WO2015190596A1 - 軟質ポリウレタンフォーム、及びシート用パッド - Google Patents
軟質ポリウレタンフォーム、及びシート用パッド Download PDFInfo
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- WO2015190596A1 WO2015190596A1 PCT/JP2015/067017 JP2015067017W WO2015190596A1 WO 2015190596 A1 WO2015190596 A1 WO 2015190596A1 JP 2015067017 W JP2015067017 W JP 2015067017W WO 2015190596 A1 WO2015190596 A1 WO 2015190596A1
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- polyurethane foam
- polyol
- flexible polyurethane
- stock solution
- catalyst
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
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- B29C44/355—Characteristics of the foam, e.g. having particular surface properties or structure
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- B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Definitions
- the present invention relates to a flexible polyurethane foam used for various molded articles such as automobile parts and indoor household goods, and a seat pad (cushion material for a seat) using the flexible polyurethane foam.
- This application claims priority based on Japanese Patent Application No. 2014-121919 for which it applied to Japan on June 12, 2014, and uses the content here.
- Soft polyurethane foam is used for various applications such as seat pads for vehicles such as automobiles, cushions for indoor chairs, bedding, and cushioning materials for flooring in houses. Various mechanical characteristics are required depending on the application, and a comfortable seating comfort is required for an automobile seat pad.
- the applicant has proposed a polyurethane foam of Patent Document 1 as a polyurethane foam having an appropriate repulsive force, light weight and excellent vibration absorption characteristics.
- This polyurethane foam is a polyurethane foam in which a polyurethane foam stock solution containing a polyol component and an isocyanate component is foam-molded, and a polyether polyol having a molecular weight, an unsaturation degree, and a molecular weight / functional group number within a specific range as a main component.
- Inorganic fillers that have been further treated with organic treatment are blended.
- seat pads for vehicles have been increasingly required for comfort and stability when seated.
- a lateral G acceleration in the centrifugal direction
- the buttock of the occupant's buttocks and back It is required to sufficiently support the above and reduce the feeling of wobbling (the feeling of lying down).
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a seat pad having a comfortable sitting comfort and a certain sense of stability, and a flexible polyurethane foam capable of realizing the seat pad.
- a flexible polyurethane foam obtained by foam-molding a foaming stock solution containing a polyol, a polyisocyanate, a crosslinking agent, a foaming agent, and a catalyst.
- the polyol has a weight average molecular weight Mw of 3000 to 12000 and a functional group number. 3 to 4 polyether polyol, and the total amount of ethylene oxide / propylene oxide groups (molar ratio) of the compound included as the crosslinking agent is 100 or more, and the crosslinking agent has a short weight average molecular weight of 1000 or less.
- the foaming stock solution forming the flexible polyurethane foam of the present invention has a novel composition. As a result, comfortable sitting comfort and stability different from conventional ones can be obtained by reducing the wobble feeling when an appropriate repulsive force and lateral acceleration are applied when sitting.
- a preferred embodiment of the flexible polyurethane foam of the present invention is a flexible polyurethane foam obtained by foam-molding a foam stock solution containing a polyol, a polyisocyanate, a crosslinking agent, a foaming agent, and a catalyst.
- the following (A) to (D) are mentioned as the characteristics of the material constituting the foaming stock solution.
- polystyrene resin As the polyol component, a polyether polyol having a weight average molecular weight Mw of 3000 to 12000 and a functional group number (number of hydroxyl groups) of 3 to 4 is contained.
- the ethylene oxide group / propylene oxide group (molar ratio) in the entire compound (total cross-linking agent) contained in the foaming stock solution as the cross-linking agent component is 100 or more.
- a short-chain polyol having a weight average molecular weight of 1000 or less is contained as a crosslinking agent component.
- D As a polyisocyanate component, 70 or more of tolylene diisocyanate (TDI) is contained in an isocyanate equivalent.
- a polyether polyol having a weight average molecular weight Mw of 3,000 to 12,000 and a functional group number (number of hydroxyl groups) of 3 to 4 is contained.
- the polyether polyol is preferably a polyether polyol obtained by ring-opening polymerization of an alkylene oxide because of good reactivity.
- the alkylene oxide include propylene oxide (PO) and ethylene oxide (EO).
- the alkylene oxide used as the material for the polyether polyol may be one kind or two or more kinds.
- the polyether polyol constituting the foaming stock solution a polyether polyol obtained by using the above PO and EO together is preferable from the viewpoint of raw material activity.
- the blending ratio (molar ratio) of PO and EO is not particularly limited.
- the EO / PO (molar ratio) is preferably 8/92 to 25/75, more preferably 13/87 to 20/80.
- the EO / PO (molar ratio) is in the above range, a polyether polyol having good reactivity can be easily produced.
- the number of hydroxyl groups (functional groups) contained in one molecule of the polyether polyol constituting the foaming stock solution is preferably 3 to 4, and more preferably 3.5 to 4. Within these preferred ranges, the viscosity of the foamed stock solution becomes moderate, and a flexible polyurethane foam having excellent physical properties can be obtained.
- a polyether polyol having two functional groups may be used in combination.
- the weight average molecular weight Mw of the polyether polyol constituting the foaming stock solution is preferably 3,000 to 12,000, more preferably 3,000 to 8,000, and further preferably 5,000 to 8,000.
- the weight average molecular weight of the polyether polyol is 12,000 or less, the viscosity of the foaming stock solution is not excessively increased, and the stirring efficiency is improved.
- the weight average molecular weight of the polyether polyol is 3,000 or more, a flexible polyurethane foam having good rebound resilience can be obtained.
- the weight average molecular weight Mw is a value calculated as a polystyrene conversion value by gel permeation chromatography (GPC method).
- the degree of unsaturation of the polyether polyol constituting the foaming stock solution is preferably 0.03 meq / g or less.
