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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4825—Polyethers containing two hydroxy groups
• • 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
• • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
• • 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
  • C08G18/40—High-molecular-weight compounds
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• • 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
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • 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
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units
  • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
  • C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
• • 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
  • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
• • 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
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
• • 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 two-component curable foamed polyurethane composition capable of exhibiting excellent performances such as hydrolysis resistance, oil resistance, and flexibility, a foamed polyurethane molded product using the same, and a shoe sole. More specifically, for example, the sole material of various shoes such as men's shoes, women's shoes, athletic shoes, safety shoes, work shoes, and indoor shoes, the sole material of various shoes such as slippers, sandals, sandals, gloves, work clothes, Two-component curable polyurethane foam composition useful as a material for various wearing articles such as hats and masks, or as an industrial member (for example, a roll, packing, hose, sheet, cushioning material, cushion, vehicle member, packaging member, etc.)
• the present invention relates to a foamed polyurethane molded article and a shoe sole.
• foamed polyurethane is obtained by reacting polyisocyanate and polyol.
• polyol such as polyether polyol, polyester polyol, and polycarbonate polyol
• polyether-based foamed polyurethane polyester-based foamed polyurethane
• polycarbonate Classified into polyurethane foam for example, polyether-based foamed polyurethane, polyester-based foamed polyurethane, polycarbonate Classified into polyurethane foam.
• the polyether-based foamed polyurethane has good hydrolysis resistance, but is inferior in oil resistance.
• the strength of the foamed polyurethane molded product is reduced. There were problems such as changes in the surface, swelling and deterioration.
• Polyester-based foamed polyurethane has relatively good oil resistance but is poor in hydrolysis resistance. For example, under water or in a hot and humid environment, the strength of the foamed polyurethane molded product is reduced. There were problems such as changes, swelling and deterioration.
• the polycarbonate-based foamed polyurethane for example, a foamed polyurethane using polycarbonate diol of 1,6-hexanediol, has a stable carbonate bond in the polymer chain, so that it has hydrolysis resistance, weather resistance, heat resistance, etc. Although it has good performance such as flexibility, it has the disadvantage of poor flexibility due to its high crystallinity. For example, in applications that require particularly flexibility (flexibility) such as shoe soles, cushions, gloves, and hoses. There was a problem that it was difficult to use.
• the performance at the initial stage of molding is stable and stable, and has excellent oil resistance, hydrolysis resistance, bending Development of a two-pack curable foamed polyurethane composition that exhibits properties (flexibility) and a foamed polyurethane molded product using the same have been desired.
• the polymer polyol contains a specific repeating unit, both terminal groups are hydroxyl groups, and a polycarbonate diol having a number average molecular weight of 300 to 10,000.
• a certain foam is known (for example, patent document 1).
• Patent Document 1 it is possible to provide a polyurethane foam having a good balance of physical properties such as oil resistance, flexibility, hydrolysis resistance, and weather resistance.
• Patent Document 1 Although the polyurethane foam obtained in Patent Document 1 is improved in oil resistance, it has a problem that it is not suitable for practical use because it is inferior in flexibility (flexibility).
• Patent Document 2 a polyurethane foam produced from polyisocyanate and polycarbonate polyol is known (for example, Patent Document 2).
• a polyurethane foam having good hydrolysis resistance and heat resistance can be provided, and it can be used under conditions of high temperature and high humidity that could not be used conventionally.
• the obtained foamed polyurethane molded product (that is, polyurethane foam) has a problem in practical use because performance such as flexibility (flexibility) is still insufficient.
• the object of the present invention is to have excellent stability with no change in the performance at the initial stage of molding in oil or in an environment exposed to an oily atmosphere, in water or in a hot and humid environment, and excellent oil and water resistance.
• a two-component curable foamed polyurethane composition comprises a main agent containing a urethane prepolymer (A) having an isocyanate group at the molecular end, and an isocyanate group. It contains a curing agent containing a reactive compound (B), water (C), and a catalyst (D), and the isocyanate group reactive compound (B) contains polycarbonate diol (B1) and polyoxyethylene propylene glycol (B2).
• the two-component curable foamed polyurethane composition has excellent stability with no change in the initial molding performance, oil resistance, and hydrolysis resistance.
• the present inventors have found that excellent performance such as flexibility (flexibility) can be exhibited, and have completed the present invention.
• the two-component curable foamed polyurethane composition comprises a main component containing a urethane prepolymer (A) having an isocyanate group at the molecular end, an isocyanate group-reactive compound (B), water (C), a catalyst ( D) and a curing agent containing D), and the isocyanate group-reactive compound (B) is essentially composed of polycarbonate diol (B1), polyoxyethylene propylene glycol (B2), and glycol (B3) having a molecular weight of 50 to 300.
• the (B1) is in the range of 6 to 88% by mass
• the (B2) is in the range of 5 to 93% by mass with respect to the total amount of the (B1) to (B3).
• B3) is contained in the range of 0.5 to 20% by mass
• the content of the polycarbonate diol (B1) in the two-component curable foamed polyurethane composition is 5 to 35% by mass. It relates two-part curable polyurethane foam composition, characterized in that in the range of.
• the present invention relates to a foamed polyurethane molded product obtained by molding the two-component curable foamed polyurethane composition.
• the present invention relates to a shoe sole including the polyurethane foam molded article, wherein the density of the polyurethane foam molded article is in the range of 0.3 to 1.1 g / cm 3. .
• the two-component curable foamed polyurethane composition of the present invention is a foam that exhibits no change in initial molding performance, excellent stability, and excellent performance such as oil resistance, hydrolysis resistance, and flexibility (flexibility).
• Polyurethane molded products can be provided, especially as polyurethane elastomer foams, such as men's shoes, women's shoes, sports shoes, safety shoes, work shoes, indoor shoes, and other shoe soles, indoor slippers, sandals, sandals, etc.
• industrial members such as rolls, packing, hoses, sheets, cushioning materials, cushions, vehicle members, packaging members, etc. It can be used for various purposes.
• the two-component curable foamed polyurethane composition of the present invention comprises a urethane prepolymer (A) having an isocyanate group at the molecular end (hereinafter referred to as “isocyanate group-terminated urethane prepolymer (A)”). And a curing agent containing an isocyanate group-reactive compound (B), water (C), and a catalyst (D).
• the isocyanate group-terminated urethane prepolymer (A) used in the present invention can be obtained by reacting polyisocyanate and polyol according to a known method, and the reaction method and reaction conditions are not particularly limited.
