WO2020129806A1 - Composition de polyol pour le moulage de mousse de polyuréthane souple - Google Patents

Composition de polyol pour le moulage de mousse de polyuréthane souple Download PDF

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Publication number
WO2020129806A1
WO2020129806A1 PCT/JP2019/048707 JP2019048707W WO2020129806A1 WO 2020129806 A1 WO2020129806 A1 WO 2020129806A1 JP 2019048707 W JP2019048707 W JP 2019048707W WO 2020129806 A1 WO2020129806 A1 WO 2020129806A1
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Prior art keywords
polyurethane foam
flexible polyurethane
polyol
foam
molding
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PCT/JP2019/048707
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English (en)
Japanese (ja)
Inventor
石橋圭太
吉井直哉
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東ソー株式会社
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Priority claimed from JP2019156884A external-priority patent/JP7443696B2/ja
Application filed by 東ソー株式会社 filed Critical 東ソー株式会社
Publication of WO2020129806A1 publication Critical patent/WO2020129806A1/fr

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    • 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
    • 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
    • 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
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

Definitions

  • the present invention relates to a polyol composition for molding a flexible polyurethane foam and a flexible polyurethane foam using the composition.
  • Flexible polyurethane foams are widely used in daily necessities, automobile materials, clothing, sports/leisure products, medical materials, civil engineering materials, etc.
  • the hardness felt during initial compression when sitting and the occupant's waist and buttocks during lateral travel are also considered to be It is required to reduce the feeling of wobbling by tilting in the direction.
  • a seat cushion structure having a laminated structure in which a highly elastic polyurethane foam is arranged in an upper layer (seat surface side) and a viscoelastic foam is arranged in a lower layer (bottom surface side) is disclosed (Patent Document 1).
  • the lower layer side viscoelastic foam indirectly gives the occupant a soft fit through the upper layer side high elastic foam, and the upper layer high elasticity foam gives the occupant a cushioning feeling directly.
  • the seating comfort is improved by these synergistic effects, there are problems such as an increase in the number of parts and an increase in the number of steps for integrating the foam by adhesion or the like.
  • Patent Document 2 a technique is disclosed in which the hardness distribution is expressed by changing the density of the sheet for each part.
  • the density must be increased to increase the hardness, which leads to an increase in cost.
  • the main polymerizable group (reactive group) of the crosslinking agent component contained in the polyol composition is an ethylene oxide group, by containing glycerin, and by controlling the shape of the foam cell,
  • Patent Document 3 A technique for expressing hardness distribution even with the same density is disclosed (Patent Document 3).
  • these factors alone are insufficient to develop the hardness distribution that reduces the hardness at the time of initial compression felt at the time of sitting and suppresses the wobble feeling.
  • the present invention has been made in view of the above background art, and a flexible polyurethane foam molding polyol composition having a hardness distribution that provides a comfortable sitting comfort when used as a cushioning material, and a flexible polyurethane foam using the composition.
  • the purpose is to provide.
  • the present invention includes the embodiments described below.
  • a flexible polyurethane foam molding polyol composition comprising a polyol component (A), a catalyst (B), a foam stabilizer (C), a foaming agent (D), and a crosslinking agent (E), which comprises a crosslinking agent ( E) a saccharide (E-1) is contained, and the addition amount of the saccharide (E-1) is 0.1 to 5 mass% with respect to the polyol component (A).
  • Polyol composition for molding polyurethane foam comprising a polyol component (A), a catalyst (B), a foam stabilizer (C), a foaming agent (D), and a crosslinking agent (E), which comprises a crosslinking agent ( E) a saccharide (E-1) is contained, and the addition amount of the saccharide (E-1) is 0.1 to 5 mass% with respect to the polyol component (A).
  • Polyol composition for molding polyurethane foam comprising a polyol component (A), a catalyst (B), a foam stabilizer
  • a total degree of unsaturation of 0.001 to which is produced by using at least one selected from a complex metal cyanide complex catalyst, a phosphazene catalyst, and an imino group-containing phosphazenium salt as a catalyst in the polyol component (A). 0.04 meq. /G of polyoxyalkylene polyol (A-1) is contained, The polyol composition for flexible polyurethane foam molding according to any one of the above [1] to [3].
