WO2005028535A1 - 軟質ポリウレタンフォームおよびその製造方法 - Google Patents
軟質ポリウレタンフォームおよびその製造方法 Download PDFInfo
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- WO2005028535A1 WO2005028535A1 PCT/JP2004/013668 JP2004013668W WO2005028535A1 WO 2005028535 A1 WO2005028535 A1 WO 2005028535A1 JP 2004013668 W JP2004013668 W JP 2004013668W WO 2005028535 A1 WO2005028535 A1 WO 2005028535A1
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- polyurethane foam
- flexible polyurethane
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular 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
- C08G18/48—Polyethers
- C08G18/4866—Polyethers having a low unsaturation value
-
- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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- 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
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- 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
- C08J9/125—Water, e.g. hydrated salts
-
- 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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
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- G—PHYSICS
- G10—MUSICAL INSTRUMENTS; ACOUSTICS
- G10K—SOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
- G10K11/00—Methods or devices for transmitting, conducting or directing sound in general; Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
- G10K11/16—Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
- G10K11/162—Selection of materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/08—Insulating elements, e.g. for sound insulation
-
- 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
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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
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2350/00—Acoustic or vibration damping material
Definitions
- the present invention relates to a flexible polyurethane foam having good sound absorbing performance over a wide and wide range of low frequency force and medium frequency, and a method for producing the same. Since the flexible polyurethane foam has excellent sound absorbing performance, it does not need to be used in combination with a thermoplastic material as in the past when used as a soundproofing material for automobiles. Also, since it exhibits excellent soundproofing performance when used alone, it is also effective in reducing the weight of automobiles.
- a soundproofing material for sound absorption and sound insulation has been mounted on a dashboard portion that separates an engine room and a vehicle interior of an automobile, and vibration and noise can enter the vehicle interior from the engine room. Measures have been taken to prevent
- a sound insulating material such as a rubber, a polypropylene sheet, a Shiridani vinyl sheet or the like is integrally formed on a porous sound absorbing material such as a polyester fiber or a flexible polyurethane foam (hereinafter also referred to as a soft foam).
- a soft foam a porous sound absorbing material
- flexible foam has been used as a sound absorbing material because of its advantage that it can be manufactured at a lower cost than polyester fiber.
- Patent Document 1 discloses a flexible foam having a specific level of air permeability and hardness and a method for producing the same
- Patent Document 2 discloses a method for producing a flexible foam that is lightweight and has excellent soundproofing performance. Have been.
- Patent Document 3 proposes a soundproofing material that can also act as a single piece of flexible foam.However, although medium-frequency force exhibits excellent sound absorption performance in the high-frequency range (2000 Hz or higher), it has a low-frequency range of 100 Hz or lower, especially 500 Hz or lower. There is a problem that the sound absorption performance in the region is insufficient.
- Patent Document 1 Japanese Patent Publication No. 7-59389
- Patent Document 2 JP-A-5-209036
- Patent Document 3 JP-A-10-121597
- the present invention provides a method for producing a flexible polyurethane foam with improved low-frequency sound absorption performance, which has been insufficient conventionally.
- the present invention provides a method for producing a flexible polyurethane foam which is a flexible foam having a good sound absorbing performance over a wide range from low frequency to medium frequency and which can be used as a soundproofing material of an automobile without being used in combination with other materials.
- the present inventors have found that by controlling the air permeability of a flexible polyurethane foam, the sound absorption performance in a low-frequency force and also in a medium-frequency region is enhanced, and have completed the present invention.
- the present invention is the following invention.
- the raw material composition (E) containing the high molecular weight polyoxyalkylene polyol (A), the organic polyisocyanate conjugate (B), the blowing agent (C), and the catalyst (D) is hermetically sealed.