• polyisocyanate in the present invention refers to a compound having two or more isocyanate groups (hereinafter also referred to as NCO groups) in the molecule.
• any of known aliphatic polyisocyanate, aromatic polyisocyanate, and alicyclic polyisocyanate can be used.
• diphenylmethane diisocyanate MDI; 4,4′-form, 2,4′-form or 2,2′-form, or a mixture thereof, crude MDI
• carbodiimide-modified MDI modified MDI
• polymethylene poly Phenyl polyisocyanate carbodiimidized diphenylmethane polyisocyanate
• xylylene diisocyanate XDI
• 1,5 -Aromatic polyisocyanates such as naphthalene diisocyanate (NDI), tetramethylxylene diisocyanate, phenylene diisocyanate, or hexamethylene diisocyanate (HD
• MDI carbodiimide-modified MDI
• polyol used in the present invention examples include polyester polyol, polyether polyol, polycarbonate polyol, and low molecular weight glycol (having a molecular weight of 50 to 300).
• the polyester polyol is a known method using as raw materials a polycarboxylic acid having an aromatic skeleton or a polycarboxylic acid not having an aromatic skeleton, and a polyol having an aromatic skeleton or a polyol having no aromatic skeleton. Can be synthesized.
• polycarboxylic acid used for producing the polyester polyol examples include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid.
• Polycarboxylic acids having an aromatic skeleton such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid
• polycarboxylic acids having no aromatic skeleton such as acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, trimellitic acid, and pyromellitic acid. These may be used alone or in combination of two or more.
• polycarboxylic acid referred to in the present invention is a general term including polycarboxylic acids and acid derivatives such as lower ester compounds (for example, methyl ester compounds), acid anhydrides, and acid halides. .
• diol used in the production of the polyester polyol examples include polyols having an aromatic skeleton such as dihydroxynaphthalene, bisphenol A, bisphenol S, bisphenol AF, bisphenol Si 2 , and alkylene oxide adducts thereof, or ethylene glycol ( EG), 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butylene glycol (1,4BG), 1,5-pentanediol, 1,6-hexanediol, Neopentyl glycol, trimethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, 2-butyl -Aliphatic diols such as 2-ethyl-1,3-propanediol and 2-methyl-1,3-propanediol; 1,4-
• alcohols and saccharides such as glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, and aconite sugar; or amines can also be used as a raw material for synthesizing the polyester polyol. These may be used alone or in combination of two or more.
• the hydroxyl value of the polyester polyol is desirably set in consideration of the target viscosity of the isocyanate group-terminated urethane prepolymer (A) as the main agent.
• the hydroxyl value of the polyester polyol is preferably in the range of 25 to 240 mg KOH / g (hereinafter abbreviated as a unit), more preferably in the range of 35 to 120. If the hydroxyl value of the polyester polyol is within such a range, an urethane prepolymer having an appropriate viscosity can be obtained without causing an extreme increase in the viscosity of the isocyanate group-terminated urethane prepolymer (A). It can be expressed.
• the polyester polyol includes polyester diols, polyamide polyester diols and the like obtained by using polycarboxylic acids, polyols, polyamines and the like other than the above.
• polyether polyol examples include polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene propylene glycol (PEPG), and polytetramethylene glycol (PTMG). Among these, a hydroxyl value of 14 to PPG in the range of 120 is preferred.
• the polyether polyol may have any structure of linear, branched and cyclic.
• the hydroxyl value of the polyether polyol is preferably in the range of 14 to 120, more preferably in the range of 20 to 80. If the hydroxyl value of the polyether polyol is within such a range, the brittleness of the obtained foamed polyurethane molded article can be easily controlled, and excellent strength and wear resistance can be obtained.
• lactones for example, ⁇ -caprolactone, ⁇ -butyrolactone, etc.
• polyether polyol such as PTMG
• Examples of the polycarbonate diol include those synthesized from diol and carbonate as raw materials.
• Examples of the diol include ethylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, and 3-methyl. 1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol and the like.
• Examples of the carbonate include ethylene carbonate, phenyl carbonate, and diethyl carbonate. These may be used alone or in combination of two or more.
• the molecular weight of the low molecular weight glycol is preferably in the range of 50 to 300, more preferably in the range of 50 to 200.
• the molecular weight of the low molecular weight glycol is within such a range, it is preferable because when it is used as a polyol, the reactivity can be controlled more efficiently and the moldability (yield and molding unevenness) becomes better.
• Examples of the low molecular weight glycol include ethylene glycol (EG), 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1, Aliphatic diols such as 3-propanediol and 2-methyl-1,3-propanediol; Alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; Glycerin , Trimethylolpropane Such trifunctional or more hydroxyl group-containing compound such as pent
• polycaprolactone polyol for example, polycaprolactone polyol, aromatic polyester polyol, acrylic polyol, polyolefin polyol, castor oil-based polyol, etc. obtained by ring-opening polymerization of a caprolactone monomer can be used.
• polystyrene resin examples include alkylene oxides such as ethylene oxide (EO), propylene oxide (PO), and butylene oxide as starting materials having at least three hydroxyl groups such as glycerin, trimethylolpropane, pentaerythritol, and sorbitol.
• alkylene oxides such as ethylene oxide (EO), propylene oxide (PO), and butylene oxide as starting materials having at least three hydroxyl groups such as glycerin, trimethylolpropane, pentaerythritol, and sorbitol.
• Polyether polyols such as poly (oxyalkylene) glycol and poly (oxytetramethylene) glycol obtained by addition polymerization of carboxylic acid; or polyvalent carboxylic acids such as adipic acid, sebacic acid, azelaic acid, succinic acid, maleic acid, and phthalic acid Acid and ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, -Polyhydric alcohols such as ethanediol, neopentyl glycol, 2, -methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, glycerin, trimethylolpropane, diethylene glycol, triethylene glycol, tetraethylene glycol Polyester polyol obtained by polycondensation of poly
• the isocyanate equivalent of the isocyanate group-terminated urethane prepolymer (A) used as the main component (hereinafter referred to as “NCO equivalent”) is preferably in the range of 150 to 350, more preferably in the range of 200 to 300. If the NCO equivalent of (A) is within such a range, the viscosity becomes an appropriate viscosity that is easy to use in a foaming machine without causing an abnormal increase in melt viscosity during the operation, and excellent workability can be obtained.