- the degree of unsaturation is 0.03 meq / g or less, a flexible polyurethane foam having good physical properties such as durability can be obtained.
- the “unsaturation degree” is a method in which acetic acid liberated by acting mercuric acetate on unsaturated bonds in a sample is titrated with potassium hydroxide in accordance with Japanese Industrial Standard JIS K 1557-1970. Means the total degree of unsaturation (milliequivalent / g).
- the polyether polyol contained in the foaming stock solution as the polyol component may be one type or two or more types.
- a polyether polyol having a weight average molecular weight of 7000 or more and 4 functional groups (tetrafunctional) is contained. It is preferable.
- a polyether polyol having a weight average molecular weight of 7000 or more and 4 functional groups (tetrafunctional) is contained.
- the total content of two or more kinds of polyether polyols is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and still more preferably 40 to 60% by mass.
- a polymer polyol is preferably used in combination as the polyol component constituting the foaming stock solution.
- Appropriate hardness and elasticity can be easily imparted to the flexible polyurethane foam by using the polymer polyol in combination.
- the total content of one or more polymer polyols with respect to the total mass of the polyol component contained in the foaming stock solution is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and 40 to 60% by mass. % Is more preferable.
- polymer polyol a polymer polyol widely used for polyurethane foam moldings can be applied.
- a polymer component such as polyacrylonitrile or acrylonitrile-styrene copolymer is added to a polyether polyol made of polyalkylene oxide and having a weight average molecular weight Mw of 3,000 to 8,000, more preferably 4,000 to 7,000.
- Examples include graft-polymerized polymer polyols.
- the alkylene oxide used as the raw material of the polyalkylene oxide is preferably an alkylene oxide containing propylene oxide (PO) as a functional group (polymerizable group), an alkylene oxide containing only propylene oxide, or propylene oxide and ethylene oxide (EO). More preferred are alkylene oxides included together.
- the content of the polymer component with respect to the total mass of the polymer polyol is preferably 25 to 50% by mass.
- the mixing ratio in the case of mixing polyether polyol and polymer polyol as the polyol component constituting the foaming stock solution is preferably 80/20 to 20/80 as polyether polyol / polymer polyol (mass ratio). / 30 to 30/70 is more preferable, and 60/40 to 40/60 is still more preferable. Within the above range, it is easy to obtain a flexible polyurethane foam having desired physical properties.
- Polyisocyanate component As the polyisocyanate component constituting the foaming stock solution, 70 or more of tolylene diisocyanate is contained in an isocyanate equivalent.
- Tolylene diisocyanate is a polyisocyanate component commonly used in the field of polyurethane foam.
- TDI include 2,4-tolylene diisocyanate (2,4-TDI) and 2,6-tolylene diisocyanate (2,6-TDI).
- 2,4-TDI 2,4-tolylene diisocyanate
- 2,6-TDI 2,6-tolylene diisocyanate
- the TDI constituting the foaming stock solution may be a mixture of 2,4-TDI and 2,6-TDI, or may be 2,4-TDI alone or 2,6-TDI alone. May be. That is, in the foaming stock solution, one type of TDI may be contained alone, or two or more types of TDI may be contained.
- diphenylmethane diisocyanate (MDI) is used in combination as the polyisocyanate component constituting the foaming stock solution.
- MDI Diphenylmethane diisocyanate
- 4,4-MDI 4,4-diphenylmethane diisocyanate
- 2,4-MDI 2,4-diphenylmethane diisocyanate
- 2,2-diphenylmethane diisocyanate 2,2-diphenylmethane diisocyanate
- 2,2-MDI polymeric MDI
- crude MDI crude MDI
- one type of MDI may be contained, or two or more types of MDI may be contained.
- “Isocyanate equivalent” representing the total amount of polyisocyanate contained in the foaming stock solution means the molar ratio of isocyanate groups when the amount of active hydrogen (mole) in the foaming stock solution is 100.
- the isocyanate equivalent derived from TDI contained in the foaming stock solution is at least 70, preferably 70 to 120, more preferably 80 to 110.
- the isocyanate equivalent is 70 or more, poor stirring of the foaming stock solution can be prevented.
- the isocyanate equivalent is 120 or less, foam collapse can be prevented.
- the isocyanate equivalent derived from MDI contained in the foaming stock solution is preferably from 70 to 120, more preferably from 80 to 110.
- the total isocyanate equivalent derived from TDI and MDI contained in the foaming stock solution is preferably 70 to 120, more preferably 80 to 110.
- the isocyanate equivalent is 70 or more, poor stirring of the foaming stock solution can be prevented.
- the isocyanate equivalent is 120 or less, foam collapse can be prevented.
- the mass ratio (TDI / MDI) of TDI and MDI contained in the foaming stock solution is preferably 100/0 to 60/40, more preferably 95/5 to 70/30, and still more preferably 90/10 to 80/20. .
- mass ratio is in the preferred range, physical properties that contribute to a reduction in wobbling sensation can be easily imparted to a flexible polyurethane foam obtained by foam-molding the foamed stock solution.
- a known polyisocyanate component other than MDI may be added.
- examples thereof include triphenyl diisocyanate, xylene diisocyanate, polymethylene polyphenylene polyisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
- the total content of at least types is preferably 60% by mass or more, more preferably 70 to 100% by mass, and still more preferably 80 to 100% by mass.
- a cross-linking agent component constituting the foamed stock solution a cross-linking agent having a higher reactivity with respect to the polyisocyanate component than water is a main component. Is preferably included. Usually, the reactivity with respect to the polyisocyanate component decreases in the order of glycerin, a crosslinking agent having an ethylene oxide group (EO-based crosslinking agent), water, and a crosslinking agent having a propylene oxide group (PO-based crosslinking agent).
