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WO2008041348A1 - Composition polyisocyanate et procédé de production de mousse de polyuréthane dure au moyen de cette composition - Google Patents

Composition polyisocyanate et procédé de production de mousse de polyuréthane dure au moyen de cette composition Download PDF

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Publication number
WO2008041348A1
WO2008041348A1 PCT/JP2007/000999 JP2007000999W WO2008041348A1 WO 2008041348 A1 WO2008041348 A1 WO 2008041348A1 JP 2007000999 W JP2007000999 W JP 2007000999W WO 2008041348 A1 WO2008041348 A1 WO 2008041348A1
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WO
WIPO (PCT)
Prior art keywords
polyisocyanate composition
polyurethane foam
polyol
mass
foam
Prior art date
Application number
PCT/JP2007/000999
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English (en)
Japanese (ja)
Inventor
Akira Sugano
Toshiyuki Anzai
Kunio Hirata
Original Assignee
Nippon Polyurethane Industry Co., Ltd.
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Filing date
Publication date
Application filed by Nippon Polyurethane Industry Co., Ltd. filed Critical Nippon Polyurethane Industry Co., Ltd.
Publication of WO2008041348A1 publication Critical patent/WO2008041348A1/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
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • C08J9/12—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 by a physical blowing agent
    • C08J9/14—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 by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • 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
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08J2205/10—Rigid 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 polyisocyanate composition and a method for producing a rigid polyurethane foam using the composition. More specifically, for example, it is possible to provide a rigid polyurethane foam that has excellent storage stability in an ultra-low temperature atmosphere of, for example, 5 ° C, and also has excellent adhesion to an ultra-low temperature substrate of, for example, -5 ° C.
  • the present invention relates to a polyisocyanate composition, and a method for producing a rigid polyurethane foam using the polyisocyanate composition.
  • “rigid polyurethane foam” is a concept including “isocyanurate-modified polyurethane foam” unless otherwise specified.
  • the polyisocyanate used in the production of rigid polyurethane foam includes polymeric MDI including diphenylmethane diisocyanate (hereinafter abbreviated as “MD I”) and MD I multinuclear condensate. (Polyphenylene polymethylene polyisocyanate) is used.
  • H FC_245 fa 1, 1, 1, 3, 3_Pentafluoropropane
  • HF C-365m fc 1, 1, 1, 3, 3_ Hydrofluorocarbons such as pentafluorobutane
  • the rigid polyurethane foam based on the water foaming formulation does not have a sufficient adhesive force to the adherend.
  • the decrease in the adhesive strength to the adherend is a particular problem in spraying (spraying) performed in a low temperature environment.
  • This decrease in the adhesion strength to the adherend appears remarkably for an extremely low temperature adherend of, for example, -5 ° C, and this solution is particularly required.
  • the polyisocyanate used in the production of rigid polyurethane foam is required to have storage stability of the polyisocyanate at the construction site. Therefore, it is necessary to obtain storage stability in an ultra-low temperature atmosphere of, for example, ⁇ 5 ° C. in addition to the improvement in adhesion described above.
  • Patent Document 1 Japanese Patent Laid-Open No. 2000-2_3 2 2 2 3 1
  • Patent Document 2 Japanese Patent Laid-Open No. 2 0 0 2 _ 3 5 6 5 3 0
  • Patent Document 3 Japanese Patent Laid-Open No. 2 0 0 2 _ 3 5 6 5 3 2
  • Patent Document 4 Japanese Patent Laid-Open No. 2 0 0 2 _ 3 5 6 5 3 3
  • Patent Document 5 Japanese Patent Laid-Open No. 2 0 0 2 _ 3 5 6 5 3 4
  • Patent Document 6 Japanese Patent Laid-Open No. 2 0 0 2 _ 3 5 6 5 3 5
  • Patent Document 7 Japanese Patent Laid-Open No. 2 0 0 5 _ 2 1 3 3 0 6
  • a first object of the present invention is to obtain a rigid polyurethane foam having good adhesiveness to an extremely low temperature adherend of, for example, -5 ° C and excellent in shape stability. It is an object of the present invention to provide a polyisocyanate composition.
  • a second object of the present invention is to provide a polyisocyanate composition for producing a rigid polyurethane foam which is excellent in storage stability even in an ultra-low temperature atmosphere of, for example, -5 ° C.
  • a third object of the present invention is to provide good adhesion to an ultra-low temperature adherend of _5 ° C in a foaming formulation using a foamed fluorocarbon and / or water as a foaming agent. And it is providing the manufacturing method of the hard polyurethane foam excellent in the desired mechanical property etc.
  • a fourth object of the present invention is to provide a method for producing a rigid polyurethane foam having the above-described excellent performance even by a spray method.
  • the present invention is as follows (1) to (3).
  • a monovalent hydrocarbon group having 1 or more carbon atoms having 1 or more carbon atoms.
