WO2013161854A1 - ポリウレタン発泡組成物および軟質ポリウレタンフォームの製造方法 - Google Patents
ポリウレタン発泡組成物および軟質ポリウレタンフォームの製造方法 Download PDFInfo
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- WO2013161854A1 WO2013161854A1 PCT/JP2013/062008 JP2013062008W WO2013161854A1 WO 2013161854 A1 WO2013161854 A1 WO 2013161854A1 JP 2013062008 W JP2013062008 W JP 2013062008W WO 2013161854 A1 WO2013161854 A1 WO 2013161854A1
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- 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
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
- C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
- C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/14—Manufacture of cellular products
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
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- 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
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- 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
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- 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
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- 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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
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- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
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- C08G2110/00—Foam properties
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- C08G2350/00—Acoustic or vibration damping material
Definitions
- the present invention relates to a polyurethane foam composition and a method for producing a flexible polyurethane foam, and in particular, a foam composition for molding a flexible polyurethane foam in which a specific cross-linking agent composition is blended at a specific ratio, and the foam composition.
- the present invention relates to a method for producing a flexible polyurethane foam.
- Soft polyurethane foam is widely used in cushioning materials for vehicles, mats for furniture, bedding, miscellaneous goods, etc. because of its high cushioning properties.
- a flexible polyurethane foam is usually produced by reacting an organic polyisocyanate with two or more compounds containing active hydrogen in the presence of a catalyst, a foam stabilizer and other additives.
- the active hydrogen-containing compound include polyols, polymer polyols obtained by radical polymerization of acrylonitrile and styrene in polyols, primary and secondary polyamines, and water.
- starting materials are mixed with a high-pressure foaming machine, injected into a mold, molded, and then the foamed cells in the foam are forcibly connected using a compressor.
- the method of generalization is taken.
- Patent Document 2 includes polyisocyanate, water, an organic acid, and an aprotic polar solvent, thereby improving the brittleness of the foam surface without crosslinking at high temperatures, and providing adhesion.
- a composition for producing a polyurethane foam has been proposed.
- Patent Document 3 discloses a method for producing a polyurethane foam which is remarkably excellent in scorch prevention by using a cyclic lactone as a solvent.
- Patent Document 4 and Patent Document 5 show that a specific solvent is blended in order to improve the adhesive properties of the rigid polyurethane foam for building materials.
- compositions shown in Patent Documents 2 to 5 are all compositions for producing rigid polyurethane foams, and even if these compositions are used, the structure and characteristics of the cells are different from rigid polyurethane foams. A very different flexible polyurethane foam cannot be obtained. In particular, a satisfactory foam could not be obtained in terms of compressive residual strain, compressive residual strain under wet heat conditions, and feel such as sliminess and slipperiness.
- the present invention has been made in order to solve such a problem, and obtains a flexible polyurethane foam having a remarkably improved compressive residual strain under wet heat conditions and having a good feeling such as sliminess and slipperiness.
- An object of the present invention is to provide a polyurethane foam composition that can be used.
- the polyurethane foam composition of the present invention comprises: (A) a polyisocyanate; (B) an active hydrogen-containing compound containing (B1) polyol and (B2) water; A polyurethane foam composition containing 0.1 to 20 parts by mass of a catalyst, and (C) a crosslinking agent composition with respect to 100 parts by mass of the (B1) polyol,
- the (C) crosslinking agent composition is: Formula (1): HO (CH 2 CH 2 O) m H (in Formula (1), m is an integer of 3 to 30), Or Formula (2): R 1 -[(CH 2 CH 2 O) n H] x (In the formula (2), R 1 is a group selected from a glycerol group, a trimethylol group, a pentaerythritol group, and a diglycerol group, n is an integer of 1 to 15, and x is 3 or 4.
- Ethoxylate derivative (CA) having a mass average molecular weight of 2000 or less, Formula (3): H (OR 2 OCOR 3 CO) y —OR 2 OH, or Formula (4): R 4 — [(OCOR 3 CO—OR 2 ) y —OH] 3 (In the formulas (3) and (4), R 2 is an alkyl group having 2 to 10 carbon atoms, R 3 is an alkyl group having 1 to 15 carbon atoms, and y is an integer of 1 to 14).
- R 4 is an alkyl group having 1 to 15 carbon atoms.
- at least one crosslinking agent (C1) selected from ester compounds (CB) having a weight average molecular weight of 2500 or less When, (C2) containing an aprotic polar solvent, In the (C) crosslinking agent composition, the total of the content (a) of the (CA) ethoxylate derivative and the content (b) of the (CB) ester compound with respect to the content c of the (C2) aprotic polar solvent.
- the mass ratio ((a + b) / c) is 1/10 to 10/1.
- the method for producing a flexible polyurethane foam according to the present invention is characterized by using the above-mentioned polyurethane foam composition.
- the compressive residual strain is remarkably improved as compared with the prior art, and the flexible polyurethane foam is excellent in touch (smoothness and slipperiness) and the like. Can be obtained with good production efficiency.
- a polyurethane foam composition according to an embodiment of the present invention includes an active hydrogen-containing compound containing (A) polyisocyanate, (B) (B1) polyol, and (B2) water, a catalyst, and (C) a crosslinking agent composition.
- A active hydrogen-containing compound containing
- B (B1) polyol, and (B2) water, a catalyst, and
- C a crosslinking agent composition.
- polyisocyanate As the polyisocyanate as component (A), known aliphatic, alicyclic and aromatic organic isocyanate compounds having two or more isocyanate groups can be used. For example, hexamethylene diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate (also referred to as toluene diisocyanate or toluidine diisocyanate: TDI), 2,2′- or 2, Examples include alkylene diisocyanates or arylene isocyanates such as 4'- or 4,4'-diphenylmethane diisocyanate (MDI), and known triisocyanates and polymeric MDIs (crude diphenylmethane diisocyanate; referred to as crude MDI).