- EO-based crosslinking agent ethylene oxide group
- PO-based crosslinking agent a crosslinking agent having a propylene oxide group
- the molar ratio of the EO group to the PO group (the number of moles of EO groups / the number of moles of PO groups) of one or more compounds contained as a cross-linking agent in the foaming stock solution is 100. It is preferably above, more preferably 105 or more, and even more preferably 110 or more. A higher molar ratio is preferable. That is, it is preferable that the foaming stock solution does not substantially contain a crosslinking agent having a PO group.
- the ethylene oxide group means a group having a monovalent bond from which one hydrogen atom constituting ethylene oxide is removed.
- the propylene oxide group means a group having a monovalent bond in which one hydrogen atom constituting propylene oxide is removed.
- crosslinking agent component a known crosslinking agent used in the field of polyurethane foam can be applied.
- the molecular weight of the crosslinking agent is usually preferably 1000 or less.
- a particularly preferred crosslinking agent is glycerin (glycerol).
- a short-chain polyol containing glycerin and having a weight average molecular weight of 1000 or less is preferable as in the case of glycerin.
- the short-chain polyol for example, a low molecular polyol having a molecular weight of 70 to 140 is preferable, and a terminal primary polyol having a hydroxyl group at the end of the molecule is more preferable.
- the low-molecular polyol include propanediol, glycerin, trimethylolpropane, pentaerythritol and the like. Among these, glycerin is more preferable.
- the crosslinking agent contained in the foaming stock solution may be one type or two or more types.
- a cross-linking agent having an EO group / PO group (molar ratio) of 100 or more and glycerin are used in combination, the mass ratio of the cross-linking agent / glycerin is preferably 10: 1 to 1:10, preferably 5: 1 to 1: 5. More preferably, 2: 1 to 1: 2 is still more preferable, and 1: 2 to 1: 1 is particularly preferable.
- the total content of the crosslinking agent components contained in the foaming stock solution is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyol component. .
- the amount is not more than the upper limit of the above range, the closed cell property becomes too high, molding becomes difficult, and foam collapse can be prevented.
- the effect of a crosslinking agent is fully acquired as it is more than the lower limit of the said range.
- the foaming stock solution preferably contains alkanolamine as a crosslinking retarder. It is possible to prevent a rapid progress of the crosslinking reaction (polymerization reaction) at the time of foam molding and to easily obtain a flexible polyurethane foam having an appropriate hardness.
- alkanolamine as the retarder examples include 1 to 3 monovalent alkanol groups in which one or two or more hydrogen atoms of an acyclic saturated hydrocarbon are substituted with a hydroxyl group. Amines are preferred.
- alkanolamine as the retarder examples include monoethanolamine, diethanolamine, triethanolamine, aminoethylethanolamine and the like.
- the retarder is more preferably an alkanolamine other than diethanolamine.
- Diethanolamine is preferably added as a catalyst to be described later, not the retarder.
- the alkanolamine contained in the foaming stock solution may be one type or two or more types.
- the content of alkanolamine with respect to 100 parts by mass of the polyol component is preferably 0.1 to 1.0 part by mass, more preferably 0.2 to 0.7 part by mass, and 0.3 to 0. More preferably, 5 parts by mass.
- the mass ratio is in the preferred range, physical properties that contribute to a reduction in wobbling sensation can be easily imparted to a flexible polyurethane foam obtained by foam-molding the foamed stock solution.
- a foaming agent component constituting the foaming stock solution it is preferable to use water. Since water reacts with polyisocyanate to generate carbon dioxide, it functions as a foaming agent.
- the content of water in the foaming stock solution is preferably 1 to 7 parts by mass and more preferably 2 to 5 parts by mass with respect to 100 parts by mass of the polyol component.
- Catalyst component examples include known catalysts used in the field of polyurethane foam.
- Known catalysts include amine catalysts and tin catalysts.
- known catalysts are roughly classified into a resination catalyst that promotes the resinization of polyurethane and a foaming catalyst that promotes foaming of the polyisocyanate component.
- Suitable resination catalysts are tertiary amine catalysts that specifically promote the reaction of polyisocyanates and polyols, such as, but not limited to, triethylenediamine, 1,8-diazabicyclo [5.4.0].
- Undecene-7, and imidazoles such as 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1,1 ′-(3- (dimethylamino) propyl) imino) bis (2- Propanol).
- a suitable foaming catalyst is a tertiary amine catalyst that particularly accelerates the reaction between isocyanate and water and effectively generates carbon dioxide, and is generally used for improving the fluidity and dimensional stability of foam.
- the foaming catalyst is not particularly limited, but is bis (2-dimethylaminoethyl) ether, N, N, N ′, N ′′, N ′′ -pentamethyldiethylenetriamine, and N, N, N ′, N ′′. , N ′ ′′, N ′ ′′ -hexamethyltriethylenetetramine and the like.
- the foaming stock solution preferably contains at least a resination catalyst as a catalyst component among a resination catalyst and a foaming catalyst.
- the mass ratio of the resinification catalyst: foaming catalyst contained in the foaming stock solution is preferably 100: 0 to 100: 100, more preferably 100: 0 to 80:20, and further preferably 100: 0 to 90:10. 100: 0 to 95: 5 is particularly preferable.
- the amine-based catalyst has a ratio of the foaming catalyst constant to the gelation catalyst constant of 10 ⁇ 10 in order to accelerate the resinification (gelation) reaction between polyols and polyisocyanates and promote urethane bond formation. It is preferable to use a resinification catalyst that is ⁇ 1 or less.
- the gelation catalyst constant is a constant that determines the speed of the resinification reaction between polyols and polyisocyanates. As the value increases, the crosslink density of the foam increases and the mechanical properties of the foam increase. become good.