- Air permeability of a flexible polyurethane foam that is a polyoxyalkylene polyol (P) having a total unsaturation (USV) of 0.08 meqZg or less and foamed to a thickness of 26 mm using the raw material composition (E) method for producing a flexible polyurethane foam, characterized in that but is less than 0. 085m 3 Zmin, flexible polyurethane foams for sound insulation obtained by the manufacturing method, and a soft polyurethane Four of automobile interior materials Effect of the Invention
- the flexible polyurethane foam obtained according to the present invention has an improved sound absorbing performance in a low frequency region of about 500Hz, and thus is suitable as a soundproofing material for buildings or vehicles.
- the flexible polyurethane foam of the present invention has an effect that the foam alone can be used as a soundproofing material for automobiles, and is also effective in reducing the weight of automobiles.
- a high molecular weight polyoxyalkylene polyol (A) (hereinafter, also referred to as polyol (A)) is used.
- the polyol (A) in the present invention is preferably obtained by ring-opening addition polymerization of an alkylene oxide in the presence of an initiator and a catalyst.
- the average number of hydroxyl groups is preferably 2 or more, and the molecular weight per hydroxyl group (Mc) is 500. It is preferable that it is above.
- the polyol (A) has a molecular weight (Mc) per hydroxyl group (Mc) of preferably 500 to 5,000, more preferably 800 to 2,500, and particularly preferably 850 to 2,500.
- the polyol (A) may be a mixture of high molecular weight polyoxyalkylene polyols having a molecular weight (Mc) of 500 or more per hydroxyl group.
- the average molecular weight (Mc) per hydroxyl group is 500 — 5000-force, 800--2800 is more preferable, 850-2,500 is more preferable! /,
- the average molecular weight (Mc) per hydroxyl group is less than 500!
- a polyoxyalkylene polyol having a molecular weight per hydroxyl group of less than 500 may be used, but such a polyoxyalkylene polyol is classified in the present invention as a crosslinking agent described later.
- the polyol (A) is a polyol having an average number of hydroxyl groups of 2 or more.
- the polyol (A) may be a single kind, a mixture of two or more kinds, or a polyol produced by using a mixture as an initiator as described later. It is preferred that the average number of hydroxyl groups is 2-8. 2-4 is more preferred. 2. 2-3. 9 is even more preferred. 2. 4-3.7 is most preferred. If the average number of hydroxyl groups of the polyol is less than 2, the foam becomes too soft and the compression set deteriorates.If the number of hydroxyl groups exceeds 8, the foam becomes hard and the mechanical properties such as elongation of the foam deteriorate. , The soundproofing performance tends to be impaired.
- the number of hydroxyl groups of the polyol (A) is the same as the number of hydroxyl groups of the initiator used for producing the polyol (A).
- the initiator used for producing the polyol (A) a compound having 2 to 8 active hydrogen atoms is preferable.
- polyhydric alcohols, polyhydric phenols, and amines having 2 to 8 valences are preferred.
- Specific examples include ethylene glycol, propylene glycol, and 1,4-butane.
- Polyhydric alcohols such as diol, neopentyl glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, meso-erythritol, methyl glucoside, glucose, dextrose, sorbitol, sucrose, bisphenol 8, pyrogallol, hydroquinone
- polyamines such as ethylenediamine, diethylenediamine, diaminodiphenylethanol, hexamethylenediamine and propylenediamine, and condensation reaction of these polyamines with phenolic resin and novolak resin. Amines such as condensation compounds to be obtained.
- a low molecular weight polyether polyol obtained by subjecting the polyhydric alcohols, polyhydric phenols, and amines to a small amount of ring-opening addition polymerization with an alkylene oxide, and having a molecular weight per hydroxyl group of about 200 to 500, Preferably 200-350 compounds can also be used. Such compounds preferably have a molecular weight of 1200 or less.
- a compound having 2 to 4 active hydrogen atoms is more preferable, and a 2-4 valent polyhydric alcohol or a 2-4 valent low molecular weight polyether polyol is preferable.
- polyols produced using polyhydric alcohols having a valency of 3 or more or low molecular weight polyether polyols as the initiator are preferable because they have the ability to balance sound insulation, foaming stability, and physical properties of flexible foams. It is preferable to use such a polyol as at least a part of the polyol (A). Two or more of these initiators may be used in combination.