• the “isocyanate equivalent” (unit: g / mol) in the present invention is a value measured in accordance with the JIS K7301-1995 test method for tolylene diisocyanate type prepolymers for thermosetting urethane elastomers.
• the isocyanate group-terminated urethane prepolymer (A) is produced by reacting an NCO group of a polyisocyanate with a hydroxyl group (hereinafter also referred to as OH group) of a polyol in an equivalent ratio by a known method. be able to.
• reaction method for obtaining the isocyanate group-terminated urethane prepolymer (A) for example, a polyisocyanate charged in a reaction vessel is charged with a polyol from which water has been removed by an appropriate method such as dropping, dividing, or batching, What is necessary is just to employ
• the production of the isocyanate group-terminated urethane prepolymer (A) is usually carried out without a solvent, but may be allowed to react in an organic solvent.
• an organic solvent that does not inhibit the reaction may be used, and usually examples thereof include ethyl acetate, n-butyl acetate, methyl ethyl ketone, toluene and the like.
• the organic solvent used for the reaction is removed by an appropriate method such as heating under reduced pressure or distilling off the thin film during or after the reaction.
• the reaction conditions (temperature, time, pressure, etc.) of the isocyanate group-terminated urethane prepolymer (A) are not particularly limited as long as the reaction behavior and product quality can be controlled normally.
• the reaction is preferably performed at a reaction temperature of 50 to 90 ° C. under a reaction time of 2 to 24 hours.
• the pressure may be normal pressure, pressurization, or reduced pressure.
• the reaction method can be selected from known reaction methods such as batch, semi-continuous, and continuous, and is not particularly limited.
• a urethanization catalyst can be used as necessary.
• the urethanization catalyst can be appropriately added in any step of reaction from raw material adjustment / preparation. There are various methods for adding the urethanization catalyst, such as batch, division, and continuous, but there is no particular limitation.
• urethanization catalyst known catalysts can be used and are not particularly limited.
• nitrogen-containing compounds such as triethylamine, tributylamine, benzyldibutylamine, triethylenediamine, and N-methylmorpholine; or titanium tetrabutoxide, dibutyltin oxide ,
• Organometallic compounds such as dibutyltin dilaurate, tin 2-ethylcaproate, zinc naphthenate, cobalt naphthenate, zinc 2-ethylcaproate, molybdenum glycolate, potassium acetate, zinc stearate, tin octylate, dibutyltin dilaurate
• inorganic compounds such as iron chloride and zinc chloride.
• the reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon, but it may be carried out in a dry air atmosphere or in a condition not containing moisture such as sealed conditions.
• an inert gas atmosphere such as nitrogen or argon
• the equivalent ratio of the NCO group of the polyisocyanate to the OH group of the polyol is preferably in the range of 2 to 90, more preferably in the range of 3 to 45.
• the reaction can be easily controlled, an abnormal reaction does not occur, and a urethane foam molded article having an excellent performance balance can be obtained.
• the curing agent used in the present invention includes, as essential components, an isocyanate group-reactive compound (B), water (C) as a foaming agent, and a catalyst (D).
• the isocyanate group-reactive compound (B) essentially contains three types of polyols: polycarbonate diol (B1), polyoxyethylene propylene glycol (B2), and glycol (B3) having a molecular weight of 50 to 300.
• the polycarbonate diol (B1) is liquid at 60 ° C., and the hydroxyl value of the (B1) is preferably in the range of 45 to 150 mgKOH / g, more preferably in the range of 50 to 120.
• the hydroxyl value of (B1) is within such a range, it is preferable because performance such as excellent moldability (yield and molding unevenness), strength, and wear resistance can be obtained.
• the hydroxyl value as used in the field of this invention means the value measured according to the measuring method mentioned later.
• a polycarbonate diol as conventionally used that is solid or semi-solid at 40 to 60 ° C. cannot be melted during production or cannot be sufficiently melted. It cannot be used.
• the polycarbonate diol (B1) used in the present invention is liquid at 60 ° C., it does not require any melting work, can simplify the manufacturing process such as weighing, transferring, and charging, and is excellent in workability. Is greatly improved. However, when the polycarbonate diol is solid or semi-solid at 60 ° C. as in the prior art, there is no fluidity, and the workability such as weighing, transferring, and charging is clearly inferior, resulting in a significant decrease in productivity. There is.
• Examples of the polycarbonate diol (B1) include those synthesized from diol and carbonate as raw materials.
• Examples of the diol include ethylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol ethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, Examples include 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2-methyl-1,3-propanediol.
• Examples of the carbonate include ethylene carbonate, phenyl carbonate, diethyl carbonate, and the like. These may be used alone or in combination of two or more.
• DURANOL T4671 (trademark: Asahi Kasei Chemicals Corporation, hydroxyl value 100-120, melting point 5-15 ° C.), T4672 (trademark: manufactured by the company, hydroxyl value 45-56, Melting point: 5 to 15 ° C.), T4691 (trademark: manufactured by the company, hydroxyl value: 100-120, melting point: 50-60 ° C), T4692 (trademark: manufactured by the company, hydroxyl value: 51-61, melting point: 50-60 ° C), T5650J (trademark) Manufactured by the same company, hydroxyl value 130 to 150, melting point ⁇ 5 ° C.
• T5651 (trademark: manufactured by the company, hydroxyl value 100 to 120, melting point ⁇ 5 ° C. or lower)
• T5652 (trademark: manufactured by the company, hydroxyl value 51 to 61 ° C., Melting point: -5 ° C or lower)
• T6001 (trademark: manufactured by the company, hydroxyl value 100-120, melting point 40-50 ° C)
• T6002 (trademark: manufactured by the company, hydroxy acid Value 51-61, melting point 40 ⁇ 50 ° C.), and the like.
• (B1) used in the present invention is not limited to these commercially available products.
• the content of the polycarbonate diol (B1) in the isocyanate group-reactive compound (B) is in the range of 6 to 88% by mass, preferably 15 to 15%, based on the total amount of the (B1) to (B3). It is in the range of 75% by mass.
• a foamed polyurethane molded article having excellent performance such as oil resistance and flexibility can be obtained.
• the (B1) is less than 6% by mass, the oil resistance tends to be inferior.
• the (B1) exceeds 88% by mass the flexibility tends to be inferior.
• the content of the polycarbonate diol (B1) in the two-component curable foamed polyurethane composition is in the range of 5 to 35% by mass, preferably in the range of 10 to 30% by mass.