- the reaction constant of the gelation reaction between tolylene diisocyanate and diethylene glycol is used.
- the foaming catalyst constant is a constant that determines the speed of the foaming reaction between the polyisocyanates and water, and the larger the value, the higher the cell connectivity of the foam.
- the reaction constant of the foaming reaction between tolylene diisocyanate and water is used.
- the ratio of the two catalyst constants represents the balance of both catalysts. Examples of suitable amine-based catalysts are exemplified below including specific examples of the resinification catalyst.
- the resinification catalyst include the above-mentioned catalysts, including triethylenediamine (TEDA), a mixture of triethylenediamine and polypropylene glycol, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ', N'-tetramethylpropylenediamine, N, N, N', N ", N" -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ', N ", N” -pentamethyldipropylene Tertiary amines such as triamine, N, N, N ′, N′-tetramethylguanidine, 135-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1-methylimidazole, 1,2-dimethyl Imidazoles such as imidazole and 1-isobutyl-2-methylimidazole, and other N, N, N, N,
- the content of the amine catalyst in the foaming stock solution is preferably 0.1 to 2.0 parts by mass, and 0.5 to 1.5 parts by mass with respect to 100 parts by mass of the polyol component. Is more preferably 0.75 to 1.0 part by mass.
- the lower limit of the above range is 0.1 parts by mass or more, foam collapse can be prevented.
- the upper limit value is 2.0 parts by mass or less in the above range, it is possible to prevent shrinkage from occurring due to closed cells.
- tin catalyst examples include known organotin catalysts such as stannous octoate, stannous laurate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, dioctyltin diacetate, and tin octylate.
- the content of the tin catalyst in the foaming stock solution is preferably 0.01 to 0.5 parts by mass, and 0.01 to 0.4 parts by mass with respect to 100 parts by mass of the polyol component. More preferred is 0.01 to 0.2 parts by mass.
- the foaming stock solution may contain a foam stabilizer.
- foam stabilizer known foam stabilizers used in the field of polyurethane foam are applicable, and examples thereof include silicone foam stabilizers, anionic foam stabilizers, and cationic foam stabilizers. These foam stabilizers include foam stabilizers having a hydroxyl group at the molecular chain terminal.
- the foam stabilizer in the foaming stock solution is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight, and more preferably 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the polyol component. Part by mass is more preferable. Usually, the effect as a foam stabilizer is sufficiently obtained at a content of 5 parts by mass or less. Moreover, the stirring rate of a polyol component and a polyisocyanate component improves that it is a content rate of 0.1 mass part or more, and the flexible polyurethane foam which has a desired physical property is easy to be obtained.
- additives may be added to the foaming stock solution as necessary.
- coloring agents such as pigments, chain extenders, fillers such as calcium carbonate, flame retardants, antioxidants, UV absorbers, light stabilizers, conductive materials such as carbon black, antibacterial agents, etc. it can.
- the compounding quantity of various additives is suitably adjusted according to a use and the objective.
- the method for preparing the foaming stock solution is not particularly limited. For example, a mixture composed of the remaining components excluding the polyisocyanate component (hereinafter sometimes abbreviated as “polyol mixture”) is prepared, and then. The preparation method which mixes with a polyisocyanate component and obtains foaming stock solution is mentioned.
- the polyol mixture is prepared by first mixing the catalyst component with the polyol component in order to reduce the contact between the foaming agent water and the catalyst component, then the foam stabilizer component, the crosslinker component, and if necessary. Accordingly, it is preferable to mix optional components and finally mix water as a blowing agent. Thereafter, in the step of foam-molding the flexible polyurethane foam, it is preferable to prepare the foaming stock solution by mixing the polyol mixture and the polyisocyanate component.
- the viscosity of the prepared polyol mixture at a liquid temperature of 25 ° C. is preferably 2,400 mPa ⁇ s or less, and more preferably 1,800 mPa ⁇ s or less.
- the stirring efficiency of the foaming stock solution is improved, and a sufficient amount of foaming is obtained uniformly throughout the foaming stock solution, thereby obtaining a flexible polyurethane foam (foamed molded product) having desired physical properties. It becomes easy to be done.
- a method for foam-molding a flexible polyurethane foam using the foaming stock solution is not particularly limited.
- a known method for foaming by injecting a foaming stock solution into a cavity formed in a mold can be applied. .
- the foaming stock solution in order to prevent separation of each component constituting the foaming stock solution, it is preferable to prepare the foaming stock solution by mixing the above-mentioned components immediately before injecting the foaming stock solution into the cavity.
- the liquid temperature of the foaming stock solution to be injected is preferably 10 to 50 ° C., more preferably 20 to 40 ° C., and further preferably 25 to 35 ° C.
- the temperature of the mold is preferably 40 to 80 ° C., more preferably 50 to 70 ° C., and further preferably 60 to 65 ° C.
- appropriate foaming can be obtained.
- the target flexible polyurethane foam is obtained by curing in a mold and then demolding.
- the flexible polyurethane foam obtained here may be further subjected to a known film removal treatment.
- the first embodiment of the flexible polyurethane foam according to the present invention is directed to the thickness direction from the lower layer to the upper layer during foam molding (that is, the upward direction along the vertical line), during foam molding.
- the lower layer has a substantially constant rigidity, and the rigidity (hardness) tends to gradually increase from the middle layer to the upper layer during foam molding. That is, in the rigidity distribution in the thickness direction of the flexible polyurethane foam according to the first embodiment of the present invention, there are a first region showing a substantially constant tendency and a second region showing a continuous increasing tendency or a decreasing tendency. .
- the rigidity distribution tends to increase when viewed from the lower layer to the upper layer during foam molding of the flexible polyurethane foam, but when the same flexible polyurethane foam is viewed from the upper layer to the lower layer during foam molding,
- the stiffness distribution shows a decreasing trend.