- MDI 4,4'-diphenylmethane diisocyanate
- crude MDI crude MDI
- Suitable isocyanates for obtaining flexible foams are a mixture of 80% by weight 2,4-TDI and 20% by weight 2,6-TDI, 65% by weight 2,4-TDI and 35% by weight 2, Mixtures of 6-TDI, all polyisocyanates of the MDI type, and mixtures of these TDI and MDI. It is preferable that 10% by mass or more of the polyisocyanate as the component (A) is 2,4-TDI and / or 2,6-TDI.
- the amount of polyisocyanate used in the production of foam (foam) is described as “Isocyanate Index”.
- the “isocyanate index” indicates the percentage of isocyanate groups relative to the active hydrogen-containing groups that can react with isocyanate groups, the theory required to react the actual amount of polyisocyanate used in the reaction mixture with all of the active hydrogens. Divided by the stoichiometric amount of polyisocyanate required and multiplied by 100.
- the isocyanate index is not particularly limited, but is generally in the range of 70 to 130 in the production of flexible foam.
- the active hydrogen-containing compound as component (B) contains (B1) polyol and (B2) water, respectively.
- the polyol is a compound having two or more active hydrogen-containing functional groups such as a hydroxyl group capable of reacting with the isocyanate group of the component (A) in the molecule, and known ones can be used.
- the number of the active hydrogen-containing functional group (hydroxyl group) of the polyol is preferably 2 to 8, and most preferably 2.3 to 6. If the number of hydroxyl groups is 2 or more, the durability of the flexible polyurethane foam will be good. In addition, by setting the average number of hydroxyl groups to 6 or less, the flexible polyurethane foam does not become too hard and mechanical properties such as elongation become good.
- the compound having two or more hydroxyl groups include polyether polyols and polyester polyols.
- it is preferably composed of only one or more kinds of polyether-based polyols, or those based on polyether-based polyols and used in combination with polyester-based polyols, polyhydric alcohols, polyamines, alkanolamines, and other active hydrogen-containing compounds. .
- the polyol that can be used in the embodiment of the present invention is not particularly limited, but those classified below are preferably used alone or in combination. That is, 1) alkylene oxide adduct of polyhydroxyalkane 2) alkylene oxide adduct of non-reducing sugar and sugar derivative 3) alkylene oxide adduct of phosphoric acid and polyphosphoric acid 4) alkylene oxide adduct of polyphenols 5) primary and secondary It is an alkylene oxide adduct of amine.
- An alkylene oxide adduct of polyhydroxyalkane suitable for obtaining a flexible foam is an ethylene oxide adduct of trihydroxyalkane and a propylene oxide adduct.
- the grafted polyol or polymer polyol is one kind of polyol useful for the embodiment of the present invention, and can be used widely in the production of flexible foam.
- the polymer polyol is, for example, a polyol containing a stable dispersion of a polymer (for example, vinyl polymer fine particles) in the polyol of type 1) among the above polyols 1) to 5).
- (B1) polyol having a hydroxyl value of 10 to 120 mgKOH / g it is preferable to use (B1) polyol having a hydroxyl value of 10 to 120 mgKOH / g.
- the hydroxyl value By setting the hydroxyl value to 10 mgKOH / g or more, the viscosity of the polyol does not increase and the workability during production is good. Moreover, durability of a flexible polyurethane foam becomes favorable because a hydroxyl value shall be 120 mgKOH / g or less. It is preferable to select the hydroxyl value of the polyol according to the use of the polyurethane foam.
- polyols as component (B1) include, for example, Sanix FA-703 (glycerin-propylene oxide / ethylene oxide adduct, hydroxyl value 33 mgKOH / g; manufactured by Sanyo Chemical Industries, Ltd.), Sanniks FA-728R (Polymer polyol, hydroxyl value 28.5 mgKOH / g; manufactured by Sanyo Chemical Industries), Actol PPG EP-901 (glycerin-propylene oxide / ethylene oxide adduct, hydroxyl value 24 mgKOH / g; manufactured by Mitsui Chemicals), Act Cole POP-36 / 90 (polymer polyol, hydroxyl value 24 mg KOH / g: manufactured by Mitsui Chemicals), Adeka polyol AM-302 (glycerin-propylene oxide / ethylene oxide adduct, hydroxyl value 57.6 mg KOH / g; manufactured by Adeka) And the like.
- Sanix FA-703 gly
- Water (B2) is blended as a chemical foaming agent that forms foam by carbon dioxide gas generated by reaction with isocyanate groups in the polyisocyanate (A). At least 50% of the gas volume forming the foam (ie, at least 50% by volume of the total foam gas) is carbon dioxide produced by the reaction of the (B2) component water and the (A) isocyanate group of the polyisocyanate. In particular, it is more preferable that water is used alone as a foaming agent, and that 100% of the foaming gas capacity is carbon dioxide produced by the reaction of water and isocyanate groups. That is, in addition to water that is a chemical foaming agent, a chemical foaming agent and a physical foaming agent that are organic acids such as formic acid can be used in combination, but it is more preferable to use water alone for foaming. .
- the catalyst promotes the reaction between the isocyanate group in the polyisocyanate as the component (A) and the active hydrogen-containing group in the active hydrogen-containing compound as the component (B), and can be referred to as a gelation catalyst.
- a catalyst include tertiary amines such as triethylenediamine, bis [(2-dimethylamino) ethyl] ether, N, N, N, N-tetramethylhexamethylenediamine, potassium acetate, and 2-ethyl.
