EP0925317A1 - Procede de production de mousse polyurethanne - Google Patents

Procede de production de mousse polyurethanne

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Publication number
EP0925317A1
EP0925317A1 EP97939231A EP97939231A EP0925317A1 EP 0925317 A1 EP0925317 A1 EP 0925317A1 EP 97939231 A EP97939231 A EP 97939231A EP 97939231 A EP97939231 A EP 97939231A EP 0925317 A1 EP0925317 A1 EP 0925317A1
Authority
EP
European Patent Office
Prior art keywords
polyol
isocyanate
weight
polyether polyol
active hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97939231A
Other languages
German (de)
English (en)
Inventor
Shinji Sumitomo Bayer Urethane Co. Ltd NISHIKAWA
Hiroshi Sumitomo Bayer Urethane Co. Ltd. YOKOTA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumika Covestro Urethane Co Ltd
Original Assignee
Sumitomo Bayer Urethane Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Bayer Urethane Co Ltd filed Critical Sumitomo Bayer Urethane Co Ltd
Publication of EP0925317A1 publication Critical patent/EP0925317A1/fr
Withdrawn legal-status Critical Current

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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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • 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
    • C08G18/6552—Compounds of group C08G18/63
    • C08G18/6558—Compounds of group C08G18/63 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
    • 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
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine 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
    • C08G2110/00—Foam properties
    • C08G2110/0016—Foam properties semi-rigid
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3
    • 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
    • C08G2125/00—Compositions for processes using internal mould release agents