  • a flexible polyurethane foam molding composition comprising the flexible polyurethane foam molding polyol composition according to any one of the above [1] to [4] and a polyisocyanate component (F), wherein the polyisocyanate is
  • the component (F) contains diphenylmethane diisocyanate in the range of 50 to 85% by mass, and the total amount of 2,2′-diphenylmethane diisocyanate and 2,4′-diphenylmethane diisocyanate contained in the diphenylmethane diisocyanate is equal to the total amount of the diphenylmethane diisocyanate.
  • a flexible polyurethane foam molding composition characterized in that it is 10 to 50 mass %.
  • a two-layer foam in which a flexible polyurethane foam molded such that the upper mold side is the lower surface and the lower mold side is the upper surface is cut out from the end surface on the upper surface side toward the lower surface side at every 45% of the thickness.
  • the polyol composition for molding a flexible polyurethane foam of the present invention it is possible to obtain a flexible polyurethane foam having a hardness distribution that provides a comfortable sitting comfort when used as a cushioning material.
  • the polyol composition for molding a flexible polyurethane foam according to the present invention contains the following polyol component (A), catalyst (B), foam stabilizer (C), foaming agent (D), and crosslinking agent (E).
  • the polyol component (A) is one that is polyadded with the polyisocyanate component (F) to form polyurethane, and in the present invention, it is at least one selected from the group consisting of polyether polyol and polyester polyol. desirable. Further, those having a number average molecular weight of 1,000 to 10,000 and a nominal number of functional groups of 2 or more are more desirable. When the number average molecular weight is less than the lower limit, the flexibility of the resulting foam tends to be insufficient, and when it exceeds the upper limit, the hardness of the foam tends to be lowered. Further, when the number of nominal functional groups is less than 2, there is a possibility that a problem such as deterioration of wet heat compression strain, which is an index of durability, may occur. Incidentally.
  • the nominal number of functional groups refers to the theoretical average number of functional groups (the number of active hydrogen atoms per molecule), assuming that side reactions do not occur during the polymerization reaction of the polyol.
  • polypropylene ether polyol for example, polypropylene ether polyol, polyethylene polypropylene ether polyol (hereinafter referred to as PPG), polytetramethylene ether glycol (hereinafter referred to as PTG), or the like
  • PPG polyethylene polypropylene ether polyol
  • PTG polytetramethylene ether glycol
  • polyester polyol for example, polycondensation can be used.
  • Polyester polyols consisting of adipic acid and a diol, which are type polyester polyols, polycaprolactone polyols such as lactone polyester polyols, and the like can be used.
  • the polyol component (A) is produced by using at least one selected from a complex metal cyanide complex catalyst, a phosphazene catalyst, and an imino group-containing phosphazenium salt as a catalyst.
  • the total unsaturation degree is 0.001 to 0.04 meq. /G of polyoxyalkylene polyol (A-1) is preferably contained.
  • the increase in the total unsaturation degree of the polyol (A-1) means that the monool component having an unsaturated group at the terminal increases, and the total unsaturation degree is 0.04 meq. If it is larger than /g, the durability may be lowered as the cross-linking density of the foam is lowered. In addition, 0.001 meq. If it is less than /g, it takes a long time to produce the polyol, which is not preferable.
  • a polyether polyol having a polyoxyalkylene chain composed of a copolymer of oxyethylene and oxypropylene in the polyol component (A) for the purpose of accelerating the foam breaking of the flexible polyurethane foam. It is preferable to include.
  • the number average molecular weight of the polyether polyol is preferably 4,000 to 8,000, more preferably 6,000 to 8,000. Further, it is preferable that the number of nominal functional groups is 2 to 4.
  • the oxyethylene unit in the polyether polyol is preferably 60 to 90% by mass, more preferably 60 to 80% by mass. By setting the oxyethylene unit to 60 to 90% by mass, the hardness distribution of the foam can be easily obtained, and the durability can be further improved. From the viewpoint of storage stability at low temperatures, the copolymer composed of oxyethylene and oxypropylene is preferably a random copolymer.