• a foamed polyurethane molded product having a performance balance such as excellent oil resistance, hydrolysis resistance, and flexibility (flexibility) can be obtained.
• the (B1) is less than 5% by mass, the obtained foamed polyurethane molded product may be inferior in oil resistance.
• said (B1) exceeds 35 mass%, there exists a possibility that the foaming polyurethane molding obtained may be inferior to a flexibility.
• polyoxyethylene propylene glycol (B2) having a hydroxyl value and an ethylene oxide addition rate in specific ranges is essential.
• the polyoxyethylene propylene glycol (B2) used in the present invention preferably has a hydroxyl value in the range of 10 to 120, and the ethylene oxide (EO) addition rate in the (B2) is 5 to 50%. More preferably, the hydroxyl value is in the range of 15 to 60, and the EO addition rate is in the range of 10 to 40%.
• excellent performance such as good compatibility with polycarbonate diol, hydrolysis resistance, flexibility (flexibility) and the like can be expressed.
• polyoxyethylene propylene glycol (B2) examples include EO-PO block polymers and EO-PO random polymers.
• EO is an abbreviation for ethylene oxide
• PO is an abbreviation for propylene oxide.
• Examples of the commercially available polyoxyethylene propylene glycol (B2) include Exenol 820 (trademark: Asahi Glass Co., Ltd., hydroxyl value 34), Adeka polyether Exenol 850 (trademark: Asahi Glass Co., Ltd., hydroxyl value 24), Preminol 7003 (Trademark: Asahi Glass Co., Ltd., hydroxyl value 27), Preminol 5005 (Trademark: Asahi Glass Co., Ltd., hydroxyl value 28.5), CM-294 (Trademark: ADEKA Corporation, EO-PO block polymer, hydroxyl group) No. 39), CM-424 (trademark: manufactured by ADEKA Corporation, EO-PO block polymer, hydroxyl value 25.5) and the like.
• the (B2) used in the present invention is not limited to these commercially available products.
• the content of polyoxyethylene propylene glycol (B2) in the isocyanate group-reactive compound (B) is in the range of 5 to 93% by mass with respect to the total amount of (B1) to (B3), preferably Is in the range of 15 to 85% by mass.
• the content ratio of (B2) is within such a range, a foamed polyurethane molded article having performances such as excellent compatibility with polycarbonate diol, hydrolysis resistance, and flexibility (flexibility) can be obtained.
• (B2) is less than 5% by mass, the flexibility (flexibility) tends to be inferior.
• the said (B2) exceeds 93 mass%, it exists in the tendency for it to be inferior to oil resistance and abrasion resistance.
• the glycol (B3) used in the present invention is a glycol having a molecular weight in the range of 50 to 300. If the molecular weight of (B3) is within such a range, it is possible to obtain performances such as excellent moldability (yield and molding unevenness), strength, wear resistance, and flexibility (flexibility).
• Examples of the low molecular weight glycol (B3) include ethylene glycol (EG), 1,2-propanediol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5 -Pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, 2-butyl-2- Aliphatic diols such as ethyl-1,3-propanediol and 2-methyl-1,3-propanediol; alicyclic groups such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A Diols; glycerin, trimethyl Rupuropan and trifunctional or more hydroxyl group-containing
• ethylene glycol (EG), propylene glycol (PG), 1,4-butylene glycol (1,4BG), and diethylene glycol (DEG) are preferable. is there.
• Said (B3) may be used alone or in combination of two or more.
• the content of glycol (B3) in the isocyanate group-reactive compound (B) is in the range of 0.5 to 20% by mass, preferably 3 with respect to the total amount of (B1) to (B3). It is in the range of ⁇ 12% by mass. If the content ratio of (B3) is within such a range, a foamed polyurethane molded product having excellent properties such as strength and abrasion resistance can be obtained. However, when the (B3) is less than 0.5% by mass, the strength and wear resistance tend to be inferior. Further, when (B3) exceeds 20% by mass, the flexibility (flexibility) tends to be inferior.
• isocyanate group-reactive compound (B) other isocyanate group-reactive compounds such as polyols and polyamines other than the above (B1) to (B3) may be used in combination as long as the object of the present invention is not impaired. Good.
• a polyol that can be used for the synthesis of the aforementioned isocyanate group-terminated urethane prepolymer (A) can also be used.
• Examples of the other isocyanate group-reactive compounds include polyaminochlorophenylmethane compounds, mixtures of polyaminochlorophenylmethane compounds and polytetramethylene glycol, and 4,4′-diamino-3 which is a dinuclear polyaminochlorophenylmethane compound. 3,3′-dichlorodiphenylmethane (hereinafter referred to as MBOCA). These may be used alone or in combination of two or more.
• the amount of the isocyanate group-reactive compound (B) is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the isocyanate group-terminated urethane prepolymer (A). Parts by weight, and more preferably in the range of 50 to 200 parts by weight. If the blending amount of (B) is within such a range, it can be efficiently stirred and mixed in a foaming machine at the time of molding, and foam cells having a uniform and fine shape can be formed.
• a two-component curable foamed polyurethane composition suitable for a foamed polyurethane molded product such as a shoe sole having excellent performance such as (flexibility) and abrasion resistance can be obtained.
• water (C) is used as a foaming agent in the water foaming method.
• the “water” as used in the present invention is, for example, liquid water, but, for example, air, inert gas (for example, nitrogen, argon, etc.), moisture in gas such as carbon dioxide, water vapor, substrate It is a generic term that includes the surface layer and moisture in the substrate.
• the amount of water (C) is usually preferably in the range of 0.01 to 1.5 parts by weight, more preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the isocyanate group-reactive compound (B).
• the range is 0.6 parts by mass. If the blending amount of the water (C) is within such a range, a two-component curable foamed polyurethane composition capable of expressing a stable foamed state can be obtained.
• the method of adding water (C) when mixing the main agent and the curing agent is not particularly limited.
• a curing agent an isocyanate group-reactive compound (B), water (C), a catalyst (D), and additives as necessary are added and mixed in advance, and then the main agent and Examples thereof include a method of mixing the curing agent and injecting, foaming, and curing into a mold.
• water (C) is used as the foaming agent, but a known foaming agent used for foaming during the urethanization reaction may be used in combination.
• a foaming aid may be used in combination, for example, 1,1-dichloro-1-fluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-penta Low boiling point compounds such as halogenated hydrocarbons such as fluorobutane and methylene chloride or hydrocarbons such as pentane can be used.