- Carboxylic acid metal salts such as potassium hexanoate, organotin compounds such as dibutyltin dilaurate, stannous octoate, and the like can be used.
- the blending amount of these catalysts is an amount usually used for promoting the reaction.
- stimulates reaction of the said (B2) water and the isocyanate group of the polyisocyanate which is (A) component can also be mix
- the crosslinking agent composition comprises (CA) one or more crosslinking agents (C1) selected from (CA) an ethoxylate derivative having a mass average molecular weight of 2000 or less and (CB) an ester compound having a mass average molecular weight of 2500 or less. , (C2) an aprotic polar solvent.
- the ratio (mass ratio) of the content of the crosslinking agent (C1) to the content of the (C2) aprotic polar solvent in (C) the crosslinking agent composition is 1/10 to 10/1. .
- the (CA) ethoxylate derivative constituting the crosslinking agent is also referred to as an ethylene oxide derivative.
- the mass average molecular weight (Mw) is preferably 1200 or less.
- m is an integer of 3 to 30. m is preferably an integer of 5 to 25.
- R 1 is a group selected from a glycerol group, a trimethylol group, a pentaerythritol group, and a diglycerol group. R 1 is preferably a glycerol group.
- n is an integer of 1 to 15, and x is 3 or 4.
- n is preferably an integer of 2 to 8, and x is preferably 3.
- ethoxylate derivative that is the component (CA) include polyoxyethylene glyceryl ether, polyethylene glycol, polyoxyethylene trimethylol ether, polyoxyethylene pentaerythritol ether, polyoxyethylene diglycerol ether, and the like. It is done.
- (CB) ester compound constituting the crosslinking agent is Formula (3): H (OR 2 OCOR 3 CO) y —OR 2 OH, or Formula (4): R 4 — [(OCOR 3 CO—OR 2 ) y —OH] 3 , represented by 2500 or less It has a mass average molecular weight (Mw).
- the mass average molecular weight (Mw) is preferably 1200 or less.
- R 2 is an alkyl group having 2 to 10 carbon atoms.
- R 2 include a 3-methyl-1,5-pentyl group, an isopropyl group, a diethylene ether group, and the like, and a 3-methyl-1,5-pentyl group is preferable.
- R 3 is an alkyl group having 1 to 15 carbon atoms. Examples of R 3 include a butylene group, a diethylene group, and a hexylene group, but a butylene group is preferable.
- y is an integer of 1 to 14. y is preferably 1-9.
- (CB) ester compound examples include Formula: H- [O (CH 2 CH 2 CH (CH 3 ) CH 2 CH 2 -O-CO-CH 2 CH 2 CH 2 CH 2 CO)] y -O-CH 2 CH 2 CH (CH 3 ) CH 2 CH 2 -OH or formula: R 4 -[(OCOCH 2 CH 2 CH 2 CH 2 CO-OCH 2 CH 2 CH (CH 3 ) CH 2 CH 2 ) y -OH] 3 (Wherein R 4 is an alkyl group such as a group represented by the following formula, and y is an integer of 1 to 9): 3-methyl-1,5-pentanediol adipate Can be mentioned.
- (C) As a crosslinking agent constituting the crosslinking composition, (C1) a crosslinking agent can be used alone from the above-mentioned (CA) ethoxylate derivative and (CB) ester compound, or two or more kinds. Can also be used together.
- CA ethoxylate derivative
- CB ester compound
- ⁇ (C2) aprotic polar solvent examples include dialkyl sulfoxide, N, N-dialkylalkanoamide, 1-methyl-2-pyrrolidone, organic carbonate, cyclic ester and the like.
- aprotic polar solvent is used in the usual sense. That is, it refers to a polar organic solvent that cannot be a source of active substituted hydrogen atoms or atomic groups suitable for forming a strong hydrogen bond with any chemical species.
- dialkyl sulfoxide examples include dimethyl sulfoxide, diethyl sulfoxide, diisobutyl sulfoxide and the like.
- N, N-dialkylalkanoamides examples include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide and the like.
- organic carbonate examples include dimethyl carbonate, ethylene carbonate, and propylene carbonate.
- cyclic ester examples include ⁇ -butyrolactone, ⁇ -caprolactone, and ⁇ -valerolactone.
- (C2) As the aprotic polar solvent, one kind selected from the aforementioned compound group may be used alone, or two or more kinds may be mixed and used.
- the mass ratio of the content of the crosslinking agent (C1) to the content of the (C2) aprotic polar solvent in the (C) crosslinking agent composition that is, (C2) the content of the aprotic polar solvent
- the total mass ratio ((a + b) / c) of the content (a) of the (CA) ethoxylate derivative and the content (b) of the (CB) ester compound with respect to the amount c is in the range of 1/10 to 10/1. ing.
- the blending ratio of the (C) crosslinking agent composition is 0.01 to 20 parts by mass with respect to 100 parts by mass of the polyol (B1). A range of 0.1 to 10 parts by mass is more preferable.
- (C) When the blending ratio of the cross-linking agent composition is less than 0.01 parts by mass, sufficient improvement of compression residual strain of the foam (foam) under wet heat conditions and an effect of suppressing an increase in the viscosity of the composition are sufficient. I ca n’t raise it. Moreover, since a fall of another physical property will arise when a mixture ratio exceeds 20 mass parts, it is unpreferable.
- the foam composition of the embodiment of the present invention is obtained by mixing the components (A) to (C) and the catalyst with a high-speed mixer or the like.
- the foam composition of the embodiment may contain a foam stabilizer in addition to the components (A) to (C) and the catalyst.