  • the amount of the polyether polyol added is preferably 0.5 to 5 mass% with respect to the polyol component (A). If it is less than the lower limit, the moldability of the foam may deteriorate, and if it exceeds the upper limit, the elongation rate of the foam may decrease.
  • the polyol component (A) of the present invention is preferably used in combination with a polymer polyol obtained by polymerizing a vinyl monomer in the polyol by a usual method for the purpose of adjusting hardness.
  • a polymer polyol include those obtained by polymerizing a vinyl-based monomer in a polyalkylene polyol such as PPG in the presence of a radical initiator and stably dispersing it.
  • the vinyl-based monomer include acrylonitrile, styrene, vinylidene chloride, hydroxyalkyl methacrylate and alkyl methacrylate, and of these, acrylonitrile and styrene are preferable.
  • polymer polyols include EL-910 and EL-923 manufactured by AGC, and FA-728R manufactured by Sanyo Kasei.
  • urethanization catalysts known in the art can be used.
  • amine catalysts having active hydrogen such as N,N-dimethylethanolamine and N,N-diethyl
  • the amount of the catalyst added is preferably 0.01 to 10 mass% with respect to the polyol component (A). If it is less than the lower limit, the curing tends to be insufficient, and if it exceeds the upper limit, the moldability may be deteriorated.
  • foam stabilizer (C) an ordinary surfactant is used, and an organosilicon-based surfactant can be preferably used.
  • an organosilicon-based surfactant can be preferably used.
  • Toray Dow Corning SZ-1327, SZ-1325, SZ-1336, SZ-3601, Momentive Y-10366, L-5309, Evonik B-8724LF2, B-8715LF2 and the like. Can be mentioned.
  • the amount of these foam stabilizers added is preferably 0.1 to 3 mass% with respect to the polyol component (A).
  • Water is mainly used as the foaming agent (D). Water reacts with an isocyanate group to form a high-hardness urea group and generates carbon dioxide gas, which allows foaming.
  • an optional foaming agent may be used.
  • a small amount of a low boiling point organic compound such as cyclopentane or isopentane may be used together, or air or nitrogen gas or liquefied carbon dioxide may be mixed and dissolved in the stock solution using a gas loading device to foam.
  • the addition amount of the foaming agent is usually 0.5 to 10% by mass with respect to the polyol component (A), but 3.0 to 6 when a low density flexible polyurethane foam having an apparent density of less than 40 kg/m 3 is obtained. It is preferably 0% by mass, and more preferably 3.0 to 5.5% by mass. If it exceeds the upper limit, foaming may be difficult to stabilize, and if it is less than the lower limit, the density of the foam may not be sufficiently lowered.
  • the cross-linking agent (E) in the present invention contains a sugar (E-1).
  • the saccharide (E-1) preferably contains at least one selected from monosaccharides to decasaccharides, and more preferably contains at least one selected from monosaccharides to hexasaccharides.
  • the monosaccharide is the minimum unit of sugar, and the disaccharide to decasaccharide means each of 2 to 10 monosaccharides dehydrated and condensed to form a glycoside bond to form one molecule.
  • examples of monosaccharides include triose, tetrose, pentose, hexose, heptose, octose, nonose, and decose. These compounds may be aldose or ketose, and dialdose (a compound of a sugar derivative in which both ends of the carbon chain are aldehyde groups, for example, tetraacetylgalactohexodialdose, idhexodialdose, xylopentodose.
  • Aldoses, etc. monosaccharides having a plurality of carbonyl groups (such as aldol alkoketose such as othone and onose), monosaccharides having a methyl group (such as methyl sugars such as altromethylose), acyl groups (especially C2 such as acetyl group) -C4 acyl group and the like) (acetylose of the aldose, for example, acetyl body such as aldehyde glucose pentaacetyl compound), carboxyl group-introduced sugar (sugar acid or uronic acid), lyo sugar , Amino sugar, deoxy sugar and the like.
  • carbonyl groups such as aldol alkoketose such as othone and onose
  • monosaccharides having a methyl group such as methyl sugars such as altromethylose
  • acyl groups especially C2 such as acetyl group
  • Such monosaccharides include, for example, tetrose (erythrose, threorose, etc.), pentose (arabinose, ribose, lyxose, deoxyribose, xylose, etc.), hexose (allose, altrose, glucose, mannose, gulose, idose, galactose, Fructose, sorbose, fucose, rhamnose, talose, galacturonic acid, glucuronic acid, mannuronic acid, glucosamine, etc.) and the like.
