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
  • C08G18/70—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
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • 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
• • 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
  • C08G2110/0008—Foam properties flexible
• • 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
  • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2205/00—Foams characterised by their properties
  • C08J2205/06—Flexible foams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes

Definitions

• the present invention relates to a flexible polyurethane foam, and more particularly to a flexible polyurethane foam that can be suitably used for a vehicle seat back and a vehicle seat cushion.
• a polyhydroxyl compound, an organic polyisocyanate, a catalyst, a foam stabilizer, a foaming agent (water) and an additive can be used as a method for producing a flexible polyurethane foam excellent in foam physical properties, moldability and surface curing properties.
• a method of using toluene diisocyanate as an isocyanate component has already been widely known as a flexible polyurethane foam (Patent Document 1).
• the freezing point of toluene diisocyanate is as high as about 17 ° C. under normal pressure, and it needs to be kept warm and controlled to solidify in winter.
• the health condition of workers due to toluene diisocyanate may be a problem.
• Patent Document 2 a flexible polyurethane foam using diphenylmethane diisocyanate having a low vapor pressure as a polyisocyanate component has also been proposed (Patent Document 2).
• the freezing point of 4,4′-diphenylmethane diisocyanate which is the main component of conventional diphenylmethane diisocyanate, is about 38 ° C. under atmospheric pressure, which is higher than that of toluene diisocyanate, and requires pretreatment such as prepolymerization. Since the viscosity is very high, there are problems such as poor workability and limitations due to production equipment conditions.
• an MDI isocyanate for flexible polyurethane foam an organic polyisocyanate modified with a polyol is used which has an isomer ratio and a high amount of pure MDI (hereinafter referred to as di-content) in all isocyanates (pure MDI and polymeric MDI).
• di-content a high amount of pure MDI
• pure MDI and polymeric MDI pure MDI and polymeric MDI
• the present invention has been made in view of the above-described problems of the prior art, and an object thereof is to provide a method for producing a flexible polyurethane foam having low density, strong mechanical properties, and durability as a vehicle cushion and seat back.
• the present inventors contain an organic polyisocyanate (A), a polyol (B), a chain extender (C), a catalyst (D) and a foaming agent (E).
• A organic polyisocyanate
• B polyol
• C chain extender
• D catalyst
• E foaming agent
• the flexible polyurethane foam of this invention and its manufacturing method are as follows.
• a flexible polyurethane foam obtained by reactive foaming of a mixed liquid containing an organic polyisocyanate (A), a polyol (B), a chain extender (C), a catalyst (D) and a foaming agent (E),
• the core density of the flexible polyurethane foam is in the range of 25 to 35 kg / m 3
• the organic polyisocyanate (A) is 70 to 90% by mass with respect to 100% by mass of the organic polyisocyanate (A).
• the diphenylmethane diisocyanate (A-1) has 50 to 90% of 2,4-diphenylmethane diisocyanate and 2,2-diphenylmethane diisocyanate, has an NCO content of 32% or more and a chlorine ion concentration of 5 ppm or less.
• the flexible polyurethane foam as described in (1) above.
• the polyol (B) has a nominal average functional group number in the range of 2 to 4 and a number average molecular weight in the range of 3000 to 8000.
• Core density is 25 to 35 kg / m 3
• wet heat compression set is 25% or less
• elongation is 100% or more
• tear strength is 4.5 N / cm 2 or more
• 25% compression stress is 80 to 120N
• the flexible polyurethane foam as described in any one of (1) to (3) above, (5) The method for producing a flexible polyurethane foam according to any one of (1) to (4).
• the flexible polyurethane foam in the present invention uses only an environmentally friendly tail pure MDI / polymeric MDI as an isocyanate raw material, a core density of 25 to 35 kg / m3, a wet heat compression set of 25% or less, an elongation of 100% or more, and a tear. It has physical properties of a strength of 4.5 N / cm 2 or more and a 25% compressive stress of 80 to 120 N. As a result, it is possible to obtain a vehicle seat cushion and a seat back flexible polyurethane foam that have good ride comfort and can withstand fogling.
• the flexible polyurethane foam of the present invention is a flexible polyurethane obtained by reaction foaming of a mixed solution containing an organic polyisocyanate (A), a polyol (B), a chain extender (C), a catalyst (D) and a foaming agent (E).
• a core density of the flexible polyurethane foam is in a range of 25 to 35 kg / m 3, and the organic polyisocyanate (A) is 70% based on 100% by mass of the organic polyisocyanate (A). It contains ⁇ 90% by mass of diphenylmethane diisocyanate (A-1) and 10 to 30% by mass of polymethylene polyphenylene polyisocyanate (A-2). Further, the diphenylmethane diisocyanate (A-1) is characterized by having 50 to 100% of 2,4-diphenylmethane diisocyanate and 2,2-diphenylmethane diisocyanate. *
• the isocyanate group content (NCO content) in such organic polyisocyanate (A) is in a range of 32% by mass or more.
