溶液6)。
架橋剤組成物溶液5をポリアクリル酸塩系吸水性樹脂10gに噴霧し、十分に混合した(1%/吸水性樹脂粒子)。また、架橋剤組成物溶液6をポリアクリル酸塩系吸水性樹脂10gに噴霧し、十分に混合した(2%/吸水性樹脂粒子)。このように処理した吸水性樹脂を150℃で60分間、加熱して、表面架橋した吸水剤を得た。この吸水剤の性能を表1に示す。
合成例3
2L容量セパラブルフラスコにグリセリン400g(4.3モル)、触媒として三フッ化ホウ素0.6gを仕込み、加熱攪拌し、内温を50℃~55℃に保ちながら、これにエピクロロヒドリン442g(4.8モル)を滴下した。滴下終了時、反応系は均一な溶液であった。滴下終了後、同温度範囲で撹拌を続け、滴定によるエポキシ基の定量に基づいてエピクロロヒドリンの消失を確認して、反応を終了させた。反応終了後、同温度範囲でイオン交換水442g、48.7%水酸化ナトリウム水溶液0.4gを加え、減圧濃縮により溶媒を留去した。濃縮残渣にイソプロピルアルコール842gを加え、ろ過を行い、グリセリンクロロヒドリン化合物を得た。
実施例11
架橋剤(A)として合成例3のグリセリンクロロヒドリン化合物0.1g(固形分換算)、吸水性向上剤(B)としてイミダゾリジン-2,4-ジオン0.005gを水0.5gで希釈して本発明組成物を調製した(架橋剤組成物溶液7)。
架橋剤組成物溶液7をポリアクリル酸塩系吸水性樹脂10gに噴霧し、十分に混合した(1%/吸水性樹脂粒子)。このように処理した吸水性樹脂を150℃で60分間、加熱して、本発明組成物により表面架橋した本発明吸水剤を得た。この吸水剤の性能を表2に示す。
実施例11において、吸水性向上剤(B)としてイミダゾリジン-2,4-ジオン0.01gを用いた以外は、実施例11と同様にして本発明吸水剤を得た。その性能を表2に示す。
実施例11において、吸水性向上剤(B)としてイミダゾリジン-2,4-ジオン0.02gを用いた以外は、実施例11と同様にして本発明吸水剤を得た。その性能を表2に示す。
実施例11において、吸水性向上剤(B)としてイミダゾリジン-2,4-ジオン0.03gを用いた以外は、実施例11と同様にして本発明吸水剤を得た。その性能を表2に示す。
実施例11において、吸水性向上剤(B)としてイミダゾリジン-2,4-ジオン0.04gを用いた以外は、実施例11と同様にして本発明吸水剤を得た。その性能を表2に示す。
Claims (5)
- 架橋剤(A)と吸水性向上剤(B)とが50:50~99:1(A:B)の重量比で含まれる、請求項1又は2に記載の吸水性樹脂架橋剤組成物。
- カルボン酸基及び/又はカルボン酸塩基を有する吸水性樹脂に、請求項1~3のいずれか一項に記載の吸水性樹脂架橋剤組成物を加え、加熱し、架橋して得られることを特徴とする吸水剤。
- カルボン酸基及び/又はカルボン酸塩基を有する吸水性樹脂に、請求項1~3のいずれか一項に記載の吸水性樹脂架橋剤組成物を加え、加熱し、架橋することを特徴とする、吸水剤の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/124,241 US20170014802A1 (en) | 2014-03-24 | 2015-03-19 | Crosslinking agent composition for water-absorbing resin |
CN201580011473.4A CN106062085B (zh) | 2014-03-24 | 2015-03-19 | 吸水性树脂交联剂组合物 |
EP15767858.2A EP3124550A4 (en) | 2014-03-24 | 2015-03-19 | Crosslinking agent composition for water-absorbing resin |
JP2016510284A JPWO2015146784A1 (ja) | 2014-03-24 | 2015-03-19 | 吸水性樹脂架橋剤組成物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014060583 | 2014-03-24 | ||
JP2014-060583 | 2014-03-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015146784A1 true WO2015146784A1 (ja) | 2015-10-01 |
Family
ID=54195305
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/058268 WO2015146784A1 (ja) | 2014-03-24 | 2015-03-19 | 吸水性樹脂架橋剤組成物 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20170014802A1 (ja) |
EP (1) | EP3124550A4 (ja) |
JP (1) | JPWO2015146784A1 (ja) |
CN (1) | CN106062085B (ja) |
WO (1) | WO2015146784A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020241123A1 (ja) * | 2019-05-31 | 2020-12-03 | 株式会社日本触媒 | 吸水剤の製造方法及びポリアクリル酸(塩)系吸水性樹脂 |
WO2021010343A1 (ja) * | 2019-07-12 | 2021-01-21 | ミドリ安全株式会社 | ディップ成形用架橋剤、ディップ成形用組成物、及び手袋 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102640374B1 (ko) | 2015-03-23 | 2024-02-26 | 바스프 코포레이션 | 실내 공기 질을 제어하기 위한 이산화탄소 수착제 |
TW201741022A (zh) | 2016-02-12 | 2017-12-01 | 巴斯夫公司 | 用於空氣品質控制的二氧化碳吸附劑 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01297430A (ja) * | 1988-05-24 | 1989-11-30 | Nippon Shokubai Kagaku Kogyo Co Ltd | 吸水性樹脂の表面処理方法 |
JP2002060544A (ja) * | 2000-06-05 | 2002-02-26 | Nagase Chemtex Corp | 吸水性樹脂架橋剤とこれを用いて得られる吸水剤 |
JP2002363340A (ja) * | 2001-03-02 | 2002-12-18 | Nagase Chemtex Corp | 吸水性樹脂架橋剤とこれを用いて得られる吸水剤 |
WO2012102407A1 (ja) * | 2011-01-28 | 2012-08-02 | 株式会社日本触媒 | ポリアクリル酸(塩)系吸水性樹脂粉末の製造方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2434414A (en) * | 1943-10-25 | 1948-01-13 | Lilly Co Eli | Process of making 2-hydroxymethyl-1, 4-dioxane |
CN1205258C (zh) * | 2000-06-05 | 2005-06-08 | 长濑化成株式会社 | 吸水性树脂交联剂和用其获得的吸水剂 |