  • tetrose erythrose, threorose, etc.
  • pentose arabinose, ribose, lyxose, deoxyribose, xylose, etc.
  • hexose allose, altrose, glucose, mannose, gulose, idose, galactose, Fructose,
  • the monosaccharide may be a cyclic isomer having a cyclic structure formed by a hemiacetal bond.
  • the monosaccharide does not have to have optical activity and may be any of D type, L type and DL type. Further, it may be a crystal or a liquid, and may be a hydrate or may contain water. These monosaccharides can be used alone or in combination of two or more.
  • isomerized liquid sugars that are liquid at room temperature, such as high-fructose liquid sugar, fructose-glucose liquid sugar, glucose-fructose liquid sugar, workability during preparation of the flexible polyurethane foam molding polyol composition, and soft polyurethane foam molding polyol composition It is more preferable in terms of storage stability.
  • disaccharides examples include trehalose (for example, ⁇ , ⁇ -trehalose, ⁇ , ⁇ -trehalose, ⁇ , ⁇ -trehalose, etc.) cozybiose, nigerose, maltose, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose. , Sucrose, palatinose, melibiose, rutinose, primeverose, turanose and the like.
  • trehalose for example, ⁇ , ⁇ -trehalose, ⁇ , ⁇ -trehalose, ⁇ , ⁇ -trehalose, etc.
  • cozybiose nigerose, maltose, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose.
  • Sucrose palatinose, melibiose, rutinose, primeverose, turanose and the like.
  • a room temperature liquid mixture of sugars that are liquid at room temperature and a room temperature liquid mixture with a hydrophilic polyol such as ethylene glycol, diethylene glycol or glycerin. It is more preferable to use as.
  • Trisaccharides to decasaccharides are also generally called oligosaccharides (hereinafter, the trisaccharides to decasaccharides may be referred to as oligosaccharides). Homo-oligosaccharides in which 3 to 10 molecules of monosaccharides are dehydrated and condensed via glycoside bonds. And, at least two or more kinds of 3 to 10 molecules of monosaccharides and/or sugar alcohols are roughly classified into hetero-oligosaccharides dehydrated and condensed via glycoside bonds.
  • the oligosaccharides that can be used in the present invention are preferably trisaccharides to decasaccharides, and more preferably trisaccharides to hexasaccharides.
  • these oligosaccharides may have a cyclic structure, and may be an anhydride or a hydrate. Further, in the oligosaccharide, a monosaccharide and a sugar alcohol may be bound to each other. These oligosaccharides can be used alone or in combination of two or more, and can also be used in combination with monosaccharides, disaccharides and polysaccharides.
  • the oligosaccharide may be an oligosaccharide composition composed of a plurality of sugar components. Even such an oligosaccharide composition may be simply referred to as an oligosaccharide.
  • those that are solid at room temperature are preferably used after being liquefied at room temperature by mixing with other sugars or hydrophilic polyols such as glycerin.
  • trisaccharides examples include homooligosaccharides such as maltotriose, isomaltotriose, panose, and cellotriose; manninotriose, solatriose, melezitose, planteose, gentianose, umbelliferose, lactosucrose, raffinose and the like.
  • tetrasaccharides include homooligosaccharides such as maltotetraose and isomalttetraose; heterooligosaccharides such as stachyose, cellotetraose, scorodose, liquinose, and telolaose having sugar or sugar alcohol attached to the reducing end of panose.
  • pentasaccharides examples include homooligosaccharides such as maltopentaose and isomaltopentaose; and heterooligosaccharides such as pentaose in which a disaccharide is bonded to the reducing end of panose.
  • hexasaccharides examples include homo-oligosaccharides such as maltohexaose and isomalthexaose.
  • cyclic oligosaccharides examples include ⁇ -cyclodextrin (hexasaccharide), ⁇ -cyclodextrin (heptasaccharide), and ⁇ -cyclodextrin (octasaccharide).
  • Oligosaccharide may be a reduced type (maltose type) or a non-reduced type (trehalose type).