  • R 3 is a divalent divalent having 2 or more carbon atoms of 1 type or 2 types or more
  • a hydrocarbon group is shown.
  • n an integer of 1 or more.
  • polyisocyanate composition of the present invention for example, a hard material having good adhesion to an ultra-low temperature adherend of 15 ° C and having excellent shape stability.
  • Polyurethane foam can be produced.
  • the polysocyanate composition of the present invention is excellent in storage stability even in an ultra-low temperature atmosphere of, for example, -5 ° C, for example, in an ultra-low temperature atmosphere of, for example, 15 ° C.
  • an ultra-low temperature atmosphere of, for example, 15 ° C At a certain construction site, it is possible to stably supply a polyisocyanate composition for producing rigid polyurethane foam.
  • the polyisocyanate composition of the present invention comprises (A 1) diphenylmethane diisocyanate isomer mixture (aid) in an amount of 20 to 80% by mass and a trinuclear or higher diphenylmethane diisocyanate system.
  • RR 2 may be the same or different
  • a monovalent hydrocarbon group having 1 or more carbon atoms having 1 or more carbon atoms.
  • a hydrocarbon group is shown.
  • n an integer of 1 or more.
  • the polymeric MD I (A 1) constituting the polyisocyanate composition of the present invention has an MD I (a 1 d) of 20 to 80% by mass, MD I polynuclear It is a mixture (polyphenylene polymethylene polyisocyanate) in which the condensate (a 1 p) consists of 80 to 20% by mass.
  • MD I (a 1 d) and M D I polynuclear condensate (a 1 p) is polymeric M D I (A 1
  • Polymeric MD I (A 1) is obtained by converting the amino group of the condensation mixture (polyamine) obtained by the condensation reaction of aniline and formalin into a silicate group by phosgenation or the like. It is possible to control the composition (nuclear distribution and isomer composition ratio) of the finally obtained polymeric MDI by changing the raw material composition ratio and reaction conditions during the condensation.
  • the polymeric MD I (A 1) used in the present invention is a reaction solution such as a reaction solution after conversion to an isocyanate group, removal of the solvent from the reaction solution, or a bottom solution obtained by partially distilling and separating MDI. It may be a mixture of several kinds having different conditions and separation conditions. Further, commercially available polymeric MD I may be mixed with MD I (aid).
  • the ratio of MD I (a 1 d) in the polymeric MD I (A 1) is in the range of 20 to 80% by mass, preferably in the range of 25 to 75% by mass.
  • the ratio of MD I (a 1 d) is a ratio determined from the peak area ratio of MD I by GPC (gel permeation chromatography).
  • MD I (aid), a binuclear body, is composed of three isomers: 4, 4 '— MD I, 2, 2' — MD I, and 2, 4 '_MD I. Yes.
  • the composition ratio of these isomers is not particularly limited. However, the above-described conditions more severe than ⁇ 5 ° C., for example, under severe ambient conditions such as ⁇ 20 ° C. However, from the viewpoint of excellent storage stability (crystals and the like do not precipitate), the 4,4′_MDI content is preferably in the range of 60 to 95%.
  • the composition ratio of isomers can be obtained from a calibration curve based on the area percentage of each peak obtained by GC (gas chromatography).
  • the average number of functional groups of the polymeric MD I (A 1) is preferably 2.2 or more, and more preferably 2.2 to 3.1.
  • the isocyanate group content of the polymeric MD I (A 1) is 28 to 33 masses. %, More preferably 28.5 to 32.5% by mass.
  • acidity of polymeric MD I (A 1) is preferably a 0.001 to 0.2 mass 0/0, is more preferably a 003 to 0.1 5 wt% 0.5. As a result, the storage stability and suitable reactivity of the resulting polyisocyanate composition are ensured.
  • “Acidity” refers to the value obtained by converting the acid component that reacts with alcohol at room temperature to liberate into hydrogen chloride, and is measured according to JIS K-1603.
  • the polymeric MDI (A1) constituting the polyisocyanate composition of the present invention has a polyisocyanate composition of the present invention to be described later when the entire polyisocyanate composition is 100% by mass. In the range of 88.0 to 98.95 mass%, taking into account the proportion of introduction in a series of constituents essential for the composition (and thus the desired performance and effects obtained by the introduction of each constituent) Is preferably used.
  • the ricinoleic acid alkyl ester (A2) used in the present invention is obtained from ricinoleic acid (12-hydroxy-9-octadecenoic acid: mainly obtained from castor oil.
  • Fatty acid obtained from castor oil fatty acid
  • monohydric alcohol methanol, ethanol, propanol, isopropanol, butanol, hexanol, 2-ethyl hexyl alcohol, decyl alcohol, isodecyl alcohol, tridecyl alcohol
  • a polyisocyanate composition of the present invention which is an esterified product (monohydroxycarboxylic acid condensate ester) with pentadecanol, isopentadecanol, stearyl alcohol, isostearyl alcohol, eicosanol, isoeicosanol, etc.