DE102004038015A1 (de) * | 2004-08-04 | 2006-03-16 | Basf Ag | Verfahren zur Nachvernetzung wasserabsorbierender Polymere mit zyklischen Carba-maten und/oder zyklischen Harnstoffen |
TW200635969A (en) * | 2005-04-06 | 2006-10-16 | Nippon Catalytic Chem Ind | Particulate water absorbing agent, water-absorbent core and absorbing article |
-
2015
- 2015-03-19 CN CN201580011473.4A patent/CN106062085B/zh active Active
- 2015-03-19 EP EP15767858.2A patent/EP3124550A4/en not_active Withdrawn
- 2015-03-19 US US15/124,241 patent/US20170014802A1/en not_active Abandoned
- 2015-03-19 WO PCT/JP2015/058268 patent/WO2015146784A1/ja active Application Filing
- 2015-03-19 JP JP2016510284A patent/JPWO2015146784A1/ja active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01297430A (ja) * | 1988-05-24 | 1989-11-30 | Nippon Shokubai Kagaku Kogyo Co Ltd | 吸水性樹脂の表面処理方法 |
JP2002060544A (ja) * | 2000-06-05 | 2002-02-26 | Nagase Chemtex Corp | 吸水性樹脂架橋剤とこれを用いて得られる吸水剤 |
JP2002363340A (ja) * | 2001-03-02 | 2002-12-18 | Nagase Chemtex Corp | 吸水性樹脂架橋剤とこれを用いて得られる吸水剤 |
WO2012102407A1 (ja) * | 2011-01-28 | 2012-08-02 | 株式会社日本触媒 | ポリアクリル酸(塩)系吸水性樹脂粉末の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3124550A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020241123A1 (ja) * | 2019-05-31 | 2020-12-03 | 株式会社日本触媒 | 吸水剤の製造方法及びポリアクリル酸(塩)系吸水性樹脂 |
WO2021010343A1 (ja) * | 2019-07-12 | 2021-01-21 | ミドリ安全株式会社 | ディップ成形用架橋剤、ディップ成形用組成物、及び手袋 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2015146784A1 (ja) | 2017-04-13 |
EP3124550A1 (en) | 2017-02-01 |
CN106062085B (zh) | 2019-06-18 |
EP3124550A4 (en) | 2017-11-22 |
CN106062085A (zh) | 2016-10-26 |
US20170014802A1 (en) | 2017-01-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1136233C (zh) | 吸水剂树脂的生产方法 | |
US7728079B2 (en) | Hydrolytically stable postcrosslinked superabsorbents | |
WO2015146784A1 (ja) | 吸水性樹脂架橋剤組成物 | |
JP4047443B2 (ja) | 吸水性樹脂組成物およびその製造方法 | |
JP4722545B2 (ja) | 吸水性樹脂組成物とその製造方法 | |
CN101050251A (zh) | 高吸水性树脂的制造方法 | |
JP4722546B2 (ja) | 吸水性樹脂組成物とその製造方法 | |
JP6464463B2 (ja) | 吸水性樹脂架橋剤 | |
WO2001094459A1 (fr) | Agent de reticulation destine a une resine absorbant l'eau et materiau absorbant l'eau obtenu au moyen de cette resine | |
JP7253618B2 (ja) | 吸水剤の製造方法及びポリアクリル酸(塩)系吸水性樹脂 | |
JP4817089B2 (ja) | 吸水性樹脂架橋剤とこれを用いて得られる吸水剤 | |
KR20190035313A (ko) | 항균성 고흡수성 수지의 제조 방법 | |
JP4067330B2 (ja) | 架橋構造を有する高吸水性樹脂を主成分とする吸水剤、およびその製造方法、並びにこれを用いた衛生材料 | |
JP2016069418A (ja) | ポリ(メタ)アクリル酸(塩)系吸水性樹脂の製造方法 | |
JP2015196675A (ja) | 吸水性樹脂架橋剤及び吸水剤 | |
JP4873208B2 (ja) | 新規化合物ならびにそれを用いた吸水性樹脂用架橋剤および吸水性樹脂 | |
JP4844783B2 (ja) | 架橋剤およびそれを用いた吸水性樹脂 | |
JP2016124995A (ja) | 吸水性樹脂架橋剤、吸水剤及びその製造方法 | |
JP2002363340A (ja) | 吸水性樹脂架橋剤とこれを用いて得られる吸水剤 | |
JPH02194010A (ja) | ポリアクリル酸金属塩の製造方法 | |
JP5557195B2 (ja) | 架橋剤およびそれを用いた吸水性樹脂 | |
JPH01223161A (ja) | 吸水性樹脂組成物 | |
JPH11315216A (ja) | 吸水剤およびその製造方法 | |
JP2002080632A (ja) | 吸水性樹脂架橋剤とこれを用いて得られる吸水剤及びその製造方法 | |
JP2022016990A (ja) | 吸水性樹脂架橋剤組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15767858 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016510284 Country of ref document: JP Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2015767858 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112016019321 Country of ref document: BR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015767858 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15124241 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 112016019321 Country of ref document: BR Kind code of ref document: A2 Effective date: 20160823 |