  • polysaccharides examples include amylose, amylopectin, glycogen, cellulose, agar, inulin, glucomannan, glycosaminoglycan (mucopolysaccharide), alginic acid, hyaluronic acid, chondroitinic acid, heparin and chitin.
  • Monosaccharides, disaccharides, oligosaccharides and mixtures thereof have ether-modified or ester-modified a part of their hydroxyl groups for the purpose of improving the compatibility with other components of the polyol molding composition and the sugar. May be.
  • the modifiable hydroxyl groups are preferably 30 mol% or less of all the hydroxyl groups.
  • the number average molecular weight of the sugar (E-1) is preferably 180 to 2,500, more preferably 180 to 1,800. If it exceeds the upper limit, foam formability and foam elongation may deteriorate.
  • the average number of sugar chains of the carbohydrate (E-1) is preferably 1.0 or more and 9.0 or less, more preferably more than 1.0 and 9.0 or less, and most preferably 1.5 or more. It is 9.0 or less.
  • the number of sugar chains is the number of linked monosaccharides
  • the average number of sugar chains is the average number of sugar chains of each component contained in the sugar (E-1). If it is less than the lower limit, it is difficult to obtain a sufficient elongation, and if it exceeds the upper limit, the formability of the foam and the elongation of the foam may be deteriorated.
  • the average number of hydroxyl groups in the sugar (E-1) is preferably 0.5 times or more the average number of carbon atoms.
  • the average number of hydroxyl groups is the average number of hydroxyl groups of each component in the sugar (E-1), and the average number of carbon atoms is the carbon number of each component in the sugar (E-1). It is the average of the number of atoms.
  • the amount of the sugar (E-1) added is 0.1 to 5% by mass, preferably 0.1 to 4% by mass, more preferably 0.3 to 4% by mass based on the polyol component (A). It is% by mass. If it is less than the lower limit, it is difficult to obtain the effect of expressing the hardness distribution, and if it exceeds the upper limit, the formability of the foam and the elongation rate of the foam may be deteriorated.
  • an alicyclic glycol is used as a crosslinking agent component other than the sugar (E-1) in the polyol composition for molding a flexible polyurethane foam.
  • at least one cyclic glycol selected from the group consisting of aromatic glycols hereinafter also simply referred to as “cyclic glycol”.
  • the cyclic glycol is a compound having a ring structure, and examples thereof include cyclohexanediol, cyclohexanedimethanol, hydroquinone bis(2-hydroxyethyl)ether, dihydroxydiphenylmethane, bisphenol A hydride, polyoxyethylene bisphenol ether, and polyoxyethylene bisphenol ether. Examples thereof include oxypropylene bisphenol ether. Among these, 1,4-cyclohexanedimethanol and polyoxyethylene bisphenol A ether are preferable from the viewpoint that the resulting flexible polyurethane foam has a high effect of improving the wet heat compression strain.
  • the content of the cyclic glycol is preferably 1.5 to 8% by mass, and more preferably 1.5 to 6% by mass based on the polyol component (A).
  • the polyisocyanate component (F) used for producing the flexible polyurethane foam of the present invention includes 4,4′-diphenylmethane diisocyanate (hereinafter, 4,4′-MDI) and 2,4′-diphenylmethane diisocyanate (hereinafter, 2,4).
  • Diphenylmethane diisocyanate (hereinafter, MDI) such as'-MDI
  • 2,2'-diphenylmethane diisocyanate hereinafter, 2,2'-MDI
  • polyphenylene polymethylene polyisocyanate hereinafter, P-MDI
  • P-MDI polyphenylene polymethylene polyisocyanate
  • various modified products such as the above-mentioned MDI, a mixture of MDI and P-MDI, a urethane modified product, a urea modified product, an allophanate modified product, a nurate modified product, and a burette modified product may be used.
  • the MDI content of the polyisocyanate component (F) according to the present invention is preferably in the range of 50 to 85 mass %. If the MDI content exceeds 85% by mass, the storage stability of the polyisocyanate component at low temperatures and the durability of the resulting flexible polyurethane foam may decrease, while if it is less than 50% by mass, the crosslinking density increases, The elongation of the flexible polyurethane foam may decrease, and it may be difficult to obtain sufficient foam strength.