  • Foaming agent especially It is a component that imparts uniform mixing properties with the hydro mouth fluorocarbons and / or foaming agents comprising water.
  • Examples of the ricinoleic acid alkyl esters (A2) include methyl ricinoleate and butyl ricinoleate. Select only one of these It may be used as a mixture of two or more. These compounds include, for example, “U ric H_3 1 (Methyl ricinoleate, manufactured by Ito Oil Co., Ltd.)”, “K_PON 1 80 (Methyl ricinoleate, manufactured by Ogura Synthetic Co., Ltd.)”, “K_PON 1 80 HP (Methyl ricinoleate (high-purity product), manufactured by Ogura Gosei Co., Ltd.) ”and“ K_PON 180 B (Butyl ricinoleate, manufactured by Ogura Gosei Co., Ltd.) ”are available from the market.
  • U ric H_3 1 Metal ricinoleate, manufactured by Ito Oil Co., Ltd.
  • K_PON 1 80 Metal ricinole
  • the ricinoleic acid alkyl ester (A2) As the ricinoleic acid alkyl ester (A2), the effect of improving uniform mixing with a foaming agent (particularly, a foaming agent composed of a hydro mouth fluorocarbon and / or water) is sufficiently obtained. It is preferable to select and use methyl ricinoleate from the viewpoint that the polyisocyanate composition obtained can be exerted and the viscosity of the resulting polyisocyanate composition is not too high and the possibility of causing a decrease in workability is extremely low.
  • the ricinoleic acid alkyl ester (A2) constituting the polyisocyanate composition of the present invention is a polyurethane obtained by the present invention when the entire polyisocyanate composition is 100% by mass.
  • the foam has good dimensional stability (when the introduction amount is excessive, the dimensional stability deteriorates), and the introduction has the desired effect in the polyisocyanate composition of the present invention (introduction amount). From the viewpoint that the effect cannot be obtained when the amount is too small), it is preferably used in the range of 0.5 to 5% by mass.
  • the ricinoleic acid alkyl esters (A 2) are present in a form reacted with a part of the isocyanate group in the polymeric MD I (A 1). In addition, it may exist in a uniformly mixed form without reacting with the isocyanate group.
  • the silicone-based foam stabilizer (A 3) which may contain a hydroxyl group constituting the polyisocyanate composition of the present invention is not particularly limited. Any conventional foam stabilizer (dimethylpolysiloxane and polysiloxane-polyether copolymer) can be used as the foam stabilizer for the rigid polyurethane foam.
  • Examples of the silicone foam stabilizer (A3) include known silicone surfactants such as L-5340, L_5420, L manufactured by Toray Dow Corning.
  • hydroxyl group-containing silicone a polysiloxane-polyether copolymer containing a hydroxyl group
  • silicone foam stabilizer A3
  • hydroxyl group-containing silicone a polysiloxane-polyether copolymer containing a hydroxyl group
  • A3 silicone foam stabilizer
  • uniform mixing with a foaming agent particularly, hydrofluorocarbons and / or The compatibility with water blowing agents and the dispersibility of the blowing agent in the composition
  • uniform mixing with a foaming agent particularly, hydrofluorocarbons and / or The compatibility with water blowing agents and the dispersibility of the blowing agent in the composition
  • the hydroxyl group-containing silicone is a block copolymer having a dimethylpolysiloxane structure and a polyoxyalkylene structure (polyether structure), and is a compound having a hydroxyl group in the molecular structure.
  • the average number of functional groups of the hydroxyl group-containing silicone (average number of hydroxyl groups in one molecule) is preferably 1 to 10, more preferably 1 to 5, particularly preferably "! To 2". If the average number of functional groups is too large, the resulting polyisocyanate composition has a high viscosity, and the workability during foaming tends to decrease.
  • the number average molecular weight of the hydroxyl group-containing silicone is preferably 500 to 20,000, and more preferably 1,000 to 18,000. Those having an excessive number average molecular weight have high viscosity and poor handleability.
  • the hydroxyl value of the hydroxyl group-containing silicone is 3 to 3 O Omg KOH / g. More preferably, it is 5 to 15 Omg KOH / g.
  • the hydroxyl value is too small, the viscosity is high and the handling property is inferior, and the formed foam does not have sufficient strength.
  • the hydroxyl value is excessive, the resulting polyisocyanate composition cannot sufficiently improve the uniform mixing property with the foaming agent.