• additives such as a foam stabilizer can be used as necessary.
• foam stabilizer all those effective for the production of foamed polyurethane moldings can be used.
• surfactants such as silicon compounds such as polydimethylsiloxane and polysiloxane-polyalkylene oxide block copolymers, metal soaps, ethylene oxide and / or propylene oxide adducts of alkylphenols and fatty acids.
• Catalyst (D) The catalyst (D) is blended with the two-component curable polyurethane foam composition of the present invention.
• the type and amount of the catalyst (D) are preferably selected in consideration of the time from mixing the catalyst to pouring into the mold, the temperature, the final foamed state of the foam, and the like.
• the catalyst (D) is not particularly limited.
• the blending amount of the catalyst (D) is preferably in the range of 0.15 to 2 parts by mass, more preferably 0.3 to 1 part per 100 parts by mass of the isocyanate group-reactive compound (B). The range is 5 parts by mass. If the blending amount of the catalyst (D) is within such a range, a two-component curable foamed polyurethane composition capable of expressing a stable foamed state can be obtained.
• the main component containing the isocyanate group-terminated urethane prepolymer (A) is mixed and mixed as a curing agent with the isocyanate group-reactive compound (B) and water (C) in the range of the blending amount. This is preferable because the reactivity can be controlled efficiently and the moldability (yield and molding unevenness) is improved.
• the two-component curable foamed polyurethane composition of the present invention can be obtained by blending the main agent and the curing agent prepared as described above according to the composition and immediately mixing them sufficiently.
• the mixing ratio of the main agent and the curing agent is [total number of moles of NCO groups ( ⁇ ) of the isocyanate group-containing urethane prepolymer (A) as the main agent], [isocyanate group-reactive compound (B) and water (C).
• the blending ratio ( ⁇ / ⁇ ) of the main agent and the curing agent is preferably in the range of 1 / 0.7 to 1 / 1.2, more preferably in the range of 1 / 0.8 to 1 / 1.0. . If the mixing ratio of the main agent and the curing agent is within such a range, a two-component curable foamed polyurethane composition capable of exhibiting excellent strength and abrasion resistance can be obtained.
• the foamed polyurethane molded article of the present invention is obtained by molding using the two-component curable foamed polyurethane composition.
• thermoplastic polyurethane resin, cast polyurethane resin, polyurethane foam (polyurethane elastomer foam) , Rigid polyurethane foam, flexible polyurethane foam, etc.) and the like, and foamed polyurethane molded bodies are preferred.
• an isocyanate group-terminated urethane prepolymer prepared by reacting the polyisocyanate and the polyol in advance is prepared.
• the foamed polyurethane molded article of the present invention for example, water (C), catalyst (D) in the isocyanate group-reactive compound (B), and additives as required (for example, antistatic agent, antistatic agent) It is preferable to use a mixture obtained by premixing an auxiliary agent, a foaming auxiliary agent, etc.) as a curing agent.
• a premixed mixture (curing agent) and the main agent containing the isocyanate group-terminated urethane prepolymer (A) can be mixed and foamed by high-speed stirring in a foam molding machine.
• a method for producing a foamed polyurethane molded product of the present invention a method using a water foaming method including the following [Step 1] to [Step 4] using a two-component curable foamed polyurethane composition is exemplified. it can.
• Step 1 Main agent adjustment step Polyisocyanate is charged into the reaction apparatus, and a predetermined amount of polyol is charged dropwise or divided while paying attention to heat generation at an internal temperature of 60 to 90 ° C., and allowed to react with stirring under a nitrogen atmosphere. A main agent containing the terminal urethane prepolymer (A) is obtained.
• Step 2 Step of adjusting a two-component curable foamed polyurethane composition (mixing of main agent and curing agent)
• the main component containing the isocyanate group-terminated urethane prepolymer (A), and the isocyanate group-reactive compound (B), water (C), catalyst (D), and other additives for example, charging
• a predetermined amount of the main agent and the curing agent is stirred and mixed to prepare a foaming reaction liquid.
• Step 3 Casting Step Immediately, the foaming reaction solution prepared in Step 2 is poured into a mold of a foam molding machine that has been heated in advance.
• Step 4 Curing step
• the foaming reaction liquid is heated and held in an appropriate temperature range (for example, 40 to 50 ° C.) while being injected into the mold, and then foamed and cured, and further at an appropriate temperature (for example, 40 to 50 ° C.). After holding (for example, for 3 to 15 minutes), the foamed polyurethane molded article is taken out.
• an appropriate temperature range for example, 40 to 50 ° C.
• an appropriate temperature for example, 40 to 50 ° C.
• the foam molding machine is not particularly limited, and known ones such as a low pressure foam molding machine and an injection foam molding machine can be used.
• the water foaming method is most preferable from the viewpoint of production efficiency, production cost, etc.
• the foaming method using hollow beads mechanical You may combine well-known foaming methods, such as a foaming method and a chemical foaming method.
• the foamed urethane molded product of the present invention is, for example, an antistatic agent, an antistatic aid, a foaming aid, a flame retardant, a foam stabilizer, a chain extender, a plasticizer, a filler, as long as the object of the present invention is not impaired.
• Known additives such as a colorant, a colorant, a weathering stabilizer, a light stabilizer, and an antioxidant can be appropriately used.
• any known one can be used.
• a substituted quaternary ammonium cation-based antistatic compound substituted with a hydrocarbon group and an oxyhydrocarbon group an organic acid metal salt
• Anionic antistatic compounds, nonionic antistatic compounds, and the like can be used.
• substituted sulfonic acid quaternary ammonium examples include dialkylsulfuric acid derivatives, methanesulfonic acid ester derivatives, p-toluenesulfonic acid ester derivatives, and the like. These can be used individually or in mixture of 2 or more types.
• organic acid metal salt-based anionic antistatic compound examples include bis (trifluoromethanesulfonyl) imide metal salt, tris (trifluoromethanesulfonyl) methane metal salt, alkylsulfonic acid metal salt, benzenesulfonic acid metal salt, Alternatively, organic metal salts such as alkylbenzene sulfonic acid metal salts can be used. These can be used individually or in mixture of 2 or more types.
• a known antistatic aid may be contained within a range not impairing the object of the present invention, and the content thereof is not particularly limited.
• antistatic aid known ones can be used, and examples thereof include cyclic ketones, sorbitan fatty acid esters, and lactone monomers.