• NCO content is in a range of 32% by mass or more.
• the content of the isomer MDI is required to be 50 to 100% by mass, more preferably 55 to 100% by mass, and particularly preferably 55 to 65% by mass. . *
• the resulting flexible urethane foam has a high 25% compressive stress, and the wet heat compressive strain exceeds 25%, making it unsuitable as a flexible polyurethane foam. Further, if the content of the isomer MDI exceeds 90% by mass, the wet heat compression strain exceeds 25%, and therefore it is preferably 90% by mass or less.
• the synthesis method for reacting the diphenylmethane diisocyanate and the polyoxyethylene polyoxypropylene polyol is not particularly limited, and is a method of pre-polymerizing MDI and polyol in a total amount, by reacting a part of MDI with the polyol. A method of mixing the remaining MDI can be applied.
• isocyanates can also be used in combination for the purpose of flowability, hardness, foaming speed adjustment and the like.
• aromatic diisocyanates such as o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5.
• -Diisocyanates such as aliphatic diisocyanates such as pentane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, and the like, biuret modified products of these diisocyanates, isocyanurates Examples include modified products, uretonimine modified products, carbodiimide modified products, and polyol modified products. *
• the polyol (B) according to the present invention is not particularly limited, but is a polyether having a nominal average functional group number of 2 to 6 and a number average molecular weight of 3,000 to 8,000, which easily develops physical properties as a flexible polyurethane foam. Those mainly composed of polyol are preferred. *
• polyether polyols known ones can be used. For example, ethylene oxide, propylene oxide using low molecular weight polyols having a number average molecular weight of less than 700, low molecular weight polyamines, low molecular weight amino alcohols and the like as initiators. And those obtained by adding a cyclic ether such as tetrahydrofuran.
• Such initiators include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-butanediol, Pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1 , 3-hexanediol, 2-n-hexadecane-1,2-ethylene glycol, 2-
• Such polyether polyols are water; polyols such as propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol; amino alcohols such as diethanolamine, triethanolamine, tripropanolamine; or ethylenediamine, It can also be obtained by subjecting amines such as 1,6-hexanediamine, triethylenetetraamine, aniline, toluylenediamine, and methylenebisaniline to ring-opening addition or random addition of ethylene oxide, propylene oxide, and the like.
• amines such as 1,6-hexanediamine, triethylenetetraamine, aniline, toluylenediamine, and methylenebisaniline to ring-opening addition or random addition of ethylene oxide, propylene oxide, and the like.
• a polymer polyol produced by polymerizing a vinyl monomer in a polyol by an ordinary method can be further used in combination.
• examples of such a polymer polyol include those obtained by polymerizing a vinyl monomer in the presence of a radical initiator using the same polyether polyol as described above and stably dispersing it.
• the vinyl monomer include acrylonitrile, styrene, vinylidene chloride, hydroxyalkyl, methacrylate, and alkyl methacrylate. Among them, acrylonitrile and styrene are preferable.
• Specific examples of such a polymer polyol include EL-910 and EL-923 manufactured by Asahi Glass Urethane Co., Ltd. and FA-728R manufactured by Sanyo Chemical Industries. *
• urethanization catalysts and trimerization catalysts known in the art can be used.
• Representative examples include triethylamine, tripropylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, dimethylbenzylamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, Tertiary amines such as N ′, N ′′ -pentamethyldiethylenetriamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, 1,8-diaza-bicyclo (5,4,0) undecene-7, dimethylethanol Reactive tertiary amines such as amines, N-trioxyethylene-N, N-dimethylamine, N, N-dimethyl-N-hexanolamine or organic acid salts thereof, 1-methimidazole, 2-methylimidazole,
• catalysts are 1,2-dimethylimidazole and bis- (2-dimethyl), because the reaction is mild and the balance between high curing properties is used. (Aminoethyl) ether. *
• the foaming agent (D) used in the present invention is foamed by carbon dioxide gas generated by the reaction between isocyanate groups and water.
• carbon dioxide is mixed in a liquid state and vaporized and foamed during foaming.
• a method can also be used together.
• the amount of water is preferably 2 to 20 parts by mass with respect to 100 parts by mass of the polyisocyanate composition.
• the amount is preferably 0.5 to 6 parts by mass with respect to 100 parts by mass of the polyisocyanate composition.
• the foam stabilizer (E) used in the present invention is an organosilicon surfactant known in the art.
• F-122 manufactured by the Company The amount of these foam stabilizers is preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the polyisocyanate composition.
• diethanolamine or triethanolamine can be added to the present invention for the purpose of stabilizing the cell.
• a preferable addition amount is 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyol component.