  • the silicone-based foam stabilizer (A3) which may contain a hydroxyl group is from 0.05 to 2.0. It is preferably used in the range of mass%, more preferably in the range of 0.1 to 1.0 mass%, and in particular, it has the liquid viscosity of the polyisocyanate composition of the present invention (increased viscosity due to excessive introduction) In addition, from the standpoint of having uniform mixing (compatibility) with the hydrated fluorocarbons (this effect cannot be obtained with slight introduction), 0.2 to 1.0% by mass It is particularly preferred to be used in a range.
  • the compound (A 4) represented by the following general formula (1) constituting the polyisocyanate composition of the present invention includes: For example, all conventionally known compounds called dialkyl glycol ethers can be used.
  • R ' (0- R ⁇ -0- R (1)
  • R ' may be the same or different.
  • a monovalent hydrocarbon group having 1 or more carbon atoms having 1 or more carbon atoms.
  • R 3 is a divalent divalent having 2 or more carbon atoms of 1 type or 2 types or more
  • a hydrocarbon group is shown.
  • n an integer of 1 or more.
  • DMDG diethylene glycol dimethyl ether
  • DMTG triethylene glycol dimethyl ether
  • DE DG coal jetyl ether
  • DBDG diethylene glycol dibutyl ether
  • DM F DG dipropylene glycol monodimethyl ether
  • the compound (A4) represented by the general formula (1) has a relatively high boiling point and flash point, a low viscosity, and compatibility with water. From the standpoint of good results, it is preferable to select and use diethylene glycol jetyl ether (DE DG).
  • DE DG diethylene glycol jetyl ether
  • the compound (A4) represented by the general formula (1) is in the range of 0.5 to 5.0% by mass. It is preferably used, and more preferably in the range of 0.5 to 3.0% by mass, and in particular, the desired dimensional stability is ensured for the resulting rigid polyurethane foam. In addition, from the viewpoint of having excellent adhesion under a low temperature atmosphere of, for example, -5 ° C (this effect cannot be obtained if the introduction amount is small). It is particularly preferable to use in the range of 5% by mass.
  • the polyisocyanate composition of the present invention contains the above-mentioned polyisocyanate composition.
  • Meric MD I (A 1) is essential, but if necessary, the polyisocyanate composition of the present invention contains an isocyanate compound other than the essential isocyanate compound (hereinafter referred to as “other isocyanate compound”). Abbreviation.) May be contained.
  • isocyanate compounds include urethanates obtained by reacting polymeric MD I (or MDI only) and active hydrogen group-containing compounds (the above-mentioned ricinoleic acid alkyl esters (A 2) and polymeric MD I).
  • the polyisocyanate composition of the present invention may contain various optional components as long as the effect is not impaired.
  • optional components all of the conventionally known substances (additives, etc.) that are contained in the polyisocyanate composition for producing a rigid polyurethane foam can be used.
  • the isocyanate group content in the polyisocyanate composition of the present invention is preferably 28.0 to 31.5% by mass, more preferably 28.5 to 31.0% by mass, in particular, the mechanical properties desired for the rigid polyurethane foam obtained by using the polyisocyanate composition of the present invention can be provided.
  • the viscosity of the isocyanate composition is suitable for the production of a rigid polyurethane foam (for example, spraying operation at the time of spray foaming), it is particularly preferably 29.0 to 31.0% by mass.
  • the viscosity (25 ° C) of the polyisocyanate composition of the present invention is preferably 50 to 50 OmPa ⁇ s, more preferably 70 to 300 mPa ⁇ s, among which rigid polyurethane foam 80 to 150 mPa ⁇ s is particularly preferable from the viewpoint of being suitable for the production of (for example, spraying work during spray foaming).
  • the polyisocyanate composition of the present invention is excellent in homogeneous mixing with the hydro mouth fluorocarbons and water (compatibility / hydrofluorocarbons and water dispersibility in the composition). Therefore, it is preferably used for producing a rigid polyurethane foam by a foaming formulation using these as a foaming agent.
  • the polyisocyanate composition of the present invention is particularly suitable for use in a low-temperature environment in which a conventionally known polyisocyanate composition cannot be applied from the viewpoint of adhesion, particularly in a very low-temperature environment such as _5 ° C. It can be applied in spraying construction (spray construction), and a rigid polyurethane foam having good adhesion to the adherend can be formed.
  • the adherend to which the polyisocyanate composition of the present invention is applied is not particularly limited, and examples thereof include woods, concretes, various metals, papers, and stones. And various plastics, ceramics, glasses, and various rubbers.
  • the usage mode (construction method) of the polyisocyanate composition of the present invention is not limited to spray construction.
  • the manufacturing method of the present invention comprises the above-described polyisocyanate composition of the present invention and a polyol (B), a foaming agent (C), a catalyst (D) and an adjusting agent.
  • R 1 (O— n -0- (1)
  • R 1 and R 2 may be the same or different.
  • a monovalent hydrocarbon group having 1 or more carbon atoms having 1 or more carbon atoms.