- additives such as a filler, a stabilizer, a coloring agent, a flame retardant, can further be mix
- a foam stabilizer is a surfactant blended to form good bubbles. Any foam stabilizer can be used as long as it is a known foam stabilizer in the polyurethane industry. For example, there are a silicone-based foam stabilizer and a fluorine-containing compound-based foam stabilizer.
- Such a polyurethane foam composition of the present invention can be used to produce a flexible polyurethane foam by a one-shot foaming method.
- the “one-shot foaming method” is a method for producing polyurethane foam in one step. In this method, all of the ingredients necessary to produce a polyurethane foam, including polyisocyanate, polyol, water, crosslinker, catalyst, foam stabilizer, optional blowing agent, etc., are simply blended together. It is casted on a moving conveyor or in a mold of an appropriate form to be foamed and cured.
- the foam (foam) obtained from the polyurethane foam composition of the present invention preferably has a density of 14 kg / m 3 or more from the viewpoint of obtaining high resilience characteristics. Moreover, it is preferable that it has a density of 80 kg / m 3 or less from the viewpoints of feeling such as sitting comfort, riding comfort, touch, and cost.
- the production efficiency is greatly improved by using a specific crosslinking agent composition.
- a flexible polyurethane foam with good physical properties can be obtained. More specifically, it is possible to obtain a flexible polyurethane foam that has improved compression residual strain and compression residual strain under wet heat conditions, has good sliminess and slipperiness, and is excellent in touch and touch.
- the resulting flexible polyurethane foam is suitable as a high resilience polyurethane foam for vehicle seats, furniture cushions, bedding mattresses, and the like.
- Examples 1 to 10 Comparative Examples 1 to 9 (A) polyisocyanate, (B1) polyol, (B2) water, and (C) component crosslinking agent-1 to crosslinking agent-5, polar solvent-6, polar solvent-7, crosslinking agent-9, Then, the crosslinking agent-10, the catalyst and the foam stabilizer were blended in the compositions (parts by mass) shown in Tables 1 and 2, respectively, and mixed by a high speed mixer. After mixing, the obtained mixture was immediately poured into a wooden mold (inner dimensions 200 ⁇ 200 ⁇ 200 mm) on which release paper was laid.
- Adeka polyol AM-302 hydroxyl value 57.6 mgKOH
- the gasification catalyst is a catalyst that promotes the reaction between (B2) water and the isocyanate group of (A) polyisocyanate, and the gelation catalyst is (A) an isocyanate group in the polyisocyanate.
- B A catalyst that promotes the reaction with the active hydrogen-containing group in the active hydrogen-containing compound.
- Crosslinker-1 to Crosslinker-5, Polar solvent-6, Polar solvent-7, Crosslinker-9, and Crosslinker-10 were respectively those described below.
- the cream time and rise time of the obtained composition were measured as shown below.
- [Cream time] The time (seconds) from the start of mixing of the liquid until the reaction mixed liquid became cloudy and rose up was measured.
- [Rise time] The time (seconds) from the start of the mixing of the liquid until the reaction mixture foamed and reached the maximum height was measured.
- the composition injected into the wooden mold was foam-molded by holding it at room temperature (23 ° C. ⁇ 2 ° C.) for 3 minutes. Thereafter, the foam was taken out from the wooden mold together with the release paper, crosslinked in an oven at 120 ° C. for 10 minutes, and then cooled to room temperature to obtain a polyurethane foam.
- the obtained polyurethane foam was cut into 10 cm ⁇ 10 cm ⁇ 10 cm, and then the density was measured.
- the hardness was measured in accordance with the hardness measurement of JIS K6401-2: 2004 (ISO 2439: 1997). Using a compression plate having a size of 314 cm 2 , hardness when compressed by 25% (25% hardness) hardness when compressed by 40% (40% hardness) and hardness when compressed by 65% ( 65% hardness) was measured.
- Adeka polyol G-3000B glycerin-propylene oxide adduct, hydroxyl value 54 mgKOH / g; manufactured by Adeka
- foam stabilizer NIAX silicon L-598 (silicone foam stabilizer: Momentive ⁇ Performance Materials Japan G.K.)
- A polyisocyanate, amine gas catalyst, tin 2-ethylhexanoate catalyst (gelation catalyst), and crosslinking agent-1, crosslinking agent-2, As the crosslinking agent-4, polar solvent-6, and polar solvent-7, those described above were used.
- the obtained foamed composition was immediately poured into a wooden mold (inner dimensions 200 ⁇ 200 ⁇ 200 mm) on which release paper was laid, and then the cream time (seconds) and the rise time (seconds) were set in the examples. Measurement was performed in the same manner as in 1 to 10.
- the composition injected into the wooden mold was foam-molded by holding it at room temperature (23 ° C. ⁇ 2 ° C.) for 3 minutes. Thereafter, the foam was taken out from the wooden mold together with the release paper, and was crosslinked by heating in an oven at 120 ° C. for 10 minutes, and then cooled to room temperature.
- the polyurethane foam thus obtained was cut into 10 cm ⁇ 10 cm ⁇ 10 cm, and the density (kg / m 3 ) was measured. Further, the compression residual strain (%), wet heat compression residual strain (%) and air permeability (L / min.) Of the obtained polyurethane foam were measured in the same manner as described above. The measurement results are shown in the lower columns of Tables 3 and 4.
- Examples 17 to 19 Comparative Examples 14 to 16 (A) polyisocyanate, (B1) polyol, (B2) water, (C) component crosslinker-1, polar solvent-6, crosslinker-8, catalyst and foam stabilizer, After blending with the composition (parts by mass) shown in Table 5 and mixing with a high-speed mixer, the mixture was immediately poured into an aluminum mold (inner dimensions 300 ⁇ 300 ⁇ 100 mm) whose temperature was adjusted to 60 ⁇ 2 ° C. It was closed and held for 5 minutes as it was for foam molding to obtain a polyurethane foam. At this time, the discharge time was measured as follows.