- the alkylene oxide includes ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like, and a combination of ethylene oxide and propylene oxide is preferable.
- a usual catalyst is used.
- potassium hydroxide, sodium hydroxide, cesium hydroxide, phosphazem-dum compound, boron trifluorofluoride Doi conjugates, double metal cyanide complexes and the like are used.
- cesium hydroxide and a complex metal cyanide complex is preferred because a polyol having a low degree of unsaturation can be produced, and a flexible foam having appropriate air permeability can be produced by using the same.
- the polyol (A) may contain polymer fine particles dispersed in the polyol.
- Polymer fine particles are particles in which polymer fine particles are stably dispersed in a base polyol as a dispersion medium, and examples of the polymer fine particles include addition-polymer-based polymers and polycondensation-based polymers.
- it is composed of an addition polymer based polymer such as acrylonitrile, styrene, alkyl methacrylate, alkyl acrylate, and other homopolymers / copolymers of butyl monomers, and polycondensation polymers such as polyester, polyurea, polyurethane, and melamine resin.
- acrylonitrile, styrene or a copolymer thereof is preferable.
- the content of the polymer fine particles in the polyol (A) is preferably from 0.1 to 10% by mass, and more preferably from 11 to 10% by mass.
- the amount of the fine polymer particles need not be particularly large or may be too large.
- the presence of polymer fine particles in the polyol (A) is not essential, but the presence thereof is effective in improving the foam hardness, air permeability, and other physical properties. Therefore, it is preferably present in an amount of 1% by mass or more, especially 3% by mass or more.
- the method of dispersing the polymer fine particles includes a method of dispersing the polymer fine particles using the polyol (A) as a base polyol, a method of manufacturing a dispersion of the polymer fine particles using a part of the polyol (A) as a base polyol, and a method of dispersing the polymer fine particles. Any other method may be used, even if the method of mixing is used.
- a polyoxyalkylene polyol (hereinafter, also referred to as a polyol (p)) is used as at least a part of the polyol (A).
- the polyol (p) is, among the above-mentioned polyols (A), particularly those having a hydroxyl number of 2 or more, a molecular weight per hydroxyl group (Mc) of 1800-2800, and a total unsaturation (USV) of O.08meqZg or less.
- Oxyalkylene polyol is, among the above-mentioned polyols (A), particularly those having a hydroxyl number of 2 or more, a molecular weight per hydroxyl group (Mc) of 1800-2800, and a total unsaturation (USV) of O.08meqZg or less.
- the molecular weight (Mc) per hydroxyl group of the polyol (p) is from 1800 to 2800, preferably from 1850 to 2500. If the molecular weight (Mc) per hydroxyl group is less than 1800, the curing of the soft form is insufficient and shrinkage tends to occur, which is not preferable. When the molecular weight is larger than 2800! / ⁇ , the elasticity of the foam is insufficient.
- the polyoxyalkylene polyol (p) has a total degree of unsaturation of not more than 0.08 meqZg.
- the total degree of unsaturation is more preferably not more than 0.06meqZg, further preferably not more than 0.05meqZg, and most preferably not more than 0.0meqZg.
- the average number of hydroxyl groups of the polyol (p) is 2 or more.
- the polyol (p) may be a single kind or a mixture of polyols having a molecular weight per hydroxyl group (Mc) of 1800 to 2800 and a total unsaturation (USV) of 0.08 meqZg or less.
- the mixture It may be manufactured by using as a data.
- the average number of hydroxyl groups is preferably 2-8, preferably 2-4, more preferably 2. 2-3.9, more preferably 2.4.3.7.
- the foam becomes soft and the compression set is deteriorated, and when the number of hydroxyl groups exceeds 8, the foam becomes hard and the mechanical properties such as elongation of the foam deteriorate. Or the soundproofing performance is impaired.
- the polyol (p) preferably has a polyoxyethylene block chain at the terminal, and particularly preferably has 5 to 25% by mass.