Definitions

  • the present invention relates to a method of producing a semi-rigid polyurethane foam having microcell, a density of 0.3 to 0.9 g/cm 3 by a reaction injection molding process in a short time, efficiently.
  • the semi-rigid polyurethane foam having microcell has excellent touch and elasticity and can be used in an armrest, a steering wheel, a console cover, a change knob, etc. of the vehicle.
  • a semi-rigid polyurethane foam is produced by adding a blowing agent to a polyisocyanate, a comparatively high-molecular weight compound having at least two hydrogen atoms capable of reacting with an isocyanate group (active hydrogen equivalent: 1000 or more, hereinafter referred to as a "polyol”), a mostly difunctional low-molecular weight cross-linking agent having an active hydrogen equivalent of 150 or less and a catalyst, and pouring the resulting mixture into a mold capable of closing by a high-pressure polyurethane foaming machine.
  • a blowing agent to a polyisocyanate
  • a comparatively high-molecular weight compound having at least two hydrogen atoms capable of reacting with an isocyanate group active hydrogen equivalent: 1000 or more, hereinafter referred to as a "polyol”
  • a mostly difunctional low-molecular weight cross-linking agent having an active hydrogen equivalent of 150 or less and a catalyst
  • the reaction mixture is foamed, expanded and cured in the mold, and then removed as a polyurethane molded article.
  • the mold is made of a material having high thermal conductivity so as to control the reaction temperature.
  • a mold made of a metal hereinafter referred to as a "mold”
  • a mold made of a resin is used.
  • chlorofluorocarbon hereinafter referred to as "CFC"
  • CFC-11 trichlorofluoromethane
  • a dense surface layer could be obtained by utilizing the fact that an increase in temperature due to urethane reaction heat varies from the portion in contact with the mold to the inside of the molded article, and the increase in temperature and the reaction of the portion in contact with the mold are slower than those of the inside of the product.
  • the present invention relates to a method of producing a semi-rigid polyurethane foam having microcell, a density of 0.3 to 0.9 g/cm 3 and excellent wear resistance by a reaction injection molding process, from a polyisocyanate, and a mixture comprising a polyol, a catalyst, a blowing agent, and optionally a cross-linking agent, an internal mold release agent, a reinforcing agent and an other aid, without using fluorinated hydrocarbon as a blowing agent.
  • a trifunctional polyol having an active hydrogen equivalent of 300 to 1000 in the present invention is handled easily because the viscosity is lower than that of a conventional polyol, and is superior in mixing property with an isocyanate and, therefore, defects such as crack, fracture, etc. in the molded article caused by the insufficient miscibility are remarkably improved.
  • the present invention provides a method of producing a semi-rigid polyurethane foam having microcell, a density of 0.3 to 0.9 g/cm 3 and Shore A hardness of 40 to 90 by a reaction injection molding process, from an isocyanate, and a polyol mixture comprising a polyether polyol, a cross-linking agent, a catalyst, a blowing agent, and optionally an internal mold release agent, a reinforcing agent and an other aid, characterized in that (A) the isocyanate contains a polyisocyanate having functionality of at least three and the content of the polyisocyanate having functionality of at least three is at least 5% by weight based on the isocyanate,
  • a trifunctional polyether polyol having an active hydrogen equivalent of 300 to 1 , 000 and an ethylene oxide content of 5 to 30% by weight is contained in an amount of at least 40% by weight based on the total polyether polyol, and the total polyether polyol has an average active hydrogen equivalent of 500 to 1 , 200 and a viscosity of 200 to 800 mPa «s/25 ⁇ C,
  • Examples of the isocyanate used in the present invention include diphenylmethane diisocyanate, polymethylenepolyphenyl polyisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophoronediicyanate, a modified polyisocyanate obtained by urethane-modifying, carbodiimide-modifying, isocyanurate-modifying or allophanate-modifying them or a mixture thereof .
  • diphenylmethane diisocyanate diphenylmethane diisocyanate, polymethylenepolyphenyl polyisocyanate, a modified polyisocyanate thereof or a mixture thereof is preferred.
  • the polyisocyanate having functionality of at least three include polymethylenepolyphenyl polyisocyanate and uretoneimine-modified diphenylmethane diisocyanate.
  • a desirable another type of a polyisocyanate includes a derivative of hexamethylene diisocyanate. In this case, there can be obtained a molded article which is superior in both weathering resistance and wear resistance.
  • an isocyanurate modified compound of hexamethylene diisocyanate is preferred. It is more preferred in view of high productivity that a content of the isocyanurate modified compound is not less than 50% by weight based on the whole isocyanate.
  • An amount of the polyisocyanate having functionality of at least three may be not less than 5% by weight, particularly not less than 10% by weight, within the range where the molded article is not drastically brittle, e.g. not less than 70% by weight, based on the whole isocyanate.
  • a content of NCO in the polyisocyanate is preferably from 17 to 29% by weight, particularly from 20 to 25% by weight .
  • a viscosity of the isocyanate is preferably from 200 to 1200 mPa-s/25°C.