• examples of the cyclic ketones include cyclopentanone, cyclohexanone, cycloheptanone, and derivatives thereof
• sorbitan fatty acid esters include, for example, sorbitan sesquioleate, sorbitan monooleate, sorbitan monostearate, sorbitan monolaurate.
• lactone monomers such as acrylate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and lactone monomers include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ - Examples include lactone monomers such as valerolactone, ⁇ -caprolactone, and ⁇ -crotonolactone. These can be used alone or in combination of two or more.
• the antistatic agent or the antistatic auxiliary agent is a plasticizer that is suitably used for adjusting the flexibility of the polyol or the foamed polyurethane molded body so as to be uniformly contained in the foamed polyurethane molded body.
• a plasticizer that is suitably used for adjusting the flexibility of the polyol or the foamed polyurethane molded body so as to be uniformly contained in the foamed polyurethane molded body.
• it is preferably used in the production of a foamed polyurethane molding in a state of being previously dissolved in an adipate polyester plasticizer, a benzoic acid polyester plasticizer, or the like.
• a method for forming the foamed polyurethane molded article of the present invention a known method can be employed. For example, a mold forming method in which the mixed foamed liquid discharged from the molding machine is open-injected into the mold, or an injection molding method in which the mixed foamed liquid is directly injected into a closed mold directly connected to the discharge port of the molding machine.
• any mold can be used as long as it is used as a mold for forming a molded body, and any shape may be used.
• it includes not only a normally used upper mold, lower mold open mold, flat mold, cylindrical mold, and concave mold, but also a closed mold used for injection molding.
• the material of the mold any known material such as iron, aluminum, or epoxy resin can be used.
• the foamed polyurethane molded article of the present invention has excellent performance such as hydrolysis resistance, oil resistance, flexibility (flexibility), etc., and as a polyurethane elastomer foam, for example, men's shoes, women's shoes, sports shoes, etc.
• a polyurethane elastomer foam for example, men's shoes, women's shoes, sports shoes, etc.
• the sole material of various footwear such as slippers, sandals, and sandals for indoor use, and the materials of various articles such as gloves, work clothes, hats, and masks.
• it is useful for various uses such as packing, hose, seat, cushioning material, cushion, vehicle member, packaging member and the like.
• the shoe sole of the present invention may include the foamed polyurethane molded product in a single layer, or may include the foamed polyurethane molded product in any one of multiple layers.
• the density of the foamed polyurethane molded product is in the range of 0.3 to 1.1 g / cm 3 , preferably in the range of 0.3 to 0.8, more preferably 0.00. It is in the range of 4 to 0.7. If the density of the polyurethane foam layer on the sole is within this range, the performance such as excellent mechanical properties (strength, elasticity), durability, flexibility (flexibility), and comfort will be improved and maintained. Can be made.
• a test piece (length 150 mm ⁇ width 25 mm ⁇ thickness 10 mm) was prepared using the two-component curable foamed polyurethane composition obtained in the examples and comparative examples, and a 2 mm notch was placed in the center of the test piece, 90 degrees. The bending test was repeated, and the flexibility was determined according to the following criteria. Criteria for flexibility. ⁇ (Good): When the growth of the notch is less than 5 mm. X (defect): When notch growth is 5 mm or more or fracture.
• Example 1 Manufacture of two-component curable polyurethane foam composition (P-1) >> In a reaction vessel, 650 parts of 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as “4,4′MDI” as polyisocyanate. Trademark: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) and carbodiimide-modified MDI (trademark: Cosmonate LL) , Manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) was started and stirring was started.
• 4,4′MDI 4,4′-diphenylmethane diisocyanate
• polypropylene glycol (trademark: Exenol 3020, manufactured by Asahi Glass Co., Ltd., hydroxyl value 37) and 80 parts of dipropylene glycol were charged in a divided manner and reacted at 60 ° C. for 8 hours under a nitrogen stream.
• Exenol 820 (trademark: manufactured by Asahi Glass Co., Ltd., having a hydroxyl value of 34) which is polyoxyethylene propylene glycol (B2), and 7.9 parts of ethylene glycol (molecular weight 62.1) which is glycol (B3)
• polytetramethylene glycol (trademark: PTMG-2000, manufactured by Mitsubishi Chemical Corporation, having a hydroxyl value of 56)
• ion-exchanged water as the foaming agent (C)
• catalyst (D) 0.5 parts of triethylenediamine and silicon Y-7006 as a foam stabilizer (trademark: Nippon Unicar Co., Ltd.) Company Ltd.) were blended 0.5 part, thoroughly stirred and mixed to obtain a polyol compound as a curing agent.
• a two-component curable foamed polyurethane composition (P-1) was prepared by stirring and mixing, and 200 g was poured into a mold (290 mm ⁇ 120 mm ⁇ 10 mm) preheated to 40 ° C. After closing the mold, the mold was left at 40 ° C. for 5 minutes, and then the cured foamed molded article was taken out.
• the foam molded product obtained using the two-part curable polyurethane foam composition (P-1) of the present invention has excellent physical properties (oil resistance, hydrolysis resistance, flexibility). Had.
• Example 2 ⁇ Production of two-component curable foamed polyurethane composition (P-2) ⁇ In the same manner as in Example 1, an isocyanate group-terminated urethane prepolymer (A-1) having an NCO equivalent of 250 as the main agent was obtained.
• B1 polycarbonate diol
• Exenol 820 trademark: manufactured by Asahi Glass Co., Ltd., having a hydroxyl value of 34
• B2 polyoxyethylene propylene glycol
• B3 7.9 parts of ethylene glycol as glycol (B3)
• PTMG-2000 Trademark: Mitsubishi Chemical Corporation, hydroxyl value 56
• water (C) as a foaming agent 0.5 parts ion-exchanged water
• catalyst (D) 0.5 parts triethylenediamine
• foam stabilizer As a blend, 0.5 parts of silicon Y-7006 (trademark: manufactured by Nihon Unicar Co., Ltd.) was mixed and stirred thoroughly.
• a polyol compound is agent.
• a two-component curable foamed polyurethane composition (P-2) was prepared by stirring and mixing, and 200 g was poured into a mold (290 mm ⁇ 120 mm ⁇ 10 mm) preheated to 40 ° C. After closing the mold, the mold was left at 40 ° C. for 5 minutes, and then the cured foamed molded article was taken out.
• the foam-molded article obtained using the two-component curable polyurethane foam composition (P-2) of the present invention has excellent physical properties (oil resistance, hydrolysis resistance, flexibility). Had.