  • R 3 is a divalent divalent having 2 or more carbon atoms of 1 type or 2 types or more
  • a hydrocarbon group is shown.
  • n an integer of 1 or more.
  • the “polyol (B)” used in the production method of the present invention is not particularly limited, and examples thereof include conventionally known polyester polyols, polyether polyols, and polycarbonate polyols. I can do it.
  • a low molecular polyol, a low molecular polyamine, a low molecular amino alcohol or the like may be used in combination.
  • polyol (B) used in the production method of the present invention it is preferable to use at least one of the following three types of polyols [polyols (b 1) to (b 3)]. It is more preferable to use the above.
  • polyol (b 1) and polyol (b 3) When only one of polyol (b 1) and polyol (b 3) is used, the formed rigid polyurethane foam may not have sufficient mechanical strength.
  • Polyol (B) consisting only of polyol (b 2) tends to be inferior in workability due to excessive viscosity.
  • polyether polyol of 100 to 900 mg KO H / g
  • a polyhydric alcohol used for obtaining polyol (b 2) and polyol (b 3) can be used in combination as an initiator.
  • Polyol (b 2) (1) Ethylene glycol, propanediol, butanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3 _Methyl mono 1,5_ A mixture of one or more polyhydric alcohols such as pentanediol, glycerin, trimethylolpropane, pentaerythritol and adipic acid, malonic acid, fumaric acid, oxalic acid, tartaric acid, oxalic acid Of compounds having at least two or more strong lpoxyl groups (or groups derived from strong lpoxyl groups), such as phthalic anhydride, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarponic acid, etc.
  • lactone for example, pro-lactone.
  • [0074] [Polyol (b 3)] Ethylene glycol, propanediol, butanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3_methyl 1 1,5_Pentanediol, Glycerin, Trimethylolpropane, Pentaerythri!
  • the initiator is a polyhydric alcohol having 2 to 6, preferably 2 to 5 hydroxyl groups in one molecule. Hydroxyl value 50 ⁇ obtained by addition reaction of alkylene oxides such as
  • each of the polyols (b 1) to (b 3) when the hydroxyl value is a certain value (lower limit) or more, sufficient mechanical strength can be imparted to the formed rigid polyurethane foam. it can. Further, when the hydroxyl value is not more than a certain value (upper limit value), brittleness of the formed rigid polyurethane foam can be suppressed.
  • the average number of functional groups of the polyol (b 1) is preferably 2 to 8, and more preferably 3 to 6.
  • the average number of functional groups of the polyol (b 2) is preferably 2 to 4, more preferably 2 to 3.
  • the average number of functional groups of the polyol (b 3) is preferably 3 to 6, and more preferably 3 to 5.
  • each of the polyols (b 1) to (b 3) when the average number of functional groups is a certain number (lower limit) or more, sufficient mechanical strength can be imparted to the formed rigid polyurethane foam. it can. In addition, when the average number of functional groups is a certain number (upper limit) or less, embrittlement of the formed rigid polyurethane foam can be suppressed.
  • the proportion of the polyol (b 1) in the polyol (B) is preferably 40 to 70% by mass.
  • the proportion of the polyol (b 2) in the polyol (B) is preferably 10 to 90% by mass.
  • the proportion of the polyol (b 3) in the polyol (B) is preferably 10 to 70% by mass.
  • the total proportion of polyol (b 1), polyol (b 2) and polyol (b 3) in the polyol (B) is preferably 80% by mass or more.
  • Polyols other than the polyols (b 1) to (b 3) constituting the polyol (B) include ethylene glycol, diethylene glycol, and hydroxyl values of 50 to 15 Om.
  • a suitable example is polypropylene glycol of g KO H / g.
  • the viscosity of the polyol (B) can be reduced.
  • a polymer polyol may be used as the other polyol constituting the polyol (B).
  • This polymer polyol is based on the above-mentioned polyether polyol or polyester polyol, and a vinyl polymer of styrene or acrylonitrile, or a polymer obtained from an active hydrogen group-containing compound and polyisocyanate ⁇ ⁇ ⁇ is introduced as a graft polymerization or filler.
  • the polymer content in the polymer polyol is preferably 1 to 20% by mass.
  • the viscosity (25 ° C) of the polyol (B) is preferably 2,000 OmPa-s or less, and more preferably from 100 to 1,800 mPas. When the viscosity exceeds the upper limit, workability particularly in winter is reduced.
  • ⁇ Foaming agent (C)> In the production method of the present invention, hydrofluorocarbon and / or water are used as the foaming agent (C).
  • the amount of foaming agent (C) to be added should be the following when using a high mouth fluorocapon such as H FC_245 fa, HF C-365m fc, H FC_ 1 34 a, etc. (B) against a 50 mass 0/0.
  • the amount of water added in the case of using the combined hydrofluorocarbon and water is 0.5 to 5.0% by mass with respect to the polyol (B).