  • the sum of the content of 2,2'-MDI and the content of 2,4'-MDI (hereinafter referred to as isomer content) is preferably 10 to 50% by mass with respect to the total amount of MDI.
  • the storage stability of the polyisocyanate component at low temperatures may be impaired, and the isocyanate storage location It may be necessary to constantly heat pipes, piping, and foam molding machines.
  • the molding stability of the flexible polyurethane foam may be impaired, and foam collapse may occur during foaming.
  • it exceeds 50% by mass the reactivity is lowered, and there is a possibility that problems such as extension of the molding cycle, increase of the closed cell ratio of the foam and shrinkage after molding may occur.
  • fillers such as calcium carbonate and barium sulfate, flame retardants, plasticizers, colorants, known various additives such as antifungal agents, and auxiliaries as necessary. Can be used.
  • a flexible polyurethane foam can be obtained from the above polyol composition for molding a flexible polyurethane foam and the polyisocyanate component, and has an apparent density of 30 kg/m 3 to 70 kg/m 3 and a skin test piece of 25.
  • a soft polyurethane foam having a% compression hardness of 100 to 350 N/314 cm 2 , an elongation of 100% or more, a rebound resilience of 45 to 75%, and a wet heat compression strain of less than 20% and having a hardness distribution in the foaming direction is suitable. Can be obtained.
  • the flexible polyurethane foam of the present invention reacts with a mixed solution of a polyol component (A), a catalyst (B), a foam stabilizer (C), a foaming agent (D), a crosslinking agent (E), and a polyisocyanate component (F). It is manufactured by foaming.
  • NCO INDEX When NCO INDEX is less than 70, durability is lowered and foaming property is excessively increased, and when it is more than 120, the unreacted isocyanate remains for a long time to extend the molding cycle and delay the high molecular weight during foaming. Foam collapse may occur.
  • a mixed liquid of the polyol component (A), the catalyst (B), the foam stabilizer (C), the foaming agent (D), the crosslinking agent (E), and the polyisocyanate component (F) is used.
  • the method for producing a flexible polyurethane mold foam (hereinafter, soft mold foam), which comprises injecting the undiluted foaming solution into a mold and then foaming and curing the same can be used.
  • the mold temperature at the time of injecting the foaming stock solution into the mold is usually 30 to 80° C., preferably 45 to 65° C. If the mold temperature at the time of injecting the above foaming undiluted solution into the mold is less than 30° C., the production cycle is prolonged due to a decrease in reaction rate, while if it is higher than 80° C., the reaction between the polyol and the isocyanate is If the reaction between water and isocyanate is excessively promoted, the foam may collapse during foaming.
  • the curing time for foaming and curing the above-mentioned foaming undiluted solution is preferably 10 minutes or less, more preferably 7 minutes or less, in consideration of a general flexible mold foam production cycle.
  • the above components can be mixed using a high-pressure foaming machine, a low-pressure foaming machine, etc., as in the case of a normal soft mold foam.
  • the isocyanate component and the polyol component immediately before foaming.
  • Other components can be mixed in advance with the isocyanate component or the polyol component as long as they do not affect the storage stability of the raw material or the change with time of the reactivity.
  • the mixture may be used immediately after mixing, or may be used in an appropriate amount after storage.
  • a foaming device capable of simultaneously introducing more than two components into the mixing section, it is also possible to individually introduce a polyol, a foaming agent, an isocyanate, a catalyst, a foam stabilizer, an additive and the like into the mixing section.
  • the mixing method may be either dynamic mixing for mixing in the machine head mixing chamber of the foaming machine or static mixing for mixing in the liquid feed pipe, or both may be used together.
  • mixing of a gaseous component such as a physical foaming agent and a liquid component is performed by static mixing, and mixing of components that can be stably stored as a liquid is performed by dynamic mixing.
  • the foaming device used in the present invention is preferably a high-pressure foaming device that does not require solvent cleaning of the mixing section.
  • the mixed solution obtained by such mixing is discharged into the mold, foamed and cured, and then demolded.
  • a mold release agent to the mold in advance.
  • a releasing agent usually used in the field of molding and processing may be used.