- the proportion of the polyol (p) in the polyol (A) is preferably 5 to 100% by mass.
- the proportion of polyol (p) is preferably from 8 to 100% by weight, most preferably from 8 to 70% by weight.
- the ratio of the polyol (p) in the polyol (A) is calculated based on the mass of the polyol (A) excluding the fine polymer particles.
- polyol (A) in addition to polyol (A).
- the amount of use is preferably 20 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the polyol (A).
- the organic polyisocyanate conjugate (B) used in the present invention is not particularly limited, but is preferably an aromatic, alicyclic, or aliphatic polyisocyanate having two or more isocyanate groups; And the like. Modified polyisosinates obtained by modifying the above; and a mixture of two or more kinds of the above-mentioned polyisocyanates.
- TDI tolylene diisocyanate
- MDI diphenyl-norethanediisocyanate
- XDI polymethylene polyphenylene-isocyanate
- XDI xylylene diisocyanate
- Polyisocyanates such as isophorone diisocyanate (HIPDI) and hexamethylene diisocyanate (HMDI), and modified prepolymers, isocyanurates, perylenes, and carbodiimides thereof.
- TDI, MDI, crude MDI, or a modified form thereof is preferable.
- the amount of the organic polyisocyanate compound used is usually represented by the isocyanate index ((isocyanate equivalent) Z (total equivalent of all active hydrogen such as polyol, crosslinking agent, water, etc.) X 100). As shown, the amount of the polyisocyanate conjugate used in the present invention is preferably 50-110 in isocyanate index, more preferably 55-95 force! / ⁇ .
- the foaming agent (C) is not particularly limited, but it is preferable to use at least one foaming agent selected from water and an inert gas.
- the inert gas include air, nitrogen, and carbon dioxide. It is particularly preferable to use water as the blowing agent.
- the amount of these foaming agents used is not particularly limited, but when water is used, the polyol (A) (when a high molecular weight polyol other than the polyol (A) is used, the total of the polyol (A) and the other high molecular weight polyol is used. 10 parts by mass or less is preferable for 100 parts by mass. 0.1 to 18 parts by mass is more preferable.
- Other foaming agents can be used in an appropriate amount depending on the requirements such as the expansion ratio.
- a catalyst (D) When reacting the polyol (A) with the organic polyisocyanate conjugate (B), a catalyst (D) is used.
- the catalyst (D) include an amine compound and an organometallic compound.
- Examples of the tertiary amine catalyst having a molecular weight of 500 or less and having a hydroxyl group in the molecule include N, N-dimethylaminoethoxyethoxyethanol, N, N-dimethylamino-6-hexanol, There are N-dimethylaminoethoxyethanol, N, N-dimethylaminoethoxyethanol, a compound obtained by adding 2 moles of ethylene oxide, and 5- (N, N-dimethyl) amino-3-methyl-1-pentanol. It is not limited to these.
- tertiary amine catalysts can also be used, such as triethylenediamine, bis (2-dimethylaminoethyl) ether, N, N, ⁇ ', and dimethyltetramethylenediamine.
- the amount of the amine-based catalyst used is polyol ( ⁇ ) (a high molecular weight polymer other than polyol ( ⁇ )).
- the total amount is preferably 0.1 to 5 parts by mass per 100 parts by mass of the polyol (A) and the other high molecular weight polyol. If the amount is more or less than this range, the curing by reaction between the isocyanate group and the active hydrogen group becomes insufficient, and the amount is particularly preferably 0.5 to 3.0 parts by mass.
- an organometallic compound can also be used.
- the organometallic compound include an organic Suzuki compound, an organic bismuth compound, an organic lead compound, and an organic zinc compound.
- the amount of the organometallic compound used is 1.0 mass per 100 parts by mass of the polyol (A) (or the sum of the polyol (A) and the other high molecular weight polyol when a high molecular weight polyol other than the polyol (A) is used). Less than 0.005 to 1.0 parts by weight, especially 0.005 to 1.0 part by weight.
