JP2016060895A - Composition for molding flexible polyurethane form - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a seat cushion, a seat back and a saddle for a vehicle capable of maintaining durability required for a flexible foam and achieving both favorable riding comfortability and high safety even if the density is reduced to less than 55 kg/m3 without causing odor problems or problems to toxicity and environments.SOLUTION: There is provided a flexible polyurethane foam obtained by reacting a polyol component (A) and a polyisocyanate component (B) in the presence of an amine catalyst, a foam stabilizer and a foaming agent, wherein a polyol component (A-1) is produced using a composite metal cyanide complex catalyst, a phosphazene catalyst or an imino group-containing phosphazenium salt as a catalyst and the flexible polyurethane foam is produced using a polyoxyalkylene polyol having a hydroxyl value of 18 to 50 mgKOH/g and a total unsaturation degree of 0.001 to 0.03 meq./g or less, a modified polyphenylene polymethylene isocyanate modified with a polyethylene glycol as the polyisocyanate component and a reactive type amine catalyst.SELECTED DRAWING: None

Description

The present invention relates to a flexible polyurethane foam molding composition having low odor and high durability. More specifically, the present invention relates to a composition for molding a flexible polyurethane foam for vehicle seat cushions having low odor, high durability, and good ride comfort.

The flexible polyurethane foam is produced by reacting a polyol and a polyisocyanate in the presence of a catalyst, a foaming agent, and, if necessary, a foam stabilizer, a flame retardant, a crosslinking agent and the like.

In the production of polyurethane foams, it is known to use various metal compounds and tertiary amine compounds as catalysts in order to control the reaction rate. In the production of flexible polyurethane foams, metal compounds are often used in combination with tertiary amines in many cases, such as a decrease in productivity and moldability, and are rarely used only with metal compounds. Further, some metal-based catalysts contain heavy metals such as lead, tin, and mercury, and there are problems with toxicity and the environment. Examples of the tertiary amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine and the like can be mentioned.

The above-mentioned tertiary amine catalyst is gradually released from the polyurethane product into the atmosphere as a volatile organic compound (VOC), and causes problems such as odor problems, discoloration of PVC skin, and fogging in automobile interior materials. Further, the tertiary amine catalyst generally has a strong odor, and the working environment at the time of producing the polyurethane resin is remarkably deteriorated. Therefore, it is required to reduce the VOC volatilized from the polyurethane product. In response to these volatile tertiary amine catalysts, reactive amine catalysts having a hydroxyl group capable of reacting with polyisocyanate in the molecule and primary and secondary amino groups have been proposed as a method for solving this problem. (For example, refer to Patent Documents 1 to 3). However, a reactive amine catalyst generally has a low catalytic activity and tends to increase the amount of catalyst used. An increase in the amount of the catalyst used has a problem that the physical properties and durability of the polyurethane resin deteriorate because the amount remaining in the urethane resin or combined with the isocyanate and taken into the skeleton of the urethane resin increases.

On the other hand, flexible polyurethane foam for automobile seat cushions is required to have high durability so that the viewpoint of the driver does not change due to a shape change caused by riding for a long time from the viewpoint of safety. Particularly in recent seat cushions, the density of the flexible foam is required to be as low as possible from the viewpoint of cost reduction and fuel efficiency improvement. Since reducing the density of the foam has a significant adverse effect on the durability, establishment of a technique for maintaining sufficient durability even when the density is lowered is required. Until now, there has been no known flexible foam for automobile seat cushions that suppresses odors derived from amine catalysts and achieves sufficient durability in a low density region.

JP-A-46-4846 Japanese Patent Publication No. 61-31727 Japanese Patent Publication No.57-14762

The present invention has been made in view of the above-mentioned background art, and its purpose is to obtain a flexible foam without causing odor problems, toxicity and environmental problems, and even when the density is reduced to less than 55 kg / m 3. The present invention provides a vehicle seat cushion, a seat back, and a saddle that maintain a good durability and achieve both good riding comfort and high safety.

  That is, this invention relates to the composition for a flexible polyurethane foam manufactured using the specific polyol component which comprises a flexible polyurethane foam, a polyisocyanate component, and an amine catalyst, and the following (1)-(4) It is shown.

(1) In a flexible polyurethane foam obtained by reacting a polyol component (A) and a polyisocyanate component (B) in the presence of an amine catalyst (C), a foam stabilizer (D), and a foaming agent (E), the polyol Component (A-1) is produced using a double metal cyanide complex catalyst or phosphazene catalyst or imino group-containing phosphazenium salt as a catalyst, and has a hydroxyl value of 18 to 50 mgKOH / g and a total unsaturation of 0.001 to 0.03 meq. / G polyoxyalkylene polyol, modified polyphenylene polymethylene isocyanate urethane-modified with polyethylene glycol (F) as polyisocyanate component (B), and at least reactive amine catalyst as amine catalyst (C), polyol A composition for molding flexible polyurethane foam, which is used in an amount of 0.01 to 5% by mass based on 100% by mass of the polyol (A) containing the component (A-1).
(2) The polyol component (A-1) has a primary hydroxyl group conversion rate of 60 to 90%, and is at least 30% by mass or more based on the polyol component (A). A flexible polyurethane foam molding composition.
(3) The polyisocyanate component (B) contains diphenylmethane diisocyanate (B-1) in the range of 65 to 90% by mass, and 2,2′-diphenylmethane diisocyanate and 2,4 ′ contained in diphenylmethane diisocyanate (B-1). -The total amount of diphenylmethane diisocyanate is 10 to 50 mass% with respect to the total amount of diphenylmethane diisocyanate (B-1), and the number average molecular weight of polyethylene glycol (F) is 600 to 1600 (1) Or the composition for flexible polyurethane foam molding as described in any one of (2).
(4) The apparent density is less than 55 kg / m3, the 25% compression hardness of the foamed test piece with skin is 100 to 400 N / 314 cm2, the hysteresis loss rate is less than 30%, and the wet heat compression strain is less than 12%. The composition for molding flexible polyurethane foam according to any one of (1) to (3), wherein

As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have used a specific polyol component, polyisocyanate component and amine catalyst for the production of flexible foams, resulting in low odor and excellent durability. And found that a flexible foam satisfying ride comfort and economy can be obtained.

The polyol component (A) in the present invention forms a polyurethane by polyaddition with diisocyanate, and a bifunctional to tetrafunctional short molecular polyol can be used as an initiator of the polyoxyalkylene polyol. Specifically, water, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, 2 , 2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1, 3-hexanediol, 2-n-hexadecane-1,2-ethylene glycol, 2-n-eicosane-1,2-ethylene glycol, 2-n-octacosane 1,2-ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, hydrogenated bisphenol A, 3-hydroxy-2,2-dimethylpropyl-3- Low molecular weight polyols such as hydroxy-2,2-dimethylpropionate, trimethylolpropane, glycerin, pentaerythritol; low molecular weights such as aniline, ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine Amines; low molecular weight amino alcohols such as monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, etc. That. Among these, ethylene glycol, diethylene glycol, glycerin, trimethylolpropane, and pentaerythritol are preferable because they are versatile and are inexpensive and have good supply stability.

Examples of the alkylene oxide that undergoes ring-opening addition polymerization to the initiator include epoxy compounds such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, and cyclohexene oxide. Among these, ethylene oxide, propylene oxide, 1,2-butylene oxide or styrene oxide is preferable, and ethylene oxide and propylene oxide are more preferable. Moreover, this alkylene oxide may be used independently and may use 2 or more types together. When two or more types of alkylene oxide are used in combination, the combined use of propylene oxide and ethylene oxide is particularly preferable.

  The polyol (A-1) in the present invention is a polyoxyalkylene polyol obtained by subjecting an alkylene oxide to ring-opening addition polymerization to an initiator in the presence of a ring-opening addition polymerization catalyst. In the present invention, a hydroxyl value of 18 to 50 mgKOH / g and a total unsaturation of 0.001 to 0.03 meq. / G or less of polyalkylene polyol is used. When the hydroxyl value of the polyol component (A-1) is less than 18 mgKOH / g, the hardness of the resulting polyurethane foam is too soft for a vehicle seat flexible foam, and poor mixing and poor liquid flow due to high viscosity. Is likely to occur. On the other hand, when it exceeds 50 mgKOH / g, the hardness of the polyurethane foam becomes too high, and the flexibility may be lowered.

  An increase in the total degree of unsaturation of the polyol component (A-1) means an increase in the number of monool components having an unsaturated group at the terminal, and the total degree of unsaturation is 0.03 meq. When it is larger than / g, the durability is lowered as the crosslinking density of the foam is lowered. 0.001 meq. When it is smaller than / g, it is difficult to produce industrially.

As a polyoxyalkylene polyol ring-opening addition polymerization catalyst, a KOH catalyst is generally known, but in the present invention, a double metal cyanide complex catalyst, a phosphazene catalyst, or an imino group-containing phosphazenium salt is preferably used. When a polyoxyalkylene polyol is produced using a KOH catalyst, it is known that a monool having an unsaturated group at the terminal is produced as a by-product with an increase in the molecular weight of the polyoxyalkylene polyol, and a large amount of the monool is contained. When polyoxyalkylene polyol is used as a polyurethane raw material, the resulting polyurethane may have low hardness and durability.

The primary component hydroxylation rate of the polyol component (A-1) is preferably 60 to 90%, more preferably 70 to 90%. When the terminal hydroxyl group primary ratio is lower than 60%, the molding stability of the molded flexible polyurethane foam is lowered, and collapse or sink may occur. On the other hand, when the terminal hydroxyl group primary conversion ratio is higher than 90%, the closed cell property (single cell property) of the foam becomes strong, and molding shrinkage may occur. Here, the primary rate is the ratio at which the terminal hydroxyl groups are primary, and can be represented by [(number of primary hydroxyl groups / total number of hydroxyl groups) × 100 (%)].

The polyol component (A-1) is preferably contained in an amount of at least 30% by mass or more based on the total amount of the polyol (A) used. When the amount is less than 30% by mass, the amount of the monool having an unsaturated group at the terminal is relatively increased, and the durability of the resulting flexible polyurethane foam may not be sufficiently improved.

In the method for producing a flexible foam of the present invention, for the purpose of adjusting the hardness, a polymer polyol produced by polymerizing a vinyl monomer in a polyol by an ordinary method can be used in combination. Examples of such a polymer polyol include those obtained by polymerizing and stably dispersing a vinyl monomer in the presence of a radical initiator in the same polyalkylene polyol as the polyol component (A-1). Examples of the vinyl monomer include acrylonitrile, styrene, vinylidene chloride, hydroxyalkyl, methacrylate, and alkyl methacrylate. Among them, acrylonitrile and styrene are preferable. Specific examples of such a polymer polyol include EL-910 and EL-923 manufactured by Asahi Glass Urethane Co., Ltd. and FA-728R manufactured by Sanyo Chemical Industries.

The polyisocyanate component (B) used in the present invention is a modified polyphenylene polymethylene polyurethane modified with polyethylene glycol (F) using diphenylmethane diisocyanate (B-1) or polyphenylene polymethylene polyisocyanate (B-2) as an isocyanate source. Isocyanate is used. When a flexible foam is formed by urethane modification with polyethylene glycol (F), an electrostatic interaction occurs between oxyethylene units in the resin, or between oxyethylene units and urethane or urea bonds, and a pseudo-crosslinked structure By taking a foam, a low hysteresis loss rate and high durability can be achieved even with a foam having a low impact resilience.

The polyethylene glycol (F) according to the present invention has a suitable number average molecular weight of 600 to 1600. When the number average molecular weight is less than 600, a pseudo-crosslinked structure cannot be obtained sufficiently and low hysteresis loss and high durability