  • the polyether polyol may be a polyol having 2 to 6 hydroxyl groups in the molecule and an average hydroxyl equivalent of 100 to 3,000, which is produced by adding an alkylene oxide (e.g. ethylene oxide, propylene oxide, etc . ) to a hydroxyl group-containing compound (e.g. propylene glycol, diethylene glycol, glycerine, trimethylolpropane , pentaerythritol, sorbitol, sucrose, etc . ) , a compound having an amino group and a hydroxyl group (e.g. triethanolamine, diethanolamine, etc.) or an amino group-containing compound (e.g.
  • an alkylene oxide e.g. ethylene oxide, propylene oxide, etc .
  • a hydroxyl group-containing compound e.g. propylene glycol, diethylene glycol, glycerine, trimethylolpropane , pentaerythritol, sorb
  • an amount of a polyether polyol having a hydroxyl equivalent of more than 1,500 used is preferably not larger than 30% by weight, particularly not larger than 20% by weight.
  • polyester polyol obtained by reacting polycarboxylic acid with a low-molecular weight hydroxyl group-containing compound, a polycarbonate polyol obtained by ring opening polymerization of caprolactone or a polyether polyamine which is obtained by aminating a hydroxyl group of a polyether polyol or by hydrolyzing an isocyanate prepolymer of a polyether polyol (these polyols have an average active hydrogen equivalent of 100 to 3,000).
  • a polyether polyol namely, a trifunctional polyether polyol
  • a trifunctional polyether polyol having an active hydrogen equivalent of 300 to 1,000, which is produced by adding propylene oxide and ethylene oxide to a trifunctional alcohol or alkanolamine (e.g. glycerine, trimethylolpropane, triethanolamine, etc.) in an amount of at least 40% by weight based on the total amount of the polyols.
  • a trifunctional alcohol or alkanolamine e.g. glycerine, trimethylolpropane, triethanolamine, etc.
  • an amount of ethylene oxide based on the trifunctional polyether polyol is from 5 to 30% by weight.
  • An amount of ethylene oxide is preferably from 5 to 25% by weight, more preferably from 10 to 25% by weight.
  • An amount of the polyether polyol having an active hydrogen equivalent of 300 to 1,000 is preferably not less than 50% by weight, particularly not less than 70% by weight, based on the whole polyether polyol.
  • the average active hydrogen equivalent of the polyether polyol is preferably from 500 to 1,200, particularly from 500 to 700.
  • a tertiary amine e.g. triethylenediamine, pentamethyldiethylenetriamine, 1, 8-diazabicyclo-5,4,0-undecene-7, dimethylaminoethanol, tetramethylethylenedia ine, dimethylbenzylamine, tetramethylhexamethylenediamine, bis( 2-dimethylaminoethyl )ether, etc.
  • an organic metal compound e.g. dibutyltin dilaurate, dibutyltin dimercaptide, tin octanoate, dibutyl diacetate, etc.
  • a carbon dioxide adduct of a primary or secondary amine compound having an amino group such as polyamine (e.g. ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, etc.) or alkanolamine (e.g. ethanolamine, N-methylethanolamine, diethanolamine, isopropanolamine, diisopropanolamine, etc.) (Japanese Patent Kokai Publication No. 113150/1983) is preferably used.
  • the blowing agent can be easily synthesized in a comparatively short time when the amine compound is heated to 30 to 110"C, preferably 50 to 80°C and carbon dioxide of 1 to 5 bar is blown with stirring slowly.
  • An amount of the carbon dioxide adduct is- preferably from 2 to 10 parts by weight based on 100 parts by weight of the polyol mixture.
  • Another blowing agent which is preferable for use is formic acid.
  • An amount of formic acid is preferably from 0.4 to 2.0 parts by weight based on 100 parts by weight of the polyol mixture. It is necessary that formic acid is neutralized with a tertiary amine catalyst and an organic weak base containing active hydrogen (whose equivalent is larger than that of formic acid ) in a blend polyol component and the pH of the polyol mixture is not less than 8.0. When the degree of neutralization is insufficient, a molding machine sometimes causes a problem because of corrosiveness of formic acid.
  • blowing agent a low-boiling point hydrocarbon, a fluorinated hydrocarbon blowing agent, a nitrogen gas, air, etc. may be used in combination as the blowing agent.
  • an amount of water must be not larger than 0.8% by weight, preferably not larger than 0.5% by weight, based on the polyol mixture. If the amount is larger than 0.8% by weight, when the molded article is removed from the mold in a short time, the foam expands and crack arises, which results in decrease in productivity of the polyurethane foam.
  • a dihydric alcohol having a molecular weight of 61 to 200 e.g. ethylene glycol, propylene glycol, butanediol, 1, 3-butanediol, hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, etc.
  • a diamine e.g.
  • diethyltoluenedia ine, t-butyltoluenediamine, diethylaminobenzene, triethyldiaminobenzene, tetraethyldiaminodiphenylmethane, etc. are optionally used, and polyether polyols prepared by adding an alkylene oxide to them can also be used (cf. Japanese Patent Kokoku Publication Nos. 17359/1979 and 34527/1989, Japanese Patent Kokai Publication No. 74325/1982, Japanese Patent Kokoku Publication No. 47726/1988, etc.).
  • An amount of the cross-linking agent is preferably from 2 to 20 parts by weight based on 100 parts by weight of the polyether polyol .
  • the internal mold release agent there can optionally be used a mixture of a carboxylic acid metal salt and an amine (Japanese Patent Kokoku Publication No. 52056/1988), a reaction product of a polysiloxane and an isocyanate (Japanese Patent Kokoku Publication No. 1139/1983), a mixture of an amine, an aliphatic carboxylate salt and a carboxylate ester ( Japanese Patent Kokoku Publication No. 42091/1980), a hardened castor oil (Japanese Patent Kokoku Publication No. 20925/1992), a transesterification product of an aliphatic polyester and a lower alkyl acetoacetate (Japanese Patent Kokai Publication No. 155969/1993), etc.