- a crosslinking agent can also be used.
- the crosslinking agent a compound having two or more active hydrogen-containing groups selected from a hydroxyl group, a primary amino group and a secondary amino group is preferable.
- the number of active hydrogen-containing groups is preferably 2-8.
- the molecular weight per active hydrogen-containing group of the crosslinking agent is preferably less than 30-500, more preferably 30-200. Two or more crosslinking agents may be used in combination.
- crosslinking agent examples include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, and trimethylol.
- the crosslinking agent is preferably from 0.1 to 20 parts by mass, particularly preferably from 0.5 to 10 parts by mass, per 100 parts by mass of the polyol (A).
- a foam stabilizer for forming good air bubbles is often used.
- the foam stabilizer include a silicone-based foam stabilizer and a fluorine-containing compound-based foam stabilizer.
- the present invention relates to a gold sealed with a raw material composition (E) containing a high molecular weight polyoxyalkylene polyol (A), an organic polyisocyanate compound (B), a blowing agent (C), and a catalyst (D).
- This is a method for producing a flexible polyurethane foam by foaming in a mold, wherein the air permeability of the flexible polyurethane foam foamed to a thickness of 26 mm using the raw material composition (E) is 0.085 m 3 Zmin or less.
- a flexible polyurethane foam foamed to a thickness of 26 mm is also referred to as a 26 mm thick sample. This is obtained by bubbling using a 26 mm high hermetic mold.
- 030 m 3 Zmin or less is more preferable, and 0.025 m 3 Zmin or less is preferable.
- the sound absorption performance at 500 Hz is 0.3 or more, and 2000 Hz Preferably has a sound absorption characteristic of 0.55 or more.
- the sound absorption characteristics can be measured by a method based on the JIS A1405 method (1963). 500Hz If the sound absorption characteristics of the car are less than 0.3, the sound absorption performance at low frequencies is insufficient, and it must be combined with other materials as a sound insulation material for automobiles. If the sound absorption performance at 2000 Hz is smaller than 0.55, the sound absorption at the middle frequency is insufficient, and the performance is poor as a soundproofing material, especially as a soundproofing material for automobiles.
- the sound absorption characteristic at 500 Hz is 0.35 or more, and particularly preferably 0.4 or more. Further, the sound absorption characteristic at 2000 Hz is preferably 0.57 or more, and particularly preferably 0.6 or more.
- the flexible foam of the present invention preferably has an F hardness of 80 or less.
- F hardness is 80 or less, a good soundproofing effect is obtained, and when the F hardness is more than 80, the soundproofing effect is inferior.
- the F hardness is preferably 40 or more U.
- Foam density of the flexible polyurethane foam is preferably 120KgZm 3 or less der Rukoto is preferred instrument 60- 120kg / m 3. If the foam density is larger than this range, the mass of the flexible foam increases, so that it is not possible to follow the recent reduction in the weight of automobiles. It is particularly preferred foam density is 80- 10 OkgZm 3. Further, the rebound resilience is preferably 30 to 50%. On the other hand, if the rebound resilience is larger than this range, the energy attenuation of the foam is reduced, and the acoustic characteristics are deteriorated.
- the molding of the flexible foam in the method of the present invention is carried out by using a low-pressure foaming machine or a high-pressure foaming machine to directly inject the raw material composition (E) into a closed mold (that is, a reaction injection molding method) or a metal mold. It is preferable to close the mold after injection.
- the high-pressure foaming machine preferably mixes two ordinary liquids.
- one of the two liquids contains the organic polyisocyanate conjugate
- the other liquid contains a mixture of all the raw materials other than the organic polyisocyanate conjugate (usually referred to as a polyol system liquid). )).
- a reactive mixture is formed and injected with a total of three or more components including a catalyst or a foam stabilizer (usually dispersed and dissolved in some high molecular weight polyols) and a foaming agent as separate components. You can also.