- discharge time The time (seconds) from the addition of (A) polyisocyanate to the reaction mixture until the foam first appeared through the four vent holes at the top of the mold was measured as the discharge time.
- (B1) polyether polyol is Sannix FA-703 (glycerin-propylene oxide / ethylene oxide adduct, hydroxyl value 34 mg KOH / g; manufactured by Sanyo Chemical Industries), and (B1) polymer polyol is Sun Nix FA-728R (hydroxyl value 34 mgKOH / g; manufactured by Sanyo Kasei Kogyo Co., Ltd.) was used as the catalyst.
- Niax catalyst A-1 amine gasification catalyst: manufactured by Momentive Performance Materials Japan GK
- Niax catalyst A-33 Amine-based gelation catalyst: manufactured by Momentive Performance Materials Japan LLC
- the density (kg / m 3 ) of the obtained polyurethane foam was measured. The density was measured as it was as the overall density after removing the foam from the mold. Further, the properties of the obtained polyurethane foam were measured in accordance with JIS K 6401 as shown below.
- FTC Force-to-crush
- CA ethoxylate derivative
- CB ester compound
- Crosslinking Agent-1 to Crosslinking Agent-3 and Crosslinking Agent-8 to Crosslinking Agent-10 formulated so that the mass ratio to content c ((a + b) / c) is in the range of 1/10 to 10/1.
- the polyurethane foams of Examples 1 to 19 obtained in this manner were the polyurethane foams of Comparative Example 1, Comparative Example 14 and Comparative Example 16 obtained without blending the crosslinking agent, and Crosslinking Agent-4 to Crosslinking Agent-5. Obtained using polar solvent-6 and polar solvent-7 Comparative Examples 2 to 13, and in comparison with the polyurethane foam of Comparative Example 15, a compression residual strain in wet heat conditions is significantly improved.
- the polyurethane foams of Comparative Example 14 and Comparative Example 16 obtained without blending a cross-linking agent have both poor sliminess and slipperiness in the feel test.
- the polyurethane foam of Comparative Example 14 has poor compression residual strain characteristics.
- the polyurethane foam of Comparative Example 15 in which (C2) polar solvent-6 consisting only of an aprotic polar solvent is blended has a poor compressive residual strain property, although the result of the feel test is not so bad.
- the polyurethane foam composition of the present invention compression residual strain, particularly compression residual strain under wet heat conditions, is remarkably improved, and a flexible polyurethane foam excellent in feel such as sliminess and slipperiness is produced satisfactorily. Can be obtained with efficiency.
- the resulting flexible polyurethane foam is suitable as a high resilience polyurethane foam for vehicle seats, furniture cushions, bedding mattresses, and the like.
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Abstract