  • the reinforcing agent examples include a glass, inorganic or mineral fiber (e.g. milled glass fiber, wollastonite fiber, processed mineral fiber, etc. ) or a flake (e.g. mica, glass flake, etc.), and they are optionally used.
  • the foam can also be obtained by previously setting a glass mat, a glass cloth, etc. in a mold and pouring raw materials thereon.
  • a foam stabilizer e.g. silicone surfactant, surfactant, etc.
  • a weathering agent e.g. antioxidant, etc.
  • an UV absorber e.g.
  • 2, 6-di-t-butyl-4-methylphenol, tetrakis [methylene 3-( 3 ' , 5 ' -di-t-butyl-4 ' -hydroxyphenyl )propionate] methane, a colorant, etc. may optionally be used.
  • a reaction injection molding machine e.g. a high-pressure polyurethane foaming machine manufactured by Hennecke Co., a high-pressure polyurethane foaming machine for R-RIM manufactured by Polyurethane Engineering Co., etc.
  • a NCO index is within the range from 100 to 115.
  • the wear resistance is drastically deteriorated.
  • the NCO index exceeds 115, the molded article is too soft at the time of removing from the mold and the molded article is liable to expand, which results in drastic deterioration of the- productivit .
  • the distance between portions into which a premolded horn pad is fit was measured.
  • the portion corresponding to the root of a spoke has a large cross sectional area and, when this portion expands after removing from the mold, the distance between the root parts of the spoke to which the horn pad is mounted becomes short and it becomes impossible to mount the horn pad.
  • the tensile strength was measured according to JIS K-6301.
  • the wear resistance was determined by vertically putting a No. 6 or No. 10 canvas (of 45 mm in width) having a weight of 100 g at the end over a molded article having a diameter of 28 mm, rubbing the upper surface under the condition of a stroke of 80 cm and a speed of 60 times/minute and measuring the number of times until a scratch is formed on the surface of the molded article.
  • Reference Example 1 Monoethanolamine (2.39 kg), N-methylethanolamine
  • polyol A polyether polyol having an OH value of 56 mg KOH/g (active hydrogen equivalent: 1 , 000 ) , which is prepared by adding propylene oxide and ethylene oxide in a weight ratio of 87:13 to glycerine, 6.6 parts of ethylene glycol, 3.2 parts of the amine compound obtained in Reference Example 1, 0.6 parts of a 33% ethylene glycol solution of triethylenediamine and 0.05 parts of dibutyltin dilaurate were mixed to obtain 20 kg of a polyol mixture.
  • the property of polyol A is shown in Table I .
  • Polymethylenepolyphenyl polyisocyanate (7.8 kg) containing 5% by weight of a polynuclear material was mixed with modified diphenylmethane diisocyanate (6 kg) containing 28% by weight of uretoneimine and the mixture was heated to 50°C.
  • 6.2 kg of a polyether polyol (polyol D) having an OH value of 28 mg KOH/g (active hydrogen equivalent: 2,000), which was prepared by adding propylene oxide and ethylene oxide (a weight ratio of propylene oxide to ethylene oxide 97/13) to glycerine, was slowly added, followed by maintaining at 80°C for 3 hours.
  • a content of an isocyanate group was 21.0% (isocyanate A).
  • the property of isocyanate A is shown in Table II.
  • the respective raw materials were charged in a tank of a high-pressure polyurethane foaming machine (HK-100, manufactured by Hennecke Co . ) and then poured into an steel mold for vehicle handle warmed to 55°C under the conditions of a mixing ratio of 100:82.8 (weight ratio), a NCO index of 105, a discharge amount of 200 g/second, a mixing pressure of 160 kg/cm 2 , an injection time of 2.25 seconds .
  • HK-100 high-pressure polyurethane foaming machine
  • the foam was removed after 60 seconds from the beginning of the pouring of the raw materials into the mold, and then (a) the moldability, (b) the distance between arms, (c) the physical properties and (d) the wear resistance were measured.
  • Example 3 In the same manner as in Example 1 except for using the same isocyanate as in Example 1 under the conditions of a mixing ratio of 100:94.9 (weight ratio), a NCO index of 105, a discharge amount of 200 g/second, a mixing pressure of 180 kg/cm 2 and an injection time of 2.25 seconds, a molded article was prepared and then evaluated. The results are shown in Table III.
  • Example 3
  • Example 2 In the same manner as in Example 1 except that the polyol mixture shown in Example 2 was mixed with polymethylenepolyphenyl polyisocyanate (8.2 kg) containing 5% by weight of a polynuclear material and modified diphenylmethane diisocyanate (6.4 kg) containing 28% by weight of uretoneimine and the mixture was heated to 50°C.
  • Example 3 In the same manner as in Example 3 except for using the same raw materials as in Example 3 under the conditions of the mixing ratio of 100:99.4 (weight ratio) and the NCO index of 110, a molded article was prepared and then evaluated.
  • Example 2 In the same manner as in Example 1 except for replacing 45 parts out of 90 parts of the polyether polyol (polyol A) used in Example 1 having an OH value of 56 mg KOH/g (active hydrogen equivalent: 1,000), which was prepared by adding propylene oxide and ethylene oxide in a weight ratio of 87:13 to glycerine, with a polyether polyol (polyol F) having an OH value of 112 mg KOH/g