- the flexible foam of the present invention can also be produced by a method other than the cold S method usually produced by a cold cure method, for example, including a heating step.
- Polyol (p-1) is obtained by ring-opening addition polymerization of propylene oxide (PO) to glycerin and using a compound with a molecular weight of 1,000 as an initiator.
- PO propylene oxide
- EO a molecular weight of 1,000 as an initiator.
- the polyol (p-2) was produced by ring-opening addition polymerization of PO and then EO ring-opening addition polymerization in the presence of CsOH using glycerin as an initiator.
- the polyols (A-1) and (A-5) were produced by ring-opening addition polymerization of PO in the presence of KOH using glycerin as an initiator and then ring-opening addition polymerization of EO.
- the polyol (A-2) was produced by ring-opening addition polymerization of PO using KOH and a mixture of glycerin and sucrose as initiator, followed by ring-opening addition polymerization of EO.
- the polyol (A-3) was produced by ring-opening addition polymerization of a mixture of PO and EO in the presence of KOH with glycerin as an initiator.
- the polyol (A-4) was produced by ring-opening addition polymerization of PO in the presence of KOH using glycerin as an initiator. Table 2 shows other raw materials.
- the upper and lower mold temperatures of an aluminum mold with a height of 400 mm and a width of 26 mm and a height of 26 mm were heated to 60 ° C.
- the mixture (polyol system solution) of all the raw materials and the organic polyisocyanate conjugate solution were each adjusted to a solution temperature of 25 ⁇ 1 ° C.
- Add a predetermined amount of the organic polyisocyanate compound mixture to the polyol system solution stir and mix with a high-speed mixer (3000 rpm) for 5 seconds, pour into a mold at room temperature, seal, foam and harden to soften A polyurethane foam was manufactured.
- Tables 3 and 4 show the measurement results.
- the method for measuring the physical properties of the foam conforms to the following, and the standards used for measuring the physical properties of the flexible foam are shown below. Examples 18 to 18 are working examples, and examples 9 to 11 are comparative examples. In Table 3-4, the numerical value in the prescription column indicates% by mass.
- the flexible foam obtained in Examples 18 to 18 has good sound absorbing performance, particularly good sound absorbing performance at 500 Hz (low frequency region). Furthermore, foam density and F hardness also show appropriate values. On the other hand, in Examples 911, the sound absorption performance in the low frequency region tends to be inferior.
- the flexible polyurethane foam obtained according to the present invention has an improved sound absorbing property in a low frequency region of about 500Hz, and thus is suitable as a soundproofing material for buildings or vehicles. In particular, it is suitable as a soundproofing material for vehicles such as automobiles.
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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)
- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Multimedia (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04816210A EP1666514A4 (en) | 2003-09-19 | 2004-09-17 | POLYURETHANE FUEL AND MANUFACTURING METHOD THEREFOR |