  • the product after demolding can be used as it is, but it is preferable to break the cell membrane of the foam under compression or under reduced pressure by a conventionally known method to stabilize the appearance and dimensions of the product thereafter.
  • an apparent density of 30 kg/m 3 to 70 kg/m 3 and a 25% compression hardness of the skin-attached foam test piece are 100 to 350 N/314 cm 2 , and the impact resilience is 45 to 75%.
  • a flexible polyurethane foam having a wet heat compression strain of less than 20% can be obtained. Further, the flexible polyurethane foam has a hardness distribution in the foaming direction.
  • the flexible polyurethane foam produced as described above not only has excellent physical properties such as hardness and impact resilience, but also has a hardness distribution in which the hardness increases from the upper surface side to the lower surface side, and therefore has excellent riding comfort. It becomes possible to provide it as a cushion material.
  • the liquid temperature of the mixture (polyol composition) of all raw materials other than the polyisocyanate component was adjusted to 24°C to 26°C, and the polyisocyanate component was adjusted to the liquid temperature of 24°C to 26°C. did.
  • a predetermined amount of polyisocyanate component was added to the polyol composition, mixed for 7 seconds with a mixer (7,000 rpm), and then poured into a mold to foam a flexible polyurethane foam. Then, it was taken out from the mold and the physical properties of the obtained flexible polyurethane foam were measured.
  • the NCO Index in Tables 1 to 4 is the ratio of NCO groups to the number of active hydrogen atoms present in the formulation.
  • Mold temperature 60-70°C Mold shape: 300mm ⁇ 300mm ⁇ 100mm Mold material: Aluminum Cure time: 5 minutes
  • polyoxyethylene polyoxypropylene polyol NEF-728 manufactured by Tosoh Corporation -Polyol 3: Polymer polyol having an average number of functional groups of 3.0 and a hydroxyl value of 24 (mgKOH/g), Exenol EL-923 manufactured by AGC Co.
  • Polyol 4 polyether polyol having an average number of functional groups of 3.0, a hydroxyl value of 24 (mgKOH/g), and an oxyethylene unit of 70% by mass, NEF-729 manufactured by Tosoh Corporation.
  • Polyol 5 polyoxyethylene polyoxypropylene polyol having an average number of functional groups of 4.0, a hydroxyl value of 28 (mgKOH/g), and an oxyethylene unit of 80% by mass, NEF-024 manufactured by Tosoh Corporation.
  • Polyol 6 Polyoxyethylene polyoxypropylene polyol having an average number of functional groups of 4.0, a hydroxyl value of 28 (mgKOH/g), and an oxyethylene unit of 90% by mass, NEF-730 manufactured by Tosoh Corporation.
  • ⁇ Crosslinking agent 1 D-(+)-glucose (Fujifilm Wako Pure Chemical Industries, monosaccharide) -Crosslinking agent 2: D-(-)-fructose (manufactured by Tokyo Chemical Industry Co., Ltd., monosaccharide) -Crosslinking agent 3: D-(+)-sucrose (Tokyo Chemical Industry Co., Ltd., disaccharide) -Crosslinking agent 4: D-(+)-raffinose (Tokyo Chemical Industry Co., Ltd., trisaccharide) -Crosslinking agent 5: high-fructose corn syrup (manufactured by Japan Food Processing Co., mixture of monosaccharides to decasaccharides) -Crosslinking agent 6: ⁇ -cyclodextrin (Tokyo Chemical Industry Co., Ltd., octasaccharide) Cross-linking agent 7: Maltos
  • the hardness distribution measurement sample of the present invention is a flexible polyurethane foam molded with a thickness of 100 mm so that the upper mold side is the lower surface and the lower mold side is the upper surface, and cut from the end surface on the upper surface side toward the lower surface side every 45 mm.
  • the two-layer foam is “upper surface side: 0 mm (upper surface end) to 45.0 mm, lower surface side: 45.0 mm to 90.0 mm”.
  • the pressure plate is a disc having a diameter of 200 mm.
  • the pressure plate is compressed toward the evaluation sample at a speed of 50 mm/min to 25% of the thickness of the evaluation sample. After that, the pressure plate is returned to the initial position at a speed of 50 mm/min.