  • polyether polyol having an OH value of 92 mg KOH/g (active hydrogen equivalent: 610), which was prepared by adding propylene oxide and ethylene oxide in a weight ratio of 87:13 to glycerine, 6.6 parts of ethylene glycol, 0.5 parts of formic acid, 1.5 parts of diethanolamine, 0.6 parts of a 33% ethylene glycol solution of triethylenediamine and 0.05 parts of dibutyltin dilaurate were mixed to obtain 20 kg of a polyol mixture.
  • Example 2 In the same manner as in Example 1 except for using this polyol mixture in combination with isocyanate A under the conditions of the mixing- ratio of 100:88.1 (weight ratio) and the NCO index of 105, a molded article was prepared and then evaluated.
  • polyether polyol having an OH value of 92 mg KOH/g (active hydrogen equivalent: 610), which is prepared by adding propylene oxide and ethylene oxide in a weight ratio of 87:13 to glycerine, 6.6 parts of 1, 3-butanediol, 3.2 parts of the amine compound obtained in Reference Example 1 and 0.5 parts of dibutyltin dilaurate were mixed to obtain 20 kg of a polyol mixture.
  • Example 8 In the same manner as in Example 1 except for using this polyol mixture in combination with Desmodur TPLS2025/1 (isocyanate C, manufactured by Bayer AG), which is prepared by isocyanurate-modifying hexamethylene diisocyanate, under the conditions of the mixing ratio of 100:70.1 (weight ratio) and the NCO index of 105, a molded article was prepared and then evaluated. The results are shown in Table III.
  • Example 9 In the same manner as in Example 1 except for using this polyol mixture in combination with isocyanate E, which was prepared by mixing- an experimental product (isocyanate D) of a low-viscosity isocyanurate modified material prepared by partially allophanate-modifying hexamethylene diisocyanate with isocyanate C used in Example 7 in a ratio (isocyanate D : isocyanate C) of 30:70, under the conditions of the mixing ratio of 100:81.3 (weight ratio) and the NCO index of 105, a molded article was prepared and then evaluated. The results are shown in Table III.
  • Example 9 Example 9
  • Example 8 In the same manner as in Example 1 except for replacing 45 parts out of 90 parts of the polyether polyol (polyol B) used in Example 8 having an OH value of 92 mg KOH/g (active hydrogen equivalent: 610), which was prepared by adding propylene oxide and ethylene oxide in a weight ratio of 87:13 to glycerine, with a polyether polyol (polyol H) having an OH value of 112 mg KOH/g
  • Comparative Example 1 In the same manner as in Example 1 except for replacing 90 parts of the polyether polyol (polyol A) used in Example 1 having an OH value of 56 mg KOH/g (active hydrogen equivalent: 1,000), which was prepared by adding propylene oxide and ethylene- oxide in a weight ratio of 87:13 to glycerine, with 90 parts of a polyether polyol (polyol D) having an OH value of 28 mg KOH/g (active hydrogen equivalent: 2,000) and using the polyether polyol in combination with isocyanate A under the conditions of the mixing ratio of 100:73.4 (weight ratio) and the NCO index of 105, a molded article was prepared and then evaluated.
  • Example 3 In the same manner as in Example 1 except for replacing 90 parts of the polyether polyol used in Example 1 having an OH value of 56 mg KOH/g (active hydrogen equivalent : 1 , 000 ) , which was prepared by adding propylene oxide and ethylene oxide to glycerine in a weight ratio of 87:13, with 90 parts of a polyether polyol (polyol E) having an OH value of 35 mg KOH/g (active hydrogen equivalent: 1,600) and using the polyether polyol in combination with isocyanate A under the conditions of the mixing ratio of 100:75.8 (weight ratio) and the NCO index of 105, a molded article was prepared and then evaluated. The results are shown in Table III.
  • Example 7 In the same manner as in Example 1 except for replacing 90 parts of the polyether polyol used in Example 7 having an OH value of 92 mg KOH/g (active hydrogen equivalent: 610), which was prepared by adding propylene oxide and ethylene oxide in a weight ratio of 87:13 to glycerine, with 90 parts of a polyether polyol (polyol G) having an OH value of 28 mg KOH/g ( active hydrogen equivalent: 2,000) , which was prepared by adding propylene oxide and ethylene oxide in a weight ratio of 80:20 to propylene glycol, and using the polyether polyol in combination with isocyanate C under the conditions of the mixing ratio of 100:50.9 (weight ratio) and the NCO index of 105, a molded article was prepared and then evaluated.
  • Comparative Example 5 In the same manner as in Example 1 except for replacing 90 parts of the polyether polyol used in Example 1 having an OH value of 56 mg KOH/g (active hydrogen equivalent: 1,000), which was prepared by adding propylene oxide and ethylene oxide in a weight ratio of 87:13 to glycerine, with 90 parts of a polyether polyol (polyol C) having an OH value of 178 mg KOH/g (active hydrogen equivalent: 315) and using the polyether polyol in combination with isocyanate C under the conditions of the mixing ratio of 100:124 (weight ratio) and the NCO index of 105, a molded article was prepared and then evaluated. The results are shown in Table III. Comparative Example 6
  • Example 3 In the same manner as in Example 1 except for using the same raw materials as in Example 3 under the conditions of the mixing ratio of 100:81.3 (weight ratio) and the NCO index of 90, a molded article was prepared and then evaluated.
  • Example 3 In the same manner as in Example 1 except for using the same raw materials as in Example 3 under the conditions of the mixing ratio of 100:108 (weight ratio) and the NCO index of 120, a molded article was prepared and then evaluated.
  • Viscosity 400 450 1,000 200 650 (mPa- s/25°C)
  • the present invention it is possible to demold a low-density semi-rigid polyurethane foam having excellent wear resistance in a short time.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

