Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2101/00—Manufacture of cellular products

Definitions

• the present invention relates to a porous polyurethane body having fine continuous pores.
• a polyurethane porous material having fine continuous pores is obtained, for example, by reacting a urethane emulsion with a water-soluble polyisocyanate as a primary crosslinking agent and a polyamine compound as a secondary crosslinking agent.
• a water-soluble polyisocyanate as a primary crosslinking agent
• a polyamine compound as a secondary crosslinking agent
• Patent Document 1 Japanese Patent Application Laid-Open No. 2003-48940
• the polyurethane porous material of the present invention comprises a urethane prepolymer water having a terminal isocyanate group obtained by polymerizing a polyol, a chain extender, a hydrophilic chain extender, and an isocyanate. It is characterized by being obtained by removing water from the gelled product obtained by subjecting the dispersion and the polyamine compound to a crosslinking reaction.
• the polyurethane porous body of the present invention contains a hydrophilic chain length agent and uses only a polyamine compound as a crosslinking agent, fine continuous pores suitable for various uses are formed. Manufacturing costs can also be reduced.
• FIG. 1 is a microscope photograph (magnification: 600 times) of a reaction product obtained in Example 1.
• FIG. 2 is a microscope photograph (magnification: 600 times) of a reaction product obtained in Comparative Example 1.
• the porous polyurethane of the present invention is obtained by subjecting a urethane prepolymer aqueous dispersion in which urethane prepolymer is dispersed in water to a crosslinking reaction with a polyamine conjugate.
• the urethane prepolymer in the present invention is obtained by polymerizing a polyol, a chain extender, a hydrophilic chain extender and an isocyanate and having a terminal isocyanate group.
• the polyol is not particularly limited as long as it is used in the production of ordinary polyurethane and has two or more hydroxyl groups in the molecule.
• examples thereof include polyether polyol, polyester polyol, polycarbonate polyol, and polylatatatone.
• Polyols, polyolefin polyols, acrylic polyols, castor oil-based polyols, silicone-based polyols and the like can be mentioned, and these can be used alone or in combination of two or more.
• polycarbonate polyol is preferably used from the viewpoint of suppressing deterioration of the obtained polyurethane porous body.
• the above-mentioned deterioration includes deterioration due to light, deterioration due to water, and the like.
• polyether polyol examples include those obtained by polymerizing or copolymerizing an alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide) and Z or a heterocyclic ether (eg, tetrahydrofuran), specifically, polyethylene.
• alkylene oxide eg, ethylene oxide, propylene oxide, butylene oxide
• Z or a heterocyclic ether eg, tetrahydrofuran
• Polyester polyols include aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, dartalic acid, azelaic acid, etc.) and Z or aromatic dicarboxylic acids (isophthalic acid, terephthalic acid, etc.) and low molecular weight glycols ( Ethylene glycol, propylene glycol,
• Polycarbonate polyols include organic carbonates (dimethyl carbonate, diethyl carbonate, ethylene carbonate, diphenyl carbonate, phosgene, etc.) and low molecular weight glycols (butanediol, pentanediol, hexanediol, 3-methylpentanediol) , Nonanediol, 2-methyloctanediol, cyclohexanedimethanol, etc.), specifically, polybutanediol carbonate, poly-3-methylpentanediol carbonate, polyhexanediol carbonate, Nonanediol carbonate, polybutanediol hexanediol carbonate, polypentanediol carbonate, polypentanediol hexanediol carbonate, poly-3-methyl pen Hexanedioldiol carbonate,
• polylatatatone polyol examples include polyproprotatondiol, polyproprotatone triol, and poly-3-methylvalerolatone diol.
• polystyrene resin examples include polybutadiene glycol, polyisoprene glycol or a hydride thereof.
• the silicone-based polyol is obtained by introducing a hydroxyl group into a polysiloxane main chain.
• the introduced hydroxyl group may be at both ends or one end of the polysiloxane main chain.
• the number average molecular weight of the polyol is preferably from 500 to 5000, more preferably from 500 to 4000, particularly preferably from 500 to 4,000 from the viewpoint of forming fine continuous pores in the obtained polyurethane porous material. 3000.
• the chain extender is not particularly limited as long as it is used in the production of ordinary polyurethane and is a short-chain diol conjugate having two or more hydroxyl groups in the molecule.