- the details of the mechanism by which the first embodiment of the flexible polyurethane foam according to the present invention exhibits the rigidity distribution is unclear, but it is considered that the combination of the components constituting the foaming stock solution is a factor.
- a major factor is that the main polymerizable group (reactive group) of the cross-linking agent component is an EO group, and the PO group that does not substantially exhibit the cross-linking effect is not included in the cross-linking agent component. it is conceivable that.
- glycerin is contained as a crosslinking agent component
- alkanolamine is contained as a crosslinking retarder
- a resinification catalyst is contained as a catalyst component. It is thought that it contributed not a little.
- the second embodiment of the flexible polyurethane foam according to the present invention is gradually rigid in the thickness direction from the lower layer to the upper layer during foam molding (that is, the upward direction along the vertical line).
- (Hardness) tends to increase. That is, the rigidity distribution in the thickness direction of the flexible polyurethane foam according to the present invention shows a continuous increasing tendency or a decreasing tendency.
- the rigidity distribution tends to increase when viewed from the lower layer to the upper layer during foam molding of flexible polyurethane foam, but when the same flexible polyurethane foam is viewed from the upper layer to the lower layer during foam molding, the rigidity distribution The distribution shows a decreasing trend.
- the details of the mechanism by which the second embodiment of the flexible polyurethane foam according to the present invention exhibits the rigidity distribution is not clear, but it is considered that the combination of the components constituting the foaming stock solution is a factor.
- a major factor is that the main polymerizable group (reactive group) of the cross-linking agent component is an EO group, and the PO group that does not substantially exhibit the cross-linking effect is not included in the cross-linking agent component. it is conceivable that.
- glycerin is contained as a crosslinking agent component
- alkanolamine is contained as a crosslinking retarder
- a resinification catalyst is contained as a catalyst component. It is thought that it contributed not a little.
- the degree of flatness of the foamed cell shape appearing in the cross section tends to gradually increase from the upper layer to the lower layer during foam molding. It is done.
- the foam cell located in the lower layer at the time of foam molding is crushed in the direction of gravity and exhibits a horizontally long flat shape (elliptical shape), and the foam cell located in the middle layer
- the degree of flatness is relatively relaxed and approaches a circle, and the degree of flatness in the foam cell located in the upper layer is further relaxed and tends to be closer to a circle.
- the “soft” of the flexible polyurethane foam according to the present invention has a hardness (rigidity) to the extent that the flexible polyurethane foam is deformed and dented when it is pushed by hand or sitting on it. Means.
- Examples 1 to 6, Comparative Examples 1 to 7 In the formulation shown in Table 1 and Table 2, a mixed liquid containing components other than polyisocyanate (B) and polyisocyanate (B) were mixed to prepare a foaming stock solution. The foaming stock solution was poured into a mold and foamed to produce a sheet pad having a thickness of 70 mm. About the obtained pad for sheets, hardness was measured with the following measuring method and the following evaluation was performed.
- the results of the above measurements are shown in Tables 3-4.
- the unit of the measured value is (unit: N / mm 2 ).
- the column of “depth 10.7% from the surface layer” corresponds to the first evaluation sample
- the column of “depth 32.1% from the surface layer” corresponds to the second evaluation sample
- the column “depth 53.5% from the surface layer” corresponds to the third evaluation sample
- the column “depth 75.0% from the surface layer” corresponds to the fourth evaluation sample.
- each molded body was measured for 25% hardness in accordance with Japanese Industrial Standard JIS K 6400-2.
- Each measured value (unit: N / mm 2 ) is shown in Tables 3-6.
- FIG. 1 is a graph in which the horizontal axis represents each depth position and the vertical axis represents the hardness ratio.
- the soft polyurethane foams of Examples 1 to 6 do not decrease in hardness in the thickness direction from the front surface to the back surface.
- the hardness (rigidity) is constant or increased.
- the hardness (rigidity) continuously increases from the middle layer to the lower layer with a depth of 32.1% to a depth of 75.0%. Therefore, when viewed in the thickness direction of the flexible polyurethane foams of Examples 1 to 6, the region having the lowest rigidity is located in the surface layer (upper layer), and the region having the highest rigidity is located in the lower layer.
- the flexible polyurethane foams of Examples 1 to 4 and 6 have a surface layer (upper layer) having a constant rigidity (hardness) when viewed in the thickness direction, and a middle layer and a lower layer in which the rigidity continuously increases. As a result, the feeling of wobble required in the application of the pad for a sheet is reduced. Further, since the hardness ratio in the vicinity of the surfaces of Examples 1 to 4 and 6 is smaller than that of Comparative Examples 1 to 7, the repulsive force at the time of sitting is more gentle, and the feeling of pressure from the seating surface is less, You can get a different comfortable sitting comfort.
- the rigidity of the flexible polyurethane foam of Example 5 continuously increases from the surface layer (upper layer) to the lower layer as seen in the thickness direction. As a result, the feeling of wobble required in sheet pad applications is reduced. Further, since the hardness ratio in the vicinity of the surface of Example 5 is smaller than that of Examples 1 to 4 and 6, the repulsive force at the time of sitting is further gentle, and the feeling of pressure from the seating surface is further reduced. Comfortable sitting comfort different from 4 and 6 is obtained.
- the flexible polyurethane foams of Examples 1 to 6 show the above-described rigidity distribution.
- the foamed stock solution of the flexible polyurethane foam contains TDI as a main polyisocyanate component and contains a large amount of glycerin as a crosslinking agent. That it contains a large amount of alkanolamine as a crosslinking retarder, is substantially free of PO crosslinking agent, and contains EO crosslinking agent as the main crosslinking agent component Any one or more of including a resinification catalyst as a main catalyst component is conceivable.