  • the stress value exerted on the evaluation sample was measured, and this value was defined as 25% compression hardness.
  • this hardness ratio means the hardness ratio of each evaluation sample to the average hardness in the foaming height direction. If the hardness ratio of the upper surface side foam is 50 to 85% when the average value of the 25% compression hardness of the evaluation samples of each of the two layers is 100, it can be said that the foam has a hardness distribution.
  • FT-IR measurement is performed on the above-mentioned two-layer evaluation sample, and the peak height derived from the urea bond observed near the wave number of 1660 cm ⁇ 1 is divided by the peak height derived from the urethane bond observed near the wave number of 1710 cm ⁇ 1.
  • the urea binding ratio was calculated by. That is, the smaller the urea bond ratio, the more suppressed the generation of urea bonds and the harder it is to develop hardness.
  • the measurement sample of the cell anisotropy in the present invention is a flexible polyurethane foam molded with a thickness of 100 mm, which is a four-layer foam "first layer" cut out every 22.5 mm from the end face on the upper surface side to the lower surface side. 0 mm (upper end) to 22.5 mm, second layer: 22.5 mm to 45 mm, third layer: 45 mm to 67.5 mm, fourth layer: 67.5 mm to 90 mm”.
  • the first to fourth layers were divided into four layers.
  • Each of the obtained layers was divided into two equal parts in the vertical direction, and an enlarged image of the central portion (field of view: 3.2 mm ⁇ 3.2 mm) of the cross section was obtained by a microscope.
  • a value obtained by dividing the cell length in the foaming direction by the cell length orthogonal to the foaming direction was obtained for each cell, and the average value of 30 cells was used as the evaluation value of the cell anisotropy.

Abstract

L'invention a pour but de fournir une composition de polyol pour le moulage d'une mousse de polyuréthane souple ayant une telle distribution de dureté de façon à donner une sensation confortable lorsqu'elle est utilisée en tant que matériau de coussin; et une mousse de polyuréthane souple utilisant la composition.　La solution selon l'invention porte sur une composition de polyol pour le moulage d'une mousse de polyuréthane souple, ladite composition de polyol comprenant un composant polyol (A), un catalyseur (B), un stabilisant de mousse (C), un agent moussant (D) et un agent de réticulation (E), caractérisé en ce qu'un glucide (E-1) est contenu en tant qu'agent de réticulation (E) et la teneur du glucide (E-1) est de 0,1 à 5 % en masse par rapport au composant polyol (A).
PCT/JP2019/048707 2018-12-21 2019-12-12 Composition de polyol pour le moulage de mousse de polyuréthane souple WO2020129806A1 (fr)

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WO2000073368A1 (fr) * 1999-06-01 2000-12-07 Solutia Inc. Composition utilisable dans des mousses souples de polyurethane
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JP2008179736A (ja) * 2007-01-26 2008-08-07 Daiei Sangyo Kk 熱硬化性バイオプラスチックバインダー組成物、熱硬化性バイオプラスチック硬化物及び熱硬化性バイオプラスチック硬化物の製造方法
WO2013021871A1 (fr) * 2011-08-05 2013-02-14 旭硝子株式会社 Procédé de fabrication d'une mousse de polyuréthane souple
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JP2001106780A (ja) * 1998-10-20 2001-04-17 Mitsui Chemicals Inc ポリオキシアルキレンポリオール及びその誘導体の製造方法
WO2000073368A1 (fr) * 1999-06-01 2000-12-07 Solutia Inc. Composition utilisable dans des mousses souples de polyurethane
JP2002030129A (ja) * 2000-02-17 2002-01-31 Mitsui Chemicals Inc 微発泡ポリウレタンエラストマー及びその製造方法
JP2008179736A (ja) * 2007-01-26 2008-08-07 Daiei Sangyo Kk 熱硬化性バイオプラスチックバインダー組成物、熱硬化性バイオプラスチック硬化物及び熱硬化性バイオプラスチック硬化物の製造方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021215309A1 (fr) * 2020-04-23 2021-10-28 東ソー株式会社 Composition de polyol pour moulage de mousse de polyuréthane souple, composition pour moulage de mousse de polyuréthane souple, mousse de polyuréthane souple et son procédé de production

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