• the amount of the chain extender is preferably 0.1 to 10 parts by weight, more preferably 0 to 10 parts by weight, based on 100 parts by weight of the polyol, from the viewpoint of obtaining a polyurethane porous material having good product properties. 5-7 parts by weight, particularly preferably 115 parts by weight.
• an a-on chain extender such as a polyhydroxy conjugate having at least one a-on hydrophilic group (carboxyl group or sulfone group) in the molecule;
• a non-ionic chain extender such as an ethylene oxide compound
• a cationic chain extender such as N-methyljetanolamine.
• an a-on chain lengthening agent is preferably used.
• 2,2-dimethylol lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, 2-dimethylol butyric acid, 2,2-dimethylolvaleric acid, 1,4-butanediol-2-sulfonic acid and the like can be mentioned, and these can be used alone or in combination of two or more.
• the amount of the hydrophilic chain extender depends on the type of polyol used and the type of isocyanate described below, from the viewpoint of improving the water dispersibility of the urethane prepolymer obtained and the gelling properties described below, and the fine continuous pores. from the viewpoint of obtaining a polyurethane porous body having a urethane Prevost in all reaction components Rimmer constituting, preferably 0. 1- 4 wt 0/0, more preferably 1 one 4 wt%, particularly preferably 1 one 3 % By weight. That is, when the amount of the hydrophilic chain extender is less than 0.1% by weight, the water dispersibility of the obtained urethane prepolymer may be extremely reduced. On the other hand, if the amount of the hydrophilic chain extender exceeds 4% by weight, the gelling properties of the resulting aqueous dispersion of urethane prepolymer may be impaired.
• the isocyanate is not particularly limited as long as it is used in the production of ordinary polyurethane and has two or more isocyanate groups at its terminals.
• examples thereof include 2,4-toluene diisocyanate and 2,6 -Toluenediisocyanate, 4,4, -diphenylmethanediisocyanate, 3,3, -dichloro-4,4, -diphenylmethanediisocyanate, 2,2, -diphenyl Methane diisocyanate, 2,4-, diphenyl methane diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 1,5-naphthalenedi isocyanate, hydrogenated diphenyl dimethane methane diisoate Aromatic polyisocyanates such as cyanates and hydrogenated xylylene diisocyanates and their hydrogenated mashes; 1,4-cyclohexanediisocyanate, isophor
• the blending amount of the isocyanate is not particularly limited as long as the terminal of the obtained urethane prepolymer has an isocyanate group, and the amount of the active hydrogen group contained in each of the polyol, the chain extender and the hydrophilic chain extender is determined. What is necessary is just to mix
• the urethane prepolymer can be produced by a known method and is not particularly limited.
• a urethane prepolymer can be produced by combining a polyol with a chain in the presence or absence of an organic solvent containing no active hydrogen group in the molecule.
• the long agent, the hydrophilic chain extender and the isocyanate are reacted by the one-shot method or the multistage method, preferably at 20 ° C to 150 ° C, more preferably at 60 to 120 ° C for 2 to 10 hours. Method and the like.
• the addition order of each component is not particularly limited.
• the end point of the reaction is preferably monitored by viscosity.
• the above-mentioned organic solvent is also used for reducing the viscosity during the production of urethane prepolymer, and examples thereof include acetone, methyl ethyl ketone, N-methylpyrrolidone, toluene, tetrahydrofuran, dioxane, ⁇ , ⁇ , -dimethylformamide. And the like.
• the urethane prepolymer aqueous dispersion in the present invention is obtained by dispersing the above urethane prepolymer in water, and the mixing ratio of the urethane prepolymer to water controls the apparent density of the obtained polyurethane porous material.
• the content is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, and particularly preferably 15 to 40% by weight.
• the method for producing the urethane prepolymer water dispersion is not particularly limited.
• a urethane prepolymer and water are mixed and dispersed using a dispersing device such as a disperser mixer, a homomixer, and a homogenizer. Method and the like.
• the hydrophilic chain-length constituting the urethane pre-bolimer can be roughly determined.
• the ionic hydrophilic group of the agent may be neutralized.
• strong neutralizing agents include, for example, trimethylamine, triethylamine, tri- ⁇ -propylamine, tri- ⁇ -butylamine and the like.
• Lower alkylamines; inorganic neutralizers such as ammonia are preferably used from the viewpoint that they are easily removed by the water removal step described later.