• the present invention further includes trichloroethyl phosphate, trichloropropyl phosphate, phosphorus-halogen liquid flame retardant represented by these condensation types, solid flame retardant represented by melamine powder, and conductivity represented by ketjen black.
• Plasticizers such as reactive carbon and dioctyl phthalate, antioxidants, ultraviolet absorbers, colorants, internal mold release agents, and other auxiliaries can be used. These auxiliaries are usually used by adding them to polyols. However, auxiliaries having no active hydrogen capable of reacting with isocyanate can be mixed in advance in the polyisocyanate composition.
• the equivalent ratio (NCO / NCO reactive group) of all isocyanate reactive groups in the isocyanate reactive compound containing water and all isocyanate groups in the polyisocyanate composition of the present invention is 0.5 to 1.5 (isocyanate index).
• the method for producing a flexible polyurethane mold foam according to the present invention includes a method for producing a flexible polyurethane mold foam characterized by injecting the soft polyurethane foam stock solution (A) to (E) into a mold and then foaming and curing. Can be used. *
• the mold temperature when the foaming stock solution is poured into the mold is usually 30 ° C. or higher, preferably 40 ° C. or higher, and the upper limit is usually 70 ° C. or lower, preferably 60 ° C. or lower.
• the mold temperature at the time of pouring the foaming stock solution into the mold is less than 30 ° C., the curing property is deteriorated. Can be a disadvantage.
• the time for curing the foaming stock solution in the mold is usually 3 minutes or longer, preferably 4 minutes or longer, and the upper limit is usually 8 minutes or shorter, preferably 6 minutes or shorter. If the curing time when the foaming stock solution is foamed and cured is shorter than 3 minutes, the curing property may be lowered. On the other hand, if it is longer than 8 minutes, the energy cost is increased and the obtained foam may shrink. is there. *
• the liquid mixture obtained by the foaming machine is discharged into a mold, foamed and cured, and then demolded.
• a release agent to the mold in advance.
• the release agent to be used may be a release agent usually used in the field of molding processing, and is not particularly limited.
• the wax solvent is used in the present invention. It is preferable to use a system release agent.
• the product after demolding can be used as it is, but in order to prevent foam shrinkage, the cell is destroyed by compression or decompression by a conventionally known method to stabilize the appearance and dimensions of the product. You can also.
• MDI-1 dimeric methane diisocyanate containing 94% isomer MDI and 6% 4,4'-MDI, manufactured by Nippon Polyurethane Industry Co., Ltd.
• MDI-2 diphenylmethane diisocyanate containing 100% 4,4'-MDI, Japan Polyurethane Industry Diphenylmethane diisocyanate containing 31%
• MDI-3 4,4'-MDI and 69% polymeric MDI, manufactured by Nippon Polyurethane Industry Co., Ltd.
• Product name KC-285P-3 polyoxyethylene polyoxypropylene polyol, nominal average functional group number 3, number average molecular weight 3,500, manufactured by Sanyo Chemical Industries, Ltd.
• C-1 Triethylenediamine 33% DPG solution, manufactured by Tosoh Corporation
• Product name TEDA-L33C-2 70% bis (dimethylaminoethyl) ether, 30% dipropylene glycol, manufactured by Tosoh Corporation
• DEA Diethanolami , Manufactured by Mitsui Chemicals, Inc.
• ⁇ foam stabilizer> S-1: silicone foam stabilizer, Momentibu product name Y-10366
• a flexible polyurethane mold foam was produced in the following manner.
• the polyol premix and the isocyanate component temperature-controlled at a raw material temperature of 23 ⁇ 2 ° C. were mixed at a high pressure under a predetermined ratio and discharged to a mold (400 mm ⁇ 400 mm ⁇ 70 mm thickness) temperature-controlled at 60 ⁇ 2 ° C. After 5 minutes, the mold was removed from the mold and the foam was crushed. The obtained foam was allowed to stand for 16 hours or more at a temperature of 23 ⁇ 2 ° C. and a relative humidity of 50 ⁇ 5%. Then, it cut
• the flexible polyurethane foam obtained by the present invention is excellent in durability, supportability, etc., and is used for furniture cushion materials such as sofas, clothing, cushion materials for automobiles and railway vehicles, automobile interior materials, mattresses, pillows, etc. It is useful for bedding, sound-absorbing materials, sound-insulating materials, household electrical appliances, electronic parts, industrial sealing materials, packing materials, and household goods.

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• 2009
  • 2009-08-29 JP JP2009199104A patent/JP2011046907A/ja active Pending
• 2010
  • 2010-08-19 KR KR1020127006140A patent/KR101389785B1/ko not_active IP Right Cessation
  • 2010-08-19 CN CN201080038410.5A patent/CN102482397B/zh not_active Expired - Fee Related
  • 2010-08-19 WO PCT/JP2010/005116 patent/WO2011024413A1/ja active Application Filing

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