• Example 3 Manufacture of two-component curable polyurethane foam composition (P-3) ⁇
• a urethane prepolymer (A-1) having an NCO equivalent of 250 as the main agent was obtained.
• Duranol T-5651 which is polycarbonate diol (B1) (trademark: manufactured by Asahi Kasei Chemicals Corporation, hydroxyl value 112, melting point -5 ° C.
• a two-component curable foamed polyurethane composition (P-3) was prepared by stirring and mixing, and 200 g was poured into a mold (290 mm ⁇ 120 mm ⁇ 10 mm) preheated to 40 ° C. After closing the mold, the mold was left at 40 ° C. for 5 minutes, and then the cured foamed molded article was taken out.
• the foam-molded article obtained using the two-component curable polyurethane foam composition (P-3) of the present invention has excellent physical properties (oil resistance, hydrolysis resistance, flexibility). Had.
• Example 4 Provide of two-component curable foamed polyurethane composition (P-4) ⁇
• a urethane prepolymer (A-1) having an NCO equivalent of 250 as the main agent was obtained.
• B-4 polycarbonate diol (B1) Duranol T-4671 (Trademark: manufactured by Asahi Kasei Chemicals Corporation, hydroxyl value 112, melting point 5 to 15 ° C.) 40 parts, 50 parts of ADEKA polyether CM-294 (trademark: ADEKA Corporation, EO-PO block polymer having a hydroxyl value of 39) which is polyoxyethylene propylene glycol (B2), and glycol (B3) 7.9 parts of ethylene glycol, 21 parts of PTMG-2000 (Trademark: Mitsubishi Chemical Corporation, hydroxyl value 56), 0.5 parts of ion-exchanged water as a foaming agent (C), catalyst (D) As a
• a two-component curable foamed polyurethane composition (P-4) was prepared by stirring and mixing, and 200 g was poured into a mold (290 mm ⁇ 120 mm ⁇ 10 mm) preheated to 40 ° C. After closing the mold, the mold was left at 40 ° C. for 5 minutes, and then the cured foamed molded article was taken out.
• the foam molded product obtained using the two-component curable polyurethane foam composition (P-4) of the present invention has excellent physical properties (oil resistance, hydrolysis resistance, flexibility). Had.
• Example 5 Provide of two-component curable foamed polyurethane composition (P-5) ⁇
• a urethane prepolymer (A-1) having an NCO equivalent of 250 as the main agent was obtained.
• Duranol T-5651 which is polycarbonate diol (B1) (trademark: manufactured by Asahi Kasei Chemicals Corporation, hydroxyl value 112, melting point -5 ° C.
• Exenol 820 (trademark: manufactured by Asahi Glass Co., Ltd., having a hydroxyl value of 34) which is polyoxyethylene propylene glycol (B2), 7.9 parts of ethylene glycol which is glycol (B3), and polytetra 5 parts of a polyol obtained by addition polymerization of ⁇ -caprolactone to methylene glycol (with a lactone addition rate of 20% and a hydroxyl value of 45), 0.5 parts of ion-exchanged water as a foaming agent (C), and a trimethyl as a catalyst (D) 0.5 parts of ethylenediamine and silicon Y-7006 (trademark: Nippon Unicar Co., Ltd.) as a foam stabilizer 0.5 parts (manufactured by the company) was blended and sufficiently stirred and mixed to obtain a polyol compound as a curing agent.
• Exenol 820 trademark: manufactured by Asahi Glass Co., Ltd., having a hydroxyl value of
• a two-component curable foamed polyurethane composition (P-5) is prepared by stirring and mixing. Preheated to 40 ° C., 200 g is poured into a mold (290 mm ⁇ 120 mm ⁇ 10 mm), and immediately After closing the mold, the mold was left at 40 ° C. for 5 minutes, and then the cured foamed molded article was taken out.
• the foamed molded product obtained using the two-component curable polyurethane foam composition (P-5) of the present invention has excellent physical properties (oil resistance, hydrolysis resistance, flexibility). Had.
• Example 6 Manufacture of two-component curable polyurethane foam composition (P-6) >> In the same manner as in Example 1, an isocyanate group-terminated urethane prepolymer (A-1) having an NCO equivalent of 250 as the main agent was obtained.
• a two-component curable foamed polyurethane composition (P-6) was prepared by stirring and mixing, and 200 g was poured into a mold (290 mm ⁇ 120 mm ⁇ 10 mm) preheated to 40 ° C. After closing the mold, the mold was left at 40 ° C. for 5 minutes, and then the cured foamed molded article was taken out.
• the foamed molded product obtained using the two-part curable polyurethane foam composition (P-6) of the present invention has excellent physical properties (oil resistance, hydrolysis resistance, flexibility). Had.
• Example 7 Manufacture of two-component curable polyurethane foam composition (P-7) ⁇
• an isocyanate group-terminated urethane prepolymer (A-1) having an NCO equivalent of 250 as the main agent was obtained.
• Duranol T4672 which is a polycarbonate diol (B1) (trademark: manufactured by Asahi Kasei Chemicals Corporation, hydroxyl value 50.5, melting point 40 to 50 ° C.) 40 parts, 50 parts of Exenol 820 (trademark: manufactured by Asahi Glass Co., Ltd., having a hydroxyl value of 34) as polyoxyethylene propylene glycol (B2), 7 parts of ethylene glycol as glycol (B3), and PTMG-2000 ( Trademarks: Mitsubishi Chemical Corporation, polytetramethylene glycol, number average molecular weight 2000, hydroxyl value 56) 10 parts, water (C) as a blowing agent 0.5 parts ion-exchanged water, catalyst (D) tri 0.5 parts of ethylenediamine and silicon Y-7006 (trademark: Nippon Unicar) as a foam stabilizer Formula Company Ltd.) were blended 0.5 part, sufficient stirring to obtain
• a two-part curable polyurethane foam composition (P-7) was prepared by stirring and mixing, and 200 g was poured into a mold (290 mm ⁇ 120 mm ⁇ 10 mm) preheated to 40 ° C. After closing the mold, the mold was left at 40 ° C. for 5 minutes, and then the cured foamed molded article was taken out.
• the foamed molded article obtained using the two-component curable polyurethane foam composition (P-7) of the present invention has excellent physical properties (oil resistance, hydrolysis resistance, flexibility). Had.
• Ethylene glycol 7.9 parts, PTMG-2000 (trademark: manufactured by Mitsubishi Chemical Corporation, polytetramethylene glycol, number average molecular weight 2000, hydroxyl value 56), water as foaming agent (C ) 0.5 parts of ion-exchanged water, 0.5 parts of triethylenediamine as catalyst (D), and 0.5 parts of silicon Y-7006 (trademark: manufactured by Nihon Unicar Co., Ltd.) as the foam stabilizer. The mixture was stirred and mixed to obtain a polyol compound as a curing agent.
• a two-component curable foamed polyurethane composition (P-8) was prepared by stirring and mixing, and 200 g was poured into a mold (290 mm ⁇ 120 mm ⁇ 10 mm) preheated to 40 ° C. After closing the mold, the mold was left at 40 ° C. for 5 minutes, and then the cured foamed molded article was taken out.
• the foam molded product obtained using the two-component curable urethane foam composition (P-8) was inferior in oil resistance.
• Exenol 820 (trademark: manufactured by Asahi Glass Co., Ltd., having a hydroxyl value of 34) which is polyoxyethylene propylene glycol (B2), 7.9 parts of ethylene glycol which is glycol (B3), and a foaming agent
• B2 polyoxyethylene propylene glycol
• B3 polyoxyethylene glycol
• B3 polyoxyethylene propylene glycol
• B3 polyoxyethylene glycol
• B3 polyoxyethylene propylene glycol
• B3 polyoxyethylene propylene glycol
• B3 polyoxyethylene propylene glycol
• B3 polyoxyethylene propylene glycol
• B3 polyoxyethylene propylene glycol
• B3 polyoxyethylene propylene glycol
• B3 polyoxyethylene propylene glycol
• B3 polyoxyethylene propylene glycol
• B3 polyoxyethylene propylene glycol
• B3 polyoxyethylene propylene glycol
• B3 polyoxyethylene propylene glycol
• D triethylenediamine
• a two-part curable polyurethane foam composition (P-9) was prepared by stirring and mixing, and 200 g was poured into a mold (290 mm ⁇ 120 mm ⁇ 10 mm) preheated to 40 ° C. After closing the mold, the mold was left at 40 ° C. for 5 minutes, and then the cured foamed molded article was taken out.
• the foamed molded product obtained using the two-component curable urethane foam composition (P-9) was inferior in flexibility.
• polyester polyol A having a hydroxyl value of 56.1 mgKOH / g synthesized from ethylene glycol (EG) / 1,4-butylene glycol (1,4BG) and adipic acid (AA) as a polyol.
• EG / 1,4BG 5/5 molar ratio. 445 parts were charged in portions and mixed, and reacted at 60 ° C. for 8 hours under a nitrogen stream to obtain an isocyanate group-terminated urethane prepolymer (A-2) having an NCO equivalent of 250 as the main agent.
• DEG diethylene glycol
• TMP trimethylolpropane
• DEG / TMP 15/1 molar ratio.
• a two-part curable polyurethane foam composition (P-10) was prepared by stirring and mixing, and 200 g was poured into a mold (290 mm ⁇ 120 mm ⁇ 10 mm) preheated to 40 ° C. After closing the mold, the mold was left at 40 ° C. for 5 minutes, and then the cured foamed molded article was taken out. As shown in Table 2, the foamed molded product obtained using the two-component curable urethane foam composition (P-10) was inferior in hydrolysis resistance.
• the mixture was stirred and mixed to obtain a polyol compound as a curing agent.
• a two-component curable foamed polyurethane composition (P-11) was prepared by stirring and mixing, and 200 g was poured into a mold (290 mm ⁇ 120 mm ⁇ 10 mm) preheated to 40 ° C. After closing the mold, the mold was left at 40 ° C. for 5 minutes, and then the cured foamed molded article was taken out.
• the foam-molded article obtained using the two-component curable foamed polyurethane composition (P-11) was inferior in oil resistance.
• B isocyanate group-reactive compound
• a two-component curable foamed polyurethane composition (P-12) was prepared by stirring and mixing, and 200 g was poured into a mold (290 mm ⁇ 120 mm ⁇ 10 mm) preheated to 40 ° C. After closing the mold, it was left at 40 ° C. for 5 minutes. Thereafter, an attempt was made to take out the foamed molded article using the two-component curable foamed polyurethane composition (P-12) from the mold, but the foam collapsed due to insufficient foaming and could not be taken out.
• Duranol T6001 (trademark: manufactured by Asahi Kasei Chemicals Corporation, hydroxyl value 112, melting point 40 to 50 ° C.) which is a polycarbonate diol (B1) as an isocyanate group reactive compound (B-13)
• Exenol 820 (trademark: manufactured by Asahi Glass Co., Ltd., having a hydroxyl value of 34) as polyoxyethylenepropylene glycol (B2), 23 parts of ethylene glycol as glycol (B3), and PTMG-2000 (trademark: 10 parts by Mitsubishi Chemical Corporation, polytetramethylene glycol, number average molecular weight 2000, hydroxyl value 56), 0.5 parts of ion-exchanged water as the foaming agent (C), and triethylenediamine 0 as the catalyst (D) .5 parts, and silicon Y-7006 (trademark: Nippon Unica as a foam stabilizer) It blended Ltd.) 0.5 parts thoroughly stirred to obtain a mixed
• a two-part curable polyurethane foam composition (P-13) was prepared by stirring and mixing, and 200 g was poured into a mold (290 mm ⁇ 120 mm ⁇ 10 mm) preheated to 40 ° C. After closing the mold, the mold was left at 40 ° C. for 5 minutes, and then the cured foamed molded article was taken out.
• the foamed molded product obtained using the two-component curable foamed polyurethane composition (P-13) was inferior in flexibility.
• the two-component curable foamed polyurethane composition of the present invention can provide a foamed polyurethane molded product having no change in the initial molding performance, excellent stability, and excellent oil resistance, hydrolysis resistance, and flexibility (flexibility).
• polyurethane elastomer foam for example, soles of various shoes such as men's shoes, women's shoes, athletic shoes, safety shoes, work shoes, indoor shoes, etc., sole materials of various footwear such as indoor slippers and sandals, sandals, or In addition to the materials of various articles such as gloves, work clothes, hats, masks, etc., they are useful as industrial members in various applications such as rolls, packings, hoses, sheets, cushioning materials, cushions, vehicle members, and packaging members.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)

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• 2013
  • 2013-04-18 WO PCT/JP2013/061505 patent/WO2013179799A1/fr not_active Ceased

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