- the surface layer (upper layer) having almost constant rigidity exists in the thickness direction of the flexible polyurethane foams of Examples 1 to 4 and 6, and the rigidity increases continuously from the middle layer to the lower layer. It is conceivable that a trifunctional polyether polyol is contained and no tetrafunctional polyether polyol is contained. Further, as seen in the thickness direction of the flexible polyurethane foam of Example 5, a tetrafunctional polyether polyol is contained as a factor that the rigidity continuously increases from the surface layer (upper layer) to the middle layer to the lower layer, It is conceivable that no trifunctional polyether polyol is contained.
- the soft polyurethane foams of Comparative Examples 1 to 7 have a hardness ratio of 32.1% lower than the hardness ratio of 10.7% deep. With such a stiffness distribution, when a lateral G is added, the soft polyurethane foam feels lying on the middle layer deeper than the surface layer close to the seating surface, and a wobbling sensation is likely to occur.
- the reason why the flexible polyurethane foams of Comparative Examples 1 to 7 show the above-mentioned rigidity distribution is that the foamed stock solution of the flexible polyurethane foam does not contain glycerin as a crosslinking agent, and contains a large amount of PO-based crosslinking agent as a crosslinking agent. Or a large amount of a foaming catalyst as the catalyst.
- Polyether polyol A1-1 is a polyether polyol having an EO / PO molar ratio of 13/87, a weight average molecular weight of 7000, and three functional groups.
- Polyether polyol A1-2 is a polyether polyol having an EO / PO molar ratio of 15/85, a weight average molecular weight of 6000, and three functional groups.
- Polyether polyol A1-3 is a polyether polyol having an EO / PO molar ratio of 15/85, a weight average molecular weight of 5000, and a functional group number of 3.
- Polyether polyol A1-4 is a polyether polyol having an EO / PO molar ratio of 16/84, a weight average molecular weight of 7000, and 4 functional groups.
- Polymer polyol A2-1 is a polymer polyol having a solid content of 33%, a hydroxyl value of 23 mg KOH / g, a weight average molecular weight of 5400, and a 3.2 functional polymer (manufactured by Sanyo Chemical Industries, Ltd., trade name: KC855).
- Crosslinking agent C-1 is a polyether polyol having an EO / PO molar ratio of 0/100, a weight average molecular weight of 700, and three functional groups.
- Crosslinking agent C-2 is a commercially available polyether polyol having an EO / PO molar ratio of 100/0, a molecular weight of 400, and a functional group number of 4.
- Crosslinking agent C-3 is glycerin.
- Crossing retarder D-1 is alkanolamine (trade name: PM-1) manufactured by Momentive.
- Catalyst E-1 is a commercially available resinification catalyst and is triethylenediamine.
- Catalyst E-2 is a commercially available foaming catalyst, and is bis [2- (dimethylamino) ethyl] ether (trade name: TOYOCAT ET33B, manufactured by Tosoh Corporation).
- Catalyst E-3 is a commercially available diethanolamine.