Description
また、低密度化を進める際に求められる技術的課題として、圧縮永久歪み(圧縮残留歪みともいう。)の低減などの耐久性の維持が挙げられる。例えば、特許文献1においては、特定の架橋剤組成物を用いることで耐久性を向上させる技術が提案されている。しかし、特許文献1の方法では、低密度化に起因する物性の低下は大幅に改善できるが、すわり心地などとして表される感触の改善には至っていない。
(A)ポリイソシアネートと、
(B)(B1)ポリオールと(B2)水を含む活性水素含有化合物と、
触媒、および
(C)架橋剤組成物を前記(B1)ポリオール100質量部に対して0.1~20質量部
含有するポリウレタン発泡組成物であり、
前記(C)架橋剤組成物は、
式(1):HO(CH2CH2O)mH(式(1)中、mは3~30の整数である。)、
または式(2):R1-[(CH2CH2O)nH]x
(式(2)中、R1は、グリセロール基、トリメチロール基、ペンタエリスリトール基、ジグリセロール基より選ばれる基であり、nは1~15の整数であり、xは3または4である。)で表わされる、質量平均分子量が2000以下のエトキシレート誘導体(CA)と、
式(3):H(OR2OCOR3CO)y-OR2OH、または
式(4):R4-[(OCOR3CO-OR2)y-OH]3
(式(3)および式(4)中、R2は炭素数2~10のアルキル基であり、R3は炭素数1~15のアルキル基であり、yは1~14の整数である。式(4)中、R4は炭素数1~15のアルキル基である。)で表わされる、質量平均分子量が2500以下のエステル化合物(CB)とから選ばれる少なくとも1種の架橋剤(C1)と、
(C2)非プロトン性極性溶媒とを含有し、
前記(C)架橋剤組成物において、前記(C2)非プロトン性極性溶媒の含有量cに対する、前記(CA)エトキシレート誘導体の含有量aと前記(CB)エステル化合物の含有量bの合計の質量比((a+b)/c)が、1/10~10/1であることを特徴とする。
(A)成分であるポリイソシアネートとしては、2個以上のイソシアネート基を有する公知の脂肪族、脂環族および芳香族の有機イソシアネート化合物を使用することができる。例えば、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、4,4-ジシクロヘキシルメタンジイソシアネート、2,4-あるいは2,6-トリレンジイソシアネート(トルエンジイソシアネートあるいはトルイジンジイソシアネートともいう。:TDI)、2,2´-または2,4´-あるいは4,4´-ジフェニルメタンジイソシアネート(MDI)のようなアルキレンジイソシアネートあるいはアリーレンイソシアネート、ならびに公知のトリイソシアネートおよびポリメリックMDI(粗製ジフェニルメタンジイソシアネート;クルードMDIと呼称されている)などが挙げられる。
(B)成分である活性水素含有化合物は、(B1)ポリオールと(B2)水をそれぞれ含有する。
1)ポリヒドロキシアルカンのアルキレンオキサイド付加物
2)非還元糖および糖誘導体のアルキレンオキサイド付加物
3)リン酸およびポリリン酸のアルキレンオキサイド付加物
4)ポリフェノール類のアルキレンオキサイド付加物
5)一級および二級アミンのアルキレンオキサイド付加物である。
触媒は、前記(A)成分であるポリイソシアネート中のイソシアネート基と(B)成分である活性水素含有化合物中の活性水素含有基との反応を促進するものであり、ゲル化触媒ということができる。このような触媒としては、例えば、トリエチレンジアミン、ビス[(2-ジメチルアミノ)エチル]エーテル、N,N,N,N-テトラメチルヘキサメチレンジアミンなどの3級アミン類、酢酸カリウム、2-エチルヘキサン酸カリウムなどのカルボン酸金属塩、ジブチルチンジラウレート、スタナスオクトエートなどの有機スズ化合物などを使用することができる。これらの触媒の配合量は、前記反応促進に通常使用される量とする。また、本発明においては、前記(B2)水と(A)成分であるポリイソシアネートのイソシアネート基との反応を促進する触媒(ガス化触媒)を配合することもできる。
(C)架橋剤組成物は、(CA)質量平均分子量が2000以下のエトキシレート誘導体と、(CB)質量平均分子量が2500以下のエステル化合物とから選ばれる1種以上の架橋剤(C1)と、(C2)非プロトン性極性溶媒とを含有する。そして、(C)架橋剤組成物中の(C2)非プロトン性極性溶媒の含有量に対する架橋剤(C1)の含有量の比(質量比)が、1/10~10/1となっている。すなわち、(CA)エトキシレート誘導体の含有量(質量)をa、(CB)エステル化合物の含有量(質量)をb、(C3)非プロトン性極性溶媒の含有量(質量)をcとするとき、(a+b)/c=1/10~10/1となっている。
(C1)架橋剤を構成する(CA)エトキシレート誘導体は、エチレンオキサイド誘導体ともいい、
式(1):HO(CH2CH2O)mH、または
式(2):R1-[(CH2CH2O)nH]xで表わされ、2000以下の質量平均分子量(Mw)を有する。質量平均分子量(Mw)は1200以下が好ましい。
(C1)架橋剤を構成する(CB)エステル化合物は、
式(3):H(OR2OCOR3CO)y-OR2OH、または
式(4):R4-[(OCOR3CO-OR2)y-OH]3で表わされ、2500以下の質量平均分子量(Mw)を有する。質量平均分子量(Mw)は1200以下が好ましい。
式:H-[O(CH2CH2CH(CH3)CH2CH2-O-CO-CH2CH2CH2CH2CO)] y-O-CH2CH2CH(CH3)CH2CH2-OHまたは
式:R4-[(OCOCH2CH2CH2CH2CO-OCH2CH2CH(CH3)CH2CH2) y-OH]3
(式中、R4は、以下の式で表される基等のアルキル基であり、yは1~9の整数である。)で表される3-メチル-1,5-ペンタンジオールアジペートが挙げられる。
(C)架橋組成物を構成する(C2)非プロトン性極性溶媒としては、ジアルキルスルフォキシド、N,N-ジアルキルアルカノアミド、1-メチル-2-ピロリドン、有機カーボネート、環状エステル等が挙げられる。
なお、本明細書において、「非プロトン性極性溶媒」は通常の意味で用いる。すなわち、任意の化学種との強固な水素結合の形成に好適な活性置換水素原子または原子団の供給源とはなり得ない、極性有機溶媒を指す。
N,N-ジアルキルアルカノアミドとしては、N,N-ジメチルフォルムアミド、N,N-ジメチルアセトアミド、N,N-ジエチルアセトアミド等が挙げられる。