US11/375,012 US20060160913A1 (en) | 2003-09-19 | 2006-03-15 | Flexible polyurethane foam and process for its production |
US12/210,509 US7588121B2 (en) | 2003-09-19 | 2008-09-15 | Flexible polyurethane foam and process for its production |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003-327588 | 2003-09-19 | ||
JP2003327588 | 2003-09-19 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/375,012 Continuation US20060160913A1 (en) | 2003-09-19 | 2006-03-15 | Flexible polyurethane foam and process for its production |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005028535A1 true WO2005028535A1 (ja) | 2005-03-31 |
Family
ID=34372874
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2004/013668 WO2005028535A1 (ja) | 2003-09-19 | 2004-09-17 | 軟質ポリウレタンフォームおよびその製造方法 |
Country Status (6)
Country | Link |
---|---|
US (2) | US20060160913A1 (ja) |
EP (1) | EP1666514A4 (ja) |
KR (1) | KR101115276B1 (ja) |
CN (1) | CN100509902C (ja) |
TW (1) | TW200516093A (ja) |
WO (1) | WO2005028535A1 (ja) |
Cited By (1)
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5998121A (ja) * | 1982-11-27 | 1984-06-06 | Bridgestone Corp | 制振材料 |
JPH08176258A (ja) * | 1994-10-24 | 1996-07-09 | Asahi Glass Co Ltd | 高弾性ポリウレタンフォームの製造方法 |
JPH08231676A (ja) * | 1995-02-28 | 1996-09-10 | Asahi Glass Co Ltd | 高弾性ポリウレタンフォームの製造方法 |
JP2002265555A (ja) * | 2001-03-07 | 2002-09-18 | Asahi Glass Co Ltd | 軟質ポリウレタンフォームの製造方法 |
JP2002322230A (ja) * | 2001-04-23 | 2002-11-08 | Asahi Glass Co Ltd | 軟質ポリウレタンフォームの製造方法及びポリオール組成物 |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5266143A (en) * | 1987-02-10 | 1993-11-30 | C.S.P. Centro Studi E Prototipi S.R.L. | Soundproofing panels for automobile applications and manufacturing processes therefor |
US5093380A (en) * | 1988-10-25 | 1992-03-03 | Asahi Glass Company, Ltd. | Polyurethane flexible foam and method for its production |
DE3942330A1 (de) * | 1989-12-21 | 1991-06-27 | Basf Ag | Verfahren zur herstellung von flexiblen polyurethan-weichschaumstoffen mit viskoelastischen, koerperschalldaempfenden eigenschaften und hierzu verwendbare polyoxyalkylen-polyol-mischungen |
JPH05209036A (ja) | 1991-08-29 | 1993-08-20 | Honda Motor Co Ltd | ポリウレタンフォームの製造方法 |
US6291638B1 (en) * | 1993-05-26 | 2001-09-18 | Laboratori Balducci S.P.A. | Hepatotropic conjugates of antiviral drugs carriers thereof and pharmaceutical compositions containing them |
JPH0759389A (ja) | 1993-08-13 | 1995-03-03 | Toshiba Corp | モータ間欠駆動制御方式及び装置 |
JPH10121597A (ja) | 1996-10-22 | 1998-05-12 | Nissan Motor Co Ltd | 吸音体及びこれを用いた車両 |
WO2000002951A1 (fr) * | 1998-07-10 | 2000-01-20 | Asahi Glass Company Ltd. | Catalyseur de polymerisation par decyclisation d'un oxyde d'alkylene, et son procede de fabrication et d'utilisation |
US6291538B1 (en) * | 1998-12-24 | 2001-09-18 | Kao Corporation | Process for preparing polyurethane foam |
DE19944762A1 (de) * | 1999-09-17 | 2001-03-22 | Basf Ag | Verfahren zur Herstellung von Blockweichschaumpolyolen |
EP1125959A1 (en) * | 2000-02-17 | 2001-08-22 | Mitsui Chemicals, Inc. | Microcellular polyurethane elastomer, and method of producing the same |