- “Foam stabilizer F-1” is a low activity silicone foam stabilizer (trade name: L3623) manufactured by Momentive.
- “Foam stabilizer F-2” is a highly active silicone foam stabilizer (trade name: B8742) manufactured by Evonik.
- “Foaming agent G-1” is water.
- the flexible polyurethane foam according to the present invention can be widely used as a vehicle seat pad.
- the present invention provides a seat pad having a comfortable sitting comfort and a certain sense of stability, and a flexible polyurethane foam capable of realizing the seat pad.
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Abstract
Description
本願は、2014年6月12日に日本に出願された特願2014-121919号に基づき優先権を主張し、その内容をここに援用する。
(B) 架橋剤成分として発泡原液中に含まれる化合物の全体(架橋剤の総体)におけるエチレンオキシド基/プロピレンオキシド基(モル比)は100以上である。
(C) 架橋剤成分として重量平均分子量が1000以下の短鎖ポリオールを含有する。
(D) ポリイソシアネート成分として、トリレンジイソシアネート(TDI)をイソシアネート当量で70以上含有する。
前記発泡原液を構成するポリオール成分として、重量平均分子量Mwが3,000~12,000であり、且つ官能基数(ヒドロキシル基の数)が3~4であるポリエーテルポリオールを含有する。上記ポリエーテルポリオールとしては、反応性が良好であることから、アルキレンオキシドの開環重合により得られるポリエーテルポリオールが好ましい。
アルキレンオキシドとしては、プロピレンオキシド(PO)、エチレンオキシド(EO)等が挙げられる。ポリエーテルポリオールの材料として使用されるアルキレンオキシドは1種類であってもよいし、2種類以上であってもよい。
前記発泡原液を構成するポリイソシアネート成分として、トリレンジイソシアネートをイソシアネート当量で70以上含有する。
前記発泡原液において、1種類のMDIが含有されてもよいし、2種類以上のMDIが含有されてもよい。
前記発泡原液が発泡成形されてなる軟質ポリウレタンフォームが所望の物性を有するために、前記発泡原液を構成する架橋剤成分として、前記ポリイソシアネート成分に対する反応性が水よりも高い架橋剤が、主成分として含まれることが好ましい。通常、グリセリン、エチレンオキシド基を有する架橋剤(EO系架橋剤)、水、プロピレンオキシド基を有する架橋剤(PO系架橋剤)の順で、前記ポリイソシアネート成分に対する反応性が低下する。これに基づいて、前記発泡原液に架橋剤として含有される1種又は2種以上の化合物の全体が有するEO基とPO基のモル比(EO基のモル数/PO基のモル数)は100以上であることが好ましく、105以上であることがより好ましく、110以上であることがさらに好ましい。このモル比は高い程好ましい。つまり、前記発泡原液において、PO基を有する架橋剤が実質的には含有されないことが好ましい。
前記発泡原液には、架橋の遅延化剤として、アルカノールアミンを含有することが好ましい。発泡成形時の架橋反応(重合反応)が急速に進むことを防ぎ、適度な硬度を備えた軟質ポリウレタンフォームが容易に得られる。
前記発泡原液を構成する発泡剤成分としては、水を用いることが好ましい。水はポリイソシアネートと反応して炭酸ガスを発生するため、発泡剤として機能する。
前記発泡原液中の水の含有量としては、ポリオール成分100質量部に対して、1~7質量部であることが好ましく、2~5質量部であることがより好ましい。上記範囲であると、所望の物性を有する軟質ポリウレタンフォームが容易に得られる。また、得られた軟質ポリウレタンフォームの熱圧縮残留歪み特性が劣化することを防止できる。
前記発泡原液を構成する触媒成分としては、ポリウレタンフォームの分野で使用される公知の触媒が挙げられる。公知の触媒としては、アミン系触媒、スズ触媒が挙げられる。
好適な樹脂化触媒は、ポリイソシアネートとポリオールの反応を特に促進する第三級アミン触媒であり、特に限定するものではないが、例えば、トリエチレンジアミン、1,8-ジアザビシクロ[5.4.0]ウンデセン-7、及び1-メチルイミダゾール、1、2-ジメチルイミダゾール、1-イソブチル-2-メチルイミダゾール等のイミダゾール類、1,1’-(3-(ジメチルアミノ)プロピル)イミノ)ビス(2-プロパノール)が挙げられる。また好適な泡化触媒は、イソシアネ-トと水の反応を特に促進し、炭酸ガスを有効に発生させる第三級アミン触媒であり、一般的にフォームの流動性、寸法安定性改良に使用される。泡化触媒としては特に限定するものではないが、ビス(2-ジメチルアミノエチル)エーテル、N,N,N′,N″,N″-ペンタメチルジエチレントリアミン、及びN,N,N′,N″,N''' ,N''' -ヘキサメチルトリエチレンテトラミン等が挙げられる。
前記発泡原液に含有される、樹脂化触媒:泡化触媒の質量比は、100:0~100:100が好ましく、100:0~80:20がより好ましく、100:0~90:10が更に好ましく、100:0~95:5が特に好ましい。
ここで、ゲル化触媒定数は、ポリオール類とポリイソシアネート類との樹脂化反応の速度を決定する定数であり、その値が大きくなると発泡体の架橋密度が高くなって発泡体の機械的物性が良好になる。具体的には、トリレンジイソシアネートとジエチレングリコールとのゲル化反応の反応定数が用いられる。一方、泡化触媒定数は、ポリイソシアネート類と水との泡化反応の速度を決定する定数であり、その値が大きくなると発泡体のセルの連通性が高められる。具体的には、トリレンジイソシアネートと水との泡化反応の反応定数が用いられる。上記2つの触媒定数の比は、両方の触媒のバランスを表す。
好適なアミン系触媒の例を、前記樹脂化触媒の具体例も含めて以下に例示する。
前記発泡原液には、整泡剤が含まれてもよい。整泡剤としては、ポリウレタンフォームの分野で使用される公知の整泡剤が適用可能であり、例えば、シリコーン系整泡剤、アニオン系整泡剤、カチオン系整泡剤が挙げられる。これらの整泡剤には、分子鎖末端に水酸基を有する整泡剤が含まれる。
前記発泡原液には、必要に応じて各種添加剤を配合することができる。例えば、顔料等の着色剤、鎖延長剤、炭酸カルシウム等の充填材、難燃剤、酸化防止剤、紫外線吸収剤、光安定剤、カーボンブラック等の導電性物質、抗菌剤などを配合することができる。各種添加剤の配合量は、用途や目的に応じて適宜調整される。