有機カーボネートとしては、ジメチルカーボネート、エチレンカーボネート、プロピレンカーボネート等が挙げられる。
環状エステルとしては、γ-ブチロラクトン、ε-カプロラクトン、γ-バレロラクトン等が挙げられる。
(a+b)/cが1/10未満の場合には、耐久性が十分ではなく、(a+b)/cが10/1を超えると、良好な感触すなわち満足できる手触りや、すわり心地の改善が得られない。
(A)ポリイソシアネートと、(B1)ポリオールと、(B2)水と、(C)成分である架橋剤-1~架橋剤-5、極性溶媒-6、極性溶媒-7、架橋剤-9、および架橋剤-10と、触媒および整泡剤を、それぞれ表1および表2に示す組成(質量部)で配合し、高速ミキサーにより混合した。混合後、得られた混合物を直ちに離型紙が敷かれた木製型(内寸200×200×200mm)内に注入した。
なお、前記したように、ガス化触媒は、(B2)水と(A)ポリイソシアネートのイソシアネート基との反応を促進する触媒であり、ゲル化触媒は、(A)ポリイソシアネート中のイソシアネート基と(B)活性水素含有化合物中の活性水素含有基との反応を促進する触媒である。
・架橋剤-1
ポリオキシエチレングリセリルエーテル(Mw=990)(UCON TPEG-990:ダウ社製)とプロピレンカーボネート(Lyondel社製)とを、20/80の質量比で混合してなる架橋剤組成物。
・架橋剤-2
ポリオキシエチレングリセリルエーテル(Mw=990)(UCON TPEG-990:ダウ社製)とγ-ブチロラクトン(和光純薬社製)とを、20/80の質量比で混合してなる架橋剤組成物。
・架橋剤-3
3-メチル-1,5-ペンタンジオールアジペート(Mw=1000)(クラレポリオーP-1010:クラレ社製)とプロピレンカーボネート(Lyondel社製)とを、20/80の質量比で混合してなる架橋剤組成物。
・架橋剤-4
3-メチル-1,5-ペンタンジオールアジペート(Mw=1000)(クラレポリオーP-1010:クラレ社製)。
・架橋剤-5
ポリオキシエチレングリセリルエーテル(Mw=990)(UCON TPEG-990:ダウ社製)。
・極性溶媒-6
プロピレンカーボネート(Lyondel社製)。
・極性溶媒-7
γ-ブチロラクトン(和光純薬社製)。
・架橋剤-9
ポリオキシエチレングリセリルエーテル(Mw=990)(UCON TPEG-990:ダウ社製)と、3-メチル-1,5-ペンタンジオールアジペート(Mw=1000)(クラレポリオーP-1010:クラレ社製)と、プロピレンカーボネート(Lyondel社製)とを、10/10/80の質量比で混合してなる架橋剤組成物。
・架橋剤-10
ポリオキシエチレングリセリルエーテル(Mw=990)(UCON TPEG-990:ダウ社製)と、3-メチル-1,5-ペンタンジオールアジペート(Mw=1000)(クラレポリオーP-1010:クラレ社製)と、γ-ブチロラクトン(和光純薬社製)とを、10/10/80の質量比で混合してなる架橋剤組成物。
[クリームタイム]
液の混合を始めてから、反応混合液がクリーム状に白濁して立ち上がってくるまでの時間(秒)を、測定した。
[ライズタイム]
液の混合を始めてから、反応混合液が泡化して最高の高さに達するまでの時間(秒)を測定した。
得られたポリウレタンフォームを10cm×10cm×10cmに切り出した後、密度を測定した。
JIS K6401-2:2004(ISO2439:1997)の硬さ測定に準じて測定した。314cm2の大きさの圧縮板を使用し、25%圧縮したときの硬さ(25%硬さ)40%圧縮したときの硬さ(40%硬さ)および65%圧縮したときの硬さ(65%硬さ)をそれぞれ測定した。
JIS K6400-4:2004(ISO1856:2000)に準じて測定した。すなわち、一辺の長さ50±1mm、厚さ25±1mmの試験片を、厚さ方向に50%圧縮した状態で70±1℃の温度に22時間放置した。その後、試験片を圧縮治具から取り出し、室温に30分間放置して回復させてから厚さを測定した。こうして圧縮残留歪みを求めた。
JIS K6400-4:2004(ISO1856:2000)に準じて湿熱老化試験を行い、圧縮縮残留歪み(%)を測定した。すなわち、一辺の長さ50±1mm、厚さ25±1mmの試験片を、厚さ方向に50%圧縮した状態で、70±1℃、95%RHに22時間放置した。その後、試験片を圧縮治具から取り出し、室温に30分間放置して回復させてから厚さを測定した。こうして湿熱圧縮残留歪みを求めた。
JIS K6400-7:2004 B法(ISO7231:1984)に準じて、一辺の長さ51.0±0.3mm、厚さ25.0±0.3mmの試験片を用い、試験片の前後の圧力差を維持するために必要な風量を測定することにより、通気性(L/min.)を測定した。
(A)ポリイソシアネートと、(B1)ポリオールと、(B2)水と、(C)成分である架橋剤-1~架橋剤-2、架橋剤-4、極性溶媒-6、および極性溶媒-7と、触媒および整泡剤を、それぞれ表3および表4に示す組成(質量部)で配合し、高速ミキサーにより混合した。(B1)ポリオールとしては、AdekaポリオールG-3000B(グリセリン-プロピレンオキサイド付加物、水酸基価54mgKOH/g;Adeka社製)、整泡剤としては、NIAX silicone L-598(シリコーン系整泡剤:モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製)を使用し、(A)ポリイソシアネート、アミン系ガス触媒、2-エチルヘキサン酸スズ触媒(ゲル化触媒)、および架橋剤-1、架橋剤-2、架橋剤-4、極性溶媒-6、および極性溶媒-7としては、それぞれ前記したものを使用した。
(A)ポリイソシアネートと、(B1)ポリオールと、(B2)水と、(C)成分である架橋剤-1、極性溶媒-6、および架橋剤-8と、触媒および整泡剤を、それぞれ表5に示す組成(質量部)で配合し、高速ミキサーにより混合した後、直ちに60±2℃に温度調整されたアルミ製金型(内寸300×300×100mm)内に注入し、フタを閉め、そのまま5分間保持して発泡成形し、ポリウレタンフォームを得た。このとき、吐出時間を以下に示すようにして測定した。
反応混合物への(A)ポリイソシアネートの添加から、金型上部の4箇所のガス抜き孔からフォームが押出されて最初に出現するまでの時間(秒)を、吐出時間として測定した。
さらに得られたポリウレタンフォームの特性を、JIS K 6401に準拠し、以下に示すようにして測定した。