On peut préparer une mousse polyuréthanne semi-rigide de faible densité présentant une excellente résistance à l'usure, laquelle est démoulée en un temps court, selon un procédé consistant à introduire une mousse polyuréthanne présentant des microcellules et une densité comprise entre 0,3 et 0,9/cm3 par moulage par injection par réaction, à partir d'un polyisocyanate et d'un mélange de polyol contenant un polyol, un catalyseur, un agent gonflant et facultativement un agent de réticulation, un agent de décollement du moule interne, un agent de renforcement et un autre auxiliaire caractérisé en ce qu'un polyol de polyéther trifonctionnel présentant un équivalent hydrogène actif compris entre 300 et 1000 et une teneur en oxyde d'éthylène comprise entre 5 et 30 % en poids est contenu en une quantité d'au moins 40 % en poids basé sur le polyol de polyéther, le polyol de polyéther présentant un équivalent hydrogène actif moyen compris entre 500 et 1200 et une viscosité comprise entre 200 et 800 mPa.s/25 °C.
EP97939231A 1996-09-10 1997-09-09 Procede de production de mousse polyurethanne Withdrawn EP0925317A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP23908196 1996-09-10
JP8239081A JP2892626B2 (ja) 1996-09-10 1996-09-10 ポリウレタン発泡体の製造法
PCT/JP1997/003169 WO1998011148A1 (fr) 1996-09-10 1997-09-09 Procede de production de mousse polyurethanne

Publications (1)

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EP0925317A1 true EP0925317A1 (fr) 1999-06-30

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EP97939231A Withdrawn EP0925317A1 (fr) 1996-09-10 1997-09-09 Procede de production de mousse polyurethanne

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EP (1) EP0925317A1 (fr)
JP (1) JP2892626B2 (fr)
KR (1) KR20000038036A (fr)
BR (1) BR9711728A (fr)
CA (1) CA2265641A1 (fr)
WO (1) WO1998011148A1 (fr)

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Also Published As

Publication number Publication date
JP2892626B2 (ja) 1999-05-17
CA2265641A1 (fr) 1998-03-19
JPH1087779A (ja) 1998-04-07
BR9711728A (pt) 1999-08-24
WO1998011148A1 (fr) 1998-03-19
KR20000038036A (ko) 2000-07-05

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