  • the foaming agent (C) a combined use of a hydro mouth carbon and water
  • the main foaming agent is hydrofluorocarbon and the secondary foaming agent is used as water.
  • the form exerts the most desired effect on the rigid polyurethane foam obtained by the production method of the present invention.
  • “primary foaming agent” and “secondary foaming agent” are some of the mass parts used, and “primary foaming agent” is more mass part than “secondary foaming agent”.
  • desired performance for example, dimensional stability (small shrinkage at room temperature)
  • adhesion to an adherend for example, -5 ° C
  • desired performance for example, dimensional stability (small shrinkage at room temperature)
  • adhesion to an adherend for example, -5 ° C
  • hydro mouth fluoro ether as a foaming agent (C) in combination with hydro fluorocapon and / or water. Is possible.
  • Hyde mouth Fluorotel there is a conventionally known one as the Hyde mouth Fluorotel, for example, H FE-254 pc (CH F 2 CF 2 OCH 3 ), CF 3 CH FOC F 3 (H FE— 227me), CF 3 CH FOCH F 2 (H FE-236me), CF 3 CH 2 OC F 3 (H FE-236m f), CHF 2 CF 2 OCH F 2 (H FE-236 pc) , CF 3 CF 2 OCH 3 (H FE—
  • any one of these may be selected and used in combination with a hydrofluorocapon and / or water, or two or more of these may be used in combination. It may be used in combination with a forceful pump and / or water.
  • Catalyst (D) As the “catalyst (D)” used in the production method of the present invention, a known catalyst usually used for urethane foaming can be used.
  • a known catalyst usually used for urethane foaming can be used.
  • tin compounds such as hexylamine, dibutyltin diacetate and dibutyltin dilaurate
  • metal complex compounds such as acetylethylaceton metal salt.
  • Trimerization catalysts include 2, 4, 6-tris (dimethylaminomethyl) phenol, 1, 3, 5-tris (dimethylaminopropyl) hexahydro _ s-triazines such as triazine, 2, 4_bis (Dimethylaminomethyl) Phenyl, 2-ethylhexyl hexanoate, 2-ethylhexyl sodium acetate, potassium acetate, sodium acetate, amine compounds such as aziridines such as 2-ethylaziridine, tertiary Quaternary ammonium compounds such as carboxylic acid salts of amines, lead compounds such as diazabicycloundecene, lead naphthenate and lead octylate, alcoholic compounds such as sodium methoxide, potassium phenoxide And the like, and the like. These catalysts can be used alone or in combination of two or more.
  • the amount of the catalyst (D) used is suitably from 0 to 1 to 15% by mass based on the polyol (B).
  • the above-mentioned silicone-based foam stabilizer (A 3) is not particularly limited, and conventionally known foam stabilizers for rigid polyurethane foam (dimethylpolysiloxane and polysiloxane-polyether copolymer) are used. All can be used. Specific examples thereof include those listed in the aforementioned silicone foam stabilizer (A 3).
  • the amount of the foam stabilizer (E) used is suitably 0.1 to 5% by mass relative to the polyol (B).
  • the foam stabilizer (E) used in the production method of the present invention has the performance desired for the rigid polyurethane foam obtained by the present invention, and the aforementioned silicone foam stabilizer (A 3).
  • the same one as that used in the above may be used, or another one may be used.
  • an additive can be used (the polyisocyanate mixture (A) and the polyol (B) are reacted in the presence of the additive).
  • these additives include plasticizers, fillers, colorants, flame retardants, organic or inorganic fillers, antioxidants, UV absorbers, plasticizers, pigments, dyes, antibacterial agents, and antifungal agents.
  • a flame retardant it is preferable to use a flame retardant.
  • the flame retardant examples include phosphate esters such as triethyl phosphate and tris (S-clopropyl) phosphate, and phosphate compounds of phosphites such as ethyl phosphite and jetyl phosphite. It is done.
  • phosphate esters such as triethyl phosphate and tris (S-clopropyl) phosphate
  • phosphate compounds of phosphites such as ethyl phosphite and jetyl phosphite. It is done.
  • a multi-component system having three or more components may be used.
  • the "I liquid” containing the polyisocyanate composition of the present invention as a main component.
  • the polyisocyanate composition of the present invention is referred to as “Liquid I”, and the polyol (B) is referred to as “R liquid”.
  • the foaming agent (C), the catalyst (D), the foam stabilizer (E) and the additive (optional component) are mixed in the “I liquid” and / or “R liquid”.
  • the foaming agent (C), catalyst (D) and foam stabilizer (E) are preferably mixed in the “R liquid”.
  • the silicone-based foam stabilizer (A 2) contained in “Liquid I” from the beginning is handled as a constituent of the foam stabilizer (E) in the subsequent steps.