FTCは、型から出して1分後から測定し、発泡体(フォームパッド)を最初の厚さから50%まで圧縮させるのに必要なピーク力である。硬さ測定に使用されるものと同じ設定の荷重試験器を用いて測定した。FTC値(N)は気泡の連通性を評価する良好な尺度である。FTC値が低いほど発泡の連通性が高い。
JIS K6401の硬さ測定に準じ、型から出して室温で1日静置後に、FTC測定について使用したと同じパッドの硬さ(N)を測定した。
室温で1日放置したフォーム表面を素手で触り、感触を評価した。ヌメリ性、滑り性を3段階で評価した。
架橋剤を配合することなく得られた比較例14および比較例16のポリウレタンフォームは、感触試験において、ヌメリ性、滑り性がともに不良となっている。特に、比較例14のポリウレタンフォームは、圧縮残留歪み特性も悪くなっている。さらに、(C2)非プロトン性極性溶媒のみからなる極性溶媒-6が配合された比較例15のポリウレタンフォームは、感触試験の結果はそれほど悪くないが、圧縮残留歪み特性が悪くなっている。
Claims (13)
- (A)ポリイソシアネートと、
(B)(B1)ポリオールと(B2)水を含む活性水素含有化合物と、
触媒、および
(C)架橋剤組成物を前記(B1)ポリオール100質量部に対して0.1~20質量部
含有するポリウレタン発泡組成物であり、
前記(C)架橋剤組成物は、
式(1):HO(CH2CH2O)mH(式(1)中、mは3~30の整数である。)、
または式(2):R1-[(CH2CH2O)nH]x
(式(2)中、R1は、グリセロール基、トリメチロール基、ペンタエリスリトール基、ジグリセロール基より選ばれる基であり、nは1~15の整数であり、xは3または4である。)で表わされる、質量平均分子量が2000以下のエトキシレート誘導体(CA)と、
式(3):H(OR2OCOR3CO)y-OR2OH、または
式(4):R4-[(OCOR3CO-OR2)y-OH]3
(式(3)および式(4)中、R2は炭素数2~10のアルキル基であり、R3は炭素数1~15のアルキル基であり、yは1~14の整数である。式(4)中、R4は炭素数1~15のアルキル基である。)で表わされる、質量平均分子量が2500以下のエステル化合物(CB)とから選ばれる少なくとも1種の架橋剤(C1)と、
(C2)非プロトン性極性溶媒とを含有し、
前記(C)架橋剤組成物において、前記(C2)非プロトン性極性溶媒の含有量cに対する、前記(CA)エトキシレート誘導体の含有量aと前記(CB)エステル化合物の含有量bの合計の質量比((a+b)/c)が、1/10~10/1であることを特徴とするポリウレタン発泡組成物。 - 前記(C2)非プロトン性極性溶媒は、ジアルキルスルフォキシド、N,N-ジアルキルアルカノアミド、1-メチル-2-ピロリドン、有機カーボネート、環状エステルから選ばれる1種、または2種以上の混合物であることを特徴とする請求項1記載のポリウレタン発泡組成物。
- 前記ジアルキルスルフォキシドは、ジメチルスルフォキシド、ジエチルスルフォキシド、ジイソブチルスルフォキシドから選ばれる1種、または2種以上の混合物であることを特徴とする請求項2記載のポリウレタン発泡組成物。
- 前記N,N-ジアルキルアルカノアミドは、N,N-ジメチルフォルムアミド、N,N-ジメチルアセトアミド、N,N-ジエチルアセトアミドから選ばれる1種、または2種以上の混合物であることを特徴とする請求項2記載のポリウレタン発泡組成物。
- 前記有機カーボネートは、ジメチルカーボネート、エチレンカーボネート、プロピレンカーボネートから選ばれる1種、または2種以上の混合物であることを特徴とする請求項2記載のポリウレタン発泡組成物。
- 前記環状エステルは、γ-ブチロラクトン、ε-カプロラクトン、γ-バレロラクトンから選ばれる1種、または2種以上の混合物であることを特徴とする請求項2記載のポリウレタン発泡組成物。
- 前記(CA)エトキシレート誘導体は、1200以下の質量平均分子量を有することを特徴とする請求項1乃至6のいずれか1項記載のポリウレタン発泡組成物。
- 前記(CA)エトキシレート誘導体は、式(2):R1-[(CH2CH2O)nH]x
において、R1がグリセロール基であり、xが3の化合物であることを特徴とする請求項1乃至7のいずれか1項記載のポリウレタン発泡組成物。 - 前記(CB)エステル化合物は、1200以下の質量平均分子量を有することを特徴とする請求項1乃至8のいずれか1項記載のポリウレタン発泡組成物。
- 前記(CB)エステル化合物は、
式:H-[O(CH2CH2CH(CH3)CH2CH2-O-CO-CH2CH2CH2CH2CO)] y-O-CH2CH2CH(CH3)CH2CH2-OH
(式中、yは1~14の整数である。)または
式:R4-[(OCOCH2CH2CH2CH2CO-OCH2CH2CH(CH3)CH2CH2) y-OH]3
(式中、R4は炭素数1~15のアルキル基であり、yは1~9の整数である。)
で表される3-メチル-1,5-ペンタンジオールアジペートであることを特徴とする請求項1乃至8のいずれか1項記載のポリウレタン発泡組成物。 - 前記(A)ポリイソシアネートのうちの10質量%以上は、2,4-トリレンジイソシアネートおよび/または2,6-トリレンジイソシアネートであることを特徴とする請求項1乃至10のいずれか1項記載のポリウレタン発泡組成物。
- 得られる発泡体の密度が14kg/m3以上80kg/m3以下であることを特徴とする請求項1乃至11のいずれか1項記載のポリウレタン発泡組成物。
- 請求項1乃至12のいずれか1項記載のポリウレタン発泡組成物を用いることを特徴とする軟質ポリウレタンフォームの製造方法。
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EP13781481.0A EP2842979A4 (en) | 2012-04-26 | 2013-04-24 | POLYURETHANEUM FUEL COMPOSITION AND METHOD FOR PRODUCING A FLEXIBLE POLYURETHANE FOAM |
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KR102092424B1 (ko) | 2020-03-23 |
US20150038604A1 (en) | 2015-02-05 |
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