• the blending amount of the neutralizing agent is not particularly limited, but it is usually preferable to blend the neutralizing agent in an amount substantially equal to the anionic hydrophilic group of the hydrophilic chain extender.
• a surfactant may be appropriately used.
• examples of usable surfactants include higher alcohol ethylene oxide adducts (polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc.) and higher alcohols.
• Propylene oxide adducts kamotsu with higher alcohol (ethylene oxide propylene oxide), kamotsu with alkylphenol ethylene oxide (polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, etc.), aryl With phenol ethylene oxide adduct, fatty acid ethylene oxide adduct, fatty acid polyethylene glycol ester, fatty acid amide ethylene oxide adduct, long-chain alkylamine ethylene oxide Products, polyhydric alcohol fatty acid ester ethylene oxide adduct, ethylene oxide adduct of fats and oils, glycerin fatty acid ester, polyglyceride, pentaerythritol fatty acid ester, sorbitol fatty acid ester (sorbitan ester), sorbitan ester Noon surfactants such as sucrose fatty acid esters, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanol
• the amount of the surfactant relative to polyurethane Prevost Rimmer preferably 0.5 1 20 weight 0/0, more preferably 1 one 10 wt%, particularly preferably 2 5% by weight.
• a method for producing a urethane pre-bolimer aqueous dispersion when a surfactant is blended For example, 1) a method of dispersing a urethane pre-bolimer mixed with a surfactant and water using a dispersing device such as a homomixer as described above, 2) an aqueous solution containing the urethane pre-bolimer and a surfactant In the same manner as described above using a dispersing device such as a homomixer.
• the aqueous urethane prepolymer polymer dispersion obtained in this manner is unstable with time from the viewpoint of improving the gelling characteristics described below and obtaining a polyurethane porous body having fine continuous pores.
• "unstable over time” means that when the urethane prepolymer is dispersed in water and then allowed to stand at room temperature and normal pressure, the urethane resin content becomes less than 24 hours after the dispersion. It refers to the case where a part or the whole is separated and settled.
• the above-mentioned polyamine conjugate includes, in a molecule, two or more hydrogen atoms capable of reacting with an isocyanate group of a urethane prepolymer polymer aqueous dispersion (a primary and Z or secondary amino group in one molecule).
• polyoxopolyamides such as ⁇ , ⁇ -diaminopolypropylene oxide may be used. It is also possible to use polyalkylene terminated with a terminal amino group, such as a propylene oxide addition product of a silalkyleneamine, trimethylolpropane or glycerin.
• the former has a molecular weight of 230 to 2000, and the latter has a molecular weight of 480 to 5000. Are preferably used.
• the amount of the polyamined conjugate is determined based on the active isocyanate group (theoretical value before aqueous dispersion) of the aqueous urethane prepolymer polymer dispersion and the polyamine.
• the equivalent ratio to the active hydrogen group of the conjugated product is preferably 0.1 to 90%, more preferably 1 to 50%, and particularly preferably 5 to 30%.
• the polyurethane porous body of the present invention can be produced by a known method, and is not particularly limited.
• the urethane pre-bolimer aqueous dispersion obtained above and the polyamined conjugate may be used.
• a method of uniformly mixing the mixture, pouring the obtained mixture into a mold, allowing the cross-linking reaction to proceed in a state of standing at room temperature for 10 hours or more, and removing water from the obtained gelled product can be cited.
• the polyurethane porous body of the present invention contains a coloring agent, an antibacterial agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a defoaming agent, a thickening agent as long as the object of the present invention is not impaired. It may contain additives such as an agent and a pH adjuster, and these may be added alone or as a mixture of two or more.
• a neutralizing agent When a neutralizing agent is added to an aqueous urethane prepolymer polymer dispersion containing an aionic chain-lengthening agent as a constituent component as a hydrophilic chain-lengthening agent, the resulting polyurethane porous material
• a compound capable of reacting with the anionic hydrophilic group of the anionic chain extender may be added to crosslink the urethane prepolymer.
• examples of such a compound include a carbodiimide-based compound, an oxazoline-based compound, an epoxy-based compound, and a melamine-based compound.
• the neutralizing agent which has formed a salt with the aionic hydrophilic group is dissociated by the aionic chain length agent, so that the water washing step described below can be performed efficiently. it can.
• the terminal isocyanate group of the urethane prepolymer in the urethane prepolymer aqueous dispersion reacts with water present around the urethane prepolymer, and the urethane prepolymer is dispersed in water. Thereafter, it is usually preferable to react with the polyamine compound within 48 hours.