  • the mixing device for "I liquid” and “R liquid” is not particularly limited. For example, it is used for the production of small mixers and general urethane foam. Low pressure or high pressure foaming machines, low pressure or high pressure foaming machines for slab foaming, low pressure or high pressure foaming machines for continuous lines, spray foaming machines for spraying work, etc. can be used.
  • the temperature of the “I liquid” and “R liquid” to be mixed is preferably adjusted to 15 to 50 ° C.
  • the rigid polyurethane foam obtained by the production method of the present invention has a chemical bond such as a urethane bond or urea bond (so-called urethane foam).
  • urethane foam a chemical bond
  • isocyanurate groups can be generated at the time of foaming, and isocyanurate-modified polyurethane foams (so-called isocyanurate foams) thus obtained are also included in “rigid polyurethane foam”.
  • the isocyanurate group is formed by trimerizing the isocyanate group with a trimerization catalyst, and can improve mechanical strength, heat resistance, and the like.
  • a preferred isocyanate index [(number of moles of all isocyanate groups in the polyisocyanate composition / number of moles of all active hydrogen groups in the polyol (B)) X 1 0 0] is
  • urethane foam it is preferably from 50 to 140, and more preferably from 70 to 130.
  • isocyanurate foam formed using a trimerization catalyst it is preferably from 140 to 800, more preferably from 150 to 500.
  • the isocyanate index is urethane foam 5 0 If it is less than 140 in the case of isocyanurate foam, the resulting foam may not have sufficient strength and is likely to shrink. In the case of urethane foam, exceeding 140, and in the case of isocyanurate foam exceeding 800, the resulting foam tends to become brittle and the adhesiveness tends to decrease.
  • Example 1 In accordance with the formulation shown in Table 1 below, a reactor having a capacity of 100 kg equipped with a stirrer, a cooling pipe, a nitrogen introduction pipe, and a thermometer was 84.7 kg of “Isocyanate B” and 1 1.6 kg of “Isocyanate D” were charged, respectively, and heated to 60 ° C. with stirring to obtain “Polymeric MD I (A 1)”. . Next, 2.
  • the product “N C O _ 1” was obtained.
  • the isocyanate group content (hereinafter abbreviated as “NCO content”, if necessary) of this polyisocyanate composition “NCO _ 1” is 29.6%, and the viscosity (25 ° C) is 1 21 mP a ⁇ s Met.
  • Examples 2 to 18, Comparative Examples 1 to 9 In accordance with the formulations shown in Table 1 and Table 2 below, isocyanate A to D, ricinoleic acid alkyl esters (A2) as “A2_1” or “A2_2” Except for using “A3_1” or “A3-2” as the silicone-based foam stabilizer and each of “A4_1” to “A4_5” as the dialkyl glycol ether (A4), Example 1 and Similarly, polyisocyanate compositions “NCO_2” to “NCO — 18” of the present invention and polyisocyanate compositions “NCO — 19” to “NCO — 27” as comparative examples were prepared. The isocyanate content and viscosity (25 ° C) of the obtained polyisocyanate composition are shown in Tables 1 to 5 together.
  • ⁇ Lisinolenic acid alkyl esters (A2-2)> Methyl ricinoleate “K_PON 1 80” (manufactured by Ogura Gosei Kogyo Co., Ltd.).
  • DMTG triethyleneglycoldimethylether
  • DMDG Diethylene glycol dimethyl ether
  • ⁇ Dialkylglycol ether (A4-4)> Diethylene glycol dibutyl ether “DBDG” (manufactured by Nippon Emulsifier Co., Ltd.).
  • DBDG diethylene glycol dibutyl ether
  • DM FDG Dipropylene glycol dimethyl ether
  • a rigid polyurethane foam was formed on the entire surface of the plywood (1 OO OmmX l 00 Omm) to which the adherend was applied.
  • the cream time and rise time were measured as reactivity during the formation.
  • the foam core density was measured after curing in a 15 ° C atmosphere while standing for 24 hours.
  • the blowing and foaming conditions are as follows.
  • ⁇ Foaming machine Gasmer spraying foamer "FF — 1 600 ”, ⁇ Temperature of adherend: _5 ° C, ⁇ Primary heater temperature: 45 ° C, ⁇ Foam thickness: 30-4 Omm.
  • the polyisocyanate composition of the present invention comprises a board, a panel, a refrigerator, a firewood, a door, a shutter, a sash, a concrete house, a bathtub, a cryogenic tank device, a freezer warehouse, a pipe cover, anti-condensation, a slab, etc. It can be applied to various insulation materials.
  • the polyisocyanate composition of the present invention is applied to various adherends by spraying.