前記発泡原液の調製方法は、特に限定されず、例えば、ポリイソシアネート成分を除いた、残りの各成分からなる混合物(以下、「ポリオール混合物」と略記することがある。)を調製し、その後、ポリイソシアネート成分と混合して、発泡原液を得る調製方法が挙げられる。
その後、軟質ポリウレタンフォームを発泡成形する工程において、前記ポリオール混合物とポリイソシアネート成分とを混合し、発泡原液を調製することが好ましい。
発泡成形の方法によらず、本発明にかかる軟質ポリウレタンフォームの第一実施形態は、発泡成形時の下層から上層へ向かう厚み方向(すなわち鉛直線に沿う上向きの方向)に向かって、発泡成形時の下層は略一定の剛性を有し、発泡成形時の中層から上層に渡って、徐々に剛性(硬度)が高まる傾向にある。
つまり、本発明にかかる第一実施形態の軟質ポリウレタンフォームの厚み方向の剛性分布において、略一定の傾向を示す第一領域と、連続的な増加傾向又は減少傾向を示す第二領域とが存在する。第二領域において、軟質ポリウレタンフォームの発泡成形時の下層から上層へ向かう方向に見るとその剛性分布は増加傾向を示すが、同じ軟質ポリウレタンフォームを発泡成形時の上層から下層へ向かう方向に見るとその剛性分布は減少傾向を示す。
発泡成形の方法によらず、本発明にかかる軟質ポリウレタンフォームの第二実施形態は、発泡成形時の下層から上層へ向かう厚み方向(すなわち鉛直線に沿う上向きの方向)に向かって、徐々に剛性(硬度)が高まる傾向にある。つまり、本発明にかかる軟質ポリウレタンフォームの厚み方向の剛性分布が、連続的な増加傾向又は減少傾向を示す。ここで、軟質ポリウレタンフォームの発泡成形時の下層から上層へ向かう方向に見るとその剛性分布は増加傾向を示すが、同じ軟質ポリウレタンフォームを発泡成形時の上層から下層へ向かう方向に見るとその剛性分布は減少傾向を示す。
表1及び表2に示す配合で、ポリイソシアネート(B)以外の成分を含む混合液と、ポリイソシアネート(B)とを混合して、発泡原液を調製した。この発泡原液を金型に注入して、発泡成形することにより、厚み70mmのシート用パッドを製造した。得られたシート用パッドについて、下記の測定方法により硬度を測定し、以下の評価を行った。
以下、発泡成形時の上下の向きを反転させて、発泡成形時の下面を表面と見て、発泡成形時の上面を裏面と見る。この理由は、軟質ポリウレタンフォームをシート用パッドとして使用する場合、シート用パッドの座面に対応する前記表面側が柔らかく、座面と反対側の前記裏面側が硬い構成であると、安定した座り心地が得られ易いからである。
上記で測定した硬度とは別に、各成形体について日本工業規格JIS K 6400-2に準拠して、25%硬度を測定した。各測定値(単位:N/mm2)を表3~6に示す。
上記で測定した、表面からの深さ位置が異なる4箇所の硬度の測定値の平均を算出して、その平均値に対する各箇所の硬度比を算出した。この硬度比は、発泡成形体の厚み方向の平均的な硬度に対する各箇所(各深さ位置)の硬度の比を意味する。これらの結果を表5~6に示す。また、横軸に各深さ位置をとり、縦軸に硬度比をとったグラフを図1に示す。
深さ10.7%(第一評価サンプル)の硬度比が深さ32.1%(第二評価サンプル)の硬度比よりも大きい場合、シート用パッドとして求められる安定感が足りず、横方向のGが加わった場合のぐらつき感が大きい「×」と判断した。
深さ10.7%の硬度比が深さ32.1%の硬度比よりも小さく、且つ、深さ10.7%の硬度比が0.80以上1未満である場合、シート用パッドとして求められる安定感があり、横方向のGが加わった場合のぐらつき感が低減されている「○」と判断した。
これらの評価結果を表5~6に示す。
「ポリエーテルポリオールA1-1」は、EO/POモル比13/87、重量平均分子量7000、官能基数3のポリエーテルポリオールである。
「ポリエーテルポリオールA1-2」は、EO/POモル比15/85、重量平均分子量6000、官能基数3のポリエーテルポリオールである。
「ポリエーテルポリオールA1-3」は、EO/POモル比15/85、重量平均分子量5000、官能基数3のポリエーテルポリオールである。
「ポリエーテルポリオールA1-4」は、EO/POモル比16/84、重量平均分子量7000、官能基数4のポリエーテルポリオールである。
「ポリマーポリオールA2-1」は、固形分33%、水酸基価23mgKOH/g、重量平均分子量5400、3.2官能のポリマーポリオール(三洋化成工業株式会社製、商品名:KC855)である。
「架橋剤C-2」は、EO/POモル比100/0、分子量400、官能基数4の市販のポリエーテルポリオールである。
「架橋剤C-3」は、グリセリンである。
「架橋遅延化剤D-1」は、モメンティブ社製のアルカノールアミン(商品名:PM-1)である。
「触媒E-2」は、市販の泡化触媒であり、ビス[2-(ジメチルアミノ)エチル]エーテル(東ソー株式会社製、商品名:TOYOCAT ET33B)である。
「触媒E-3」は、市販のジエタノールアミンである。
「整泡剤F-2」は、エボニック社製の高活性型のシリコーン系整泡剤(商品名:B8742)である。
「発泡剤G-1」は、水である。
「ポリイソシアネート(B)」は、市販のポリイソシアネートであり、TDI/MDI=80/20(質量比)で混合されたTDI系イソシアネートである。
Claims (8)
- ポリオール、ポリイソシアネート、架橋剤、発泡剤、及び触媒を含有する発泡原液を発泡成形して得られる軟質ポリウレタンフォームであって、
前記ポリオールとして、重量平均分子量Mwが3000~12000であり且つ官能基数が3~4であるポリエーテルポリオールを含有し、
前記架橋剤として含まれる化合物の全体におけるエチレンオキシド基/プロピレンオキシド基(モル比)が100以上であり、
前記架橋剤として重量平均分子量が1000以下の短鎖ポリオールを含有し、
前記ポリイソシアネートとして、トリレンジイソシアネートをイソシアネート当量で70以上含有する軟質ポリウレタンフォーム。 - 前記触媒として、樹脂化触媒及び泡化触媒のうち少なくとも樹脂化触媒を含有し、
前記樹脂化触媒:前記泡化触媒の質量比が100:0~100:100である請求項1に記載の軟質ポリウレタンフォーム。 - 前記発泡原液中、前記ポリオールの100質量部に対して、アルカノールアミンを0.1~1.0質量部含有する請求項1又は2に記載の軟質ポリウレタンフォーム。
- 前記発泡原液に含まれるポリエーテルポリオールが1種であり、前記ポリエーテルポリオールが有する官能基数が3.5以上である請求項1~3の何れか一項に記載の軟質ポリウレタンフォーム。
- 前記ポリオールとして、ポリマーポリオールを含有する請求項1~4の何れか一項に記載の軟質ポリウレタンフォーム。
- 前記軟質ポリウレタンフォームの厚み方向の剛性分布が、連続的な増加傾向又は減少傾向を示す請求項1~5の何れか一項に記載の軟質ポリウレタンフォーム。
- 前記軟質ポリウレタンフォームの厚み方向の剛性分布において、略一定の傾向を示す領域と、連続的な増加傾向又は減少傾向を示す領域とが存在する請求項1~5の何れか一項に記載の軟質ポリウレタンフォーム。
- 請求項1~7の何れか一項に記載の軟質ポリウレタンフォームが使用されたシート用パッド。
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