• the dispersibility of the produced urethane prevolimer aqueous dispersion can be improved by the urethane prevolimer, which is a force that certainly improves when the hydrophilic chain extender and the neutralizing agent and the surfactant are contained.
• the polyamine is usually dispersed within 48 hours, preferably within 24 hours, and more preferably within 12 hours after dispersing the urethane prepolymer in water. It is preferred to react with the dangling product.
• air may be naturally dried at room temperature, but it is usually preferable to dry at 70 ° C. or higher using a hot-air dryer or the like in order to shorten the time for removing moisture.
• a hot-air dryer or the like in order to shorten the time for removing moisture.
• the obtained gelled substance contains a neutralizing agent, a surfactant, an antifoaming agent, a thickener, a pH adjuster, and the like, before the drying step, for example, a washing machine is used. It is preferable to wash these components with water.
• the polyurethane porous body thus obtained has fine continuous pores and can satisfy practicality in product properties such as apparent density, tensile strength, and elongation.
• polycarbonate diol as a polyol [manufactured by Asahi Kasei Corporation, trade name: T 4671, number average molecular weight: 1000], ethylene glycol as a chain extender, and 2,2-dimethylolpropion as an aqueous hydrophilic chain extender 1,6-Hexamethylene diisocyanate was added as an acid and isocyanate in the mixing ratio shown in Table 1 and stirred at 90 ° C. for 3 hours to obtain a urethane prepolymer.
• the urethane prepolymer obtained above was heated to 80 ° C, and triethylamine as a neutralizing agent was added, followed by stirring for 2 minutes.
• a polyoxyethylene alkyl ether-type non-ionic surfactant manufactured by Asahi Den-Dai Kogyo Co., Ltd., trade name: Adeikitor TN-100, HLB: 13.8, cloud point: 75 ° C
• the urethane prevolimer to which the neutralizing agent and the surfactant were added was added to distilled water, and the mixture was stirred with a homomixer for 5 minutes to obtain a urethane prevolimer aqueous dispersion.
• test piece having a size of 60 mm in length, 10 mm in width, and 2 mm in thickness was cut out from the above reaction product, and measured using an autograph [manufactured by Shimadzu Corporation, model number: ASG-D]. Measure so that the tensile direction is the longitudinal direction of the test piece, and use the strength when the test piece breaks,
• a test piece having a size of 60 mm in length, 10 mm in width, and 2 mm in thickness was cut out from the above reaction product, and measured using an autograph [manufactured by Shimadzu Corporation, model number: ASG-D]. The measurement is performed at the marked line 20 mm so that the tensile direction is the longitudinal direction of the test piece, and the elongation when the test piece is cut is used.
• the formula: [elongation (%)] ([between the marked lines during cutting] Length (mm)]-[Marked line distance (mm)]) ⁇ [Marked line distance (mm)] X100 was used to determine the tensile strength. (According to QLS K 6301)
• Table 2 shows properties of the reaction products obtained in Example 17 and Comparative Examples 13 to 13.
• the reaction product obtained in Examples 17 to 17 exhibited physical properties particularly useful as a water-absorbing roll, a roll for OA equipment, a water-absorbing member, and a stamp face member.
• Example 17 and Comparative Example 13 were observed with a digital microscope [manufactured by Keyence Corporation, model number: VH-6300] at a magnification of 600 times. .
• a digital microscope manufactured by Keyence Corporation, model number: VH-6300
• an observation photograph of Example 1 is shown in FIG. 1
• an observation photograph of Comparative Example 1 is shown in FIG.
• the reaction product obtained in Example 1 has fine continuous pores, and the reaction product obtained in Examples 2-7 also Similar to 1, it was observed to have fine continuous pores.
• the reaction product obtained in Comparative Example 1 did not have a porous structure, but was in a film state, and the reaction product obtained in Comparative Example 2-3 was obtained. As for Comparative Example 1, it was observed that the film was in a film state.
• the polyurethane porous material of the present invention is a water-absorbing roll, a roll for OA equipment, and a water-absorbing member. It can be suitably used for various products such as stamping members, bed mats, cosmetic puffs, abrasive sheets, air cleaning equipment filters, artificial leather, agricultural materials, electronic device manufacturing related materials, and health and welfare products.

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• Polyurethanes Or Polyureas (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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• 2004
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