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une composition polyisocyanate qui permet d'obtenir une mousse de polyuréthane dure, laquelle possède une excellente stabilité de stockage dans une atmosphère à ultra-basse température, par exemple moins 5 °C, et qui présente une propriété d'adhésion excellente sur un objet à ultra-basse température, par exemple moins 5 °C. Cette invention concerne aussi un procédé de production de mousse de polyuréthane dure au moyen de cette composition polyisocyanate. L'invention concerne plus spécifiquement une composition polyisocyanate composée d'un MDI polymère, d'un éster alkyle d'acide riciniléique, d'un agent de contrôle de mousse de silicone et d'un éther dialkylglycol..
PCT/JP2007/000999 2006-09-29 2007-09-13 Composition polyisocyanate et procédé de production de mousse de polyuréthane dure au moyen de cette composition WO2008041348A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008260841A (ja) * 2007-04-12 2008-10-30 Nippon Polyurethane Ind Co Ltd 独立気泡を有する硬質ポリウレタンフォーム製造用ポリイソシアネート組成物および該組成物を用いた独立気泡を有する硬質ポリウレタンフォームの製造方法
JP2008260836A (ja) * 2007-04-12 2008-10-30 Nippon Polyurethane Ind Co Ltd 独立気泡を有する硬質ポリウレタンフォームの製造方法
WO2022078884A1 (fr) * 2020-10-13 2022-04-21 Covestro Deutschland Ag Composition pour former une mousse de polyuréthane, mousse de polyuréthane, et matériau d'isolation thermique
EP4011929A1 (fr) * 2020-12-14 2022-06-15 Covestro Deutschland AG Composition de formation de mousse de polyuréthane, mousse de polyuréthane, et matériau d'isolation thermique
JP7601593B2 (ja) 2020-10-13 2024-12-17 コベストロ、ドイチュラント、アクチエンゲゼルシャフト ポリウレタンフォーム形成用組成物、ポリウレタンフォーム及び断熱材

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* Cited by examiner, † Cited by third party
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JP7413667B2 (ja) * 2019-07-10 2024-01-16 東ソー株式会社 硬質ポリウレタンフォーム用組成物及び硬質ポリウレタンフォームの製造方法

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JPH0255470B2 (fr) * 1979-02-02 1990-11-27 Nhk Spring Co Ltd
JP2002356535A (ja) * 2001-05-29 2002-12-13 Nippon Polyurethane Ind Co Ltd 硬質ポリウレタンフォーム用ポリイソシアネート組成物、及びそれを用いた硬質ポリウレタンフォームの製造方法
JP2003055427A (ja) * 2001-08-21 2003-02-26 Nippon Polyurethane Ind Co Ltd 自己乳化型アロファネート変性ポリイソシアネートの製造方法
JP2004083847A (ja) * 2002-06-28 2004-03-18 Central Glass Co Ltd 発泡剤組成物、硬質ポリウレタンフォームまたはポリイソシアヌレートの調製用のプレミックスおよび該フォームの製造方法

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JP4305941B2 (ja) * 2002-12-26 2009-07-29 日本ポリウレタン工業株式会社 水発泡硬質ポリウレタンフォーム一体成型品の製造方法

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JPH0255470B2 (fr) * 1979-02-02 1990-11-27 Nhk Spring Co Ltd
JP2002356535A (ja) * 2001-05-29 2002-12-13 Nippon Polyurethane Ind Co Ltd 硬質ポリウレタンフォーム用ポリイソシアネート組成物、及びそれを用いた硬質ポリウレタンフォームの製造方法
JP2003055427A (ja) * 2001-08-21 2003-02-26 Nippon Polyurethane Ind Co Ltd 自己乳化型アロファネート変性ポリイソシアネートの製造方法
JP2004083847A (ja) * 2002-06-28 2004-03-18 Central Glass Co Ltd 発泡剤組成物、硬質ポリウレタンフォームまたはポリイソシアヌレートの調製用のプレミックスおよび該フォームの製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008260841A (ja) * 2007-04-12 2008-10-30 Nippon Polyurethane Ind Co Ltd 独立気泡を有する硬質ポリウレタンフォーム製造用ポリイソシアネート組成物および該組成物を用いた独立気泡を有する硬質ポリウレタンフォームの製造方法
JP2008260836A (ja) * 2007-04-12 2008-10-30 Nippon Polyurethane Ind Co Ltd 独立気泡を有する硬質ポリウレタンフォームの製造方法
WO2022078884A1 (fr) * 2020-10-13 2022-04-21 Covestro Deutschland Ag Composition pour former une mousse de polyuréthane, mousse de polyuréthane, et matériau d'isolation thermique
JP7601593B2 (ja) 2020-10-13 2024-12-17 コベストロ、ドイチュラント、アクチエンゲゼルシャフト ポリウレタンフォーム形成用組成物、ポリウレタンフォーム及び断熱材
EP4011929A1 (fr) * 2020-12-14 2022-06-15 Covestro Deutschland AG Composition de formation de mousse de polyuréthane, mousse de polyuréthane, et matériau d'isolation thermique

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