KR100663682B1 (ko) * | 2000-04-14 | 2007-01-02 | 아사히 가라스 가부시키가이샤 | 연질 폴리우레탄 폼의 제조방법 |
CN1257928C (zh) * | 2001-07-18 | 2006-05-31 | 旭硝子株式会社 | 多元醇和聚合物分散多元醇的制造方法 |
EP1283231A1 (en) * | 2001-08-06 | 2003-02-12 | Asahi Glass Company Ltd. | Flexible polyurethane foam, its production method and material system for its production |
ATE341572T1 (de) * | 2001-11-29 | 2006-10-15 | Asahi Glass Co Ltd | Polyurethanweichschaum und verfahren zur herstellung |
DK1316573T3 (da) * | 2001-11-30 | 2007-08-27 | Asahi Glass Co Ltd | Fleksibelt polyurethanskum og fremgangsmåde til dets fremstilling |
CN100408609C (zh) * | 2001-12-21 | 2008-08-06 | 旭硝子株式会社 | 低回弹软质聚氨酯泡沫体及其制造方法 |
AU2004293315B2 (en) | 2003-11-26 | 2009-04-02 | Asahi Glass Company, Limited | Flexible polyurethane foam, process for producing the same, and automotive sheet employing the same |
WO2006054657A1 (ja) | 2004-11-18 | 2006-05-26 | Asahi Glass Company, Limited | 軟質ポリウレタンフォームの製造方法 |
CN101061155B (zh) | 2004-11-24 | 2010-07-21 | 旭硝子株式会社 | 软质聚氨酯泡沫塑料、其制造方法以及汽车用座垫 |
WO2006115169A1 (ja) | 2005-04-21 | 2006-11-02 | Asahi Glass Company, Limited | 低反発性軟質ポリウレタンフォームおよびその製造方法 |
JP5082847B2 (ja) | 2005-05-25 | 2012-11-28 | 旭硝子株式会社 | 軟質ポリウレタンフォームおよびその製造方法、該軟質ポリウレタンフォームを用いた自動車用シート |
JP5145935B2 (ja) | 2005-05-25 | 2013-02-20 | 旭硝子株式会社 | 軟質ポリウレタンフォームおよびその製造方法、該軟質ポリウレタンフォームを用いた自動車用シート |
CN101180338B (zh) | 2005-05-25 | 2011-05-04 | 旭硝子株式会社 | 软质聚氨酯泡沫塑料及其制造方法、利用该软质聚氨酯泡沫塑料的汽车用座垫 |
KR101307632B1 (ko) | 2005-08-05 | 2013-09-12 | 아사히 가라스 가부시키가이샤 | 연질 폴리우레탄 폼, 그 제조 방법 및 자동차용 시트 |
-
2004
- 2004-09-17 KR KR1020067000383A patent/KR101115276B1/ko not_active IP Right Cessation
- 2004-09-17 WO PCT/JP2004/013668 patent/WO2005028535A1/ja active Application Filing
- 2004-09-17 TW TW093128263A patent/TW200516093A/zh not_active IP Right Cessation
- 2004-09-17 CN CNB2004800262583A patent/CN100509902C/zh not_active Expired - Fee Related
- 2004-09-17 EP EP04816210A patent/EP1666514A4/en not_active Withdrawn
-
2006
- 2006-03-15 US US11/375,012 patent/US20060160913A1/en not_active Abandoned
-
2008
- 2008-09-15 US US12/210,509 patent/US7588121B2/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5998121A (ja) * | 1982-11-27 | 1984-06-06 | Bridgestone Corp | 制振材料 |
JPH08176258A (ja) * | 1994-10-24 | 1996-07-09 | Asahi Glass Co Ltd | 高弾性ポリウレタンフォームの製造方法 |
JPH08231676A (ja) * | 1995-02-28 | 1996-09-10 | Asahi Glass Co Ltd | 高弾性ポリウレタンフォームの製造方法 |
JP2002265555A (ja) * | 2001-03-07 | 2002-09-18 | Asahi Glass Co Ltd | 軟質ポリウレタンフォームの製造方法 |
JP2002322230A (ja) * | 2001-04-23 | 2002-11-08 | Asahi Glass Co Ltd | 軟質ポリウレタンフォームの製造方法及びポリオール組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1666514A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101238163B (zh) * | 2005-08-05 | 2011-02-09 | 旭硝子株式会社 | 软质聚氨酯泡沫塑料、其制造方法以及汽车用座椅 |
Also Published As
Publication number | Publication date |
---|---|
CN1849351A (zh) | 2006-10-18 |
US7588121B2 (en) | 2009-09-15 |
US20060160913A1 (en) | 2006-07-20 |
KR20060059957A (ko) | 2006-06-02 |
KR101115276B1 (ko) | 2012-03-05 |
TWI361810B (ja) | 2012-04-11 |
EP1666514A4 (en) | 2009-04-22 |
CN100509902C (zh) | 2009-07-08 |
EP1666514A1 (en) | 2006-06-07 |
TW200516093A (en) | 2005-05-16 |
US20090008595A1 (en) | 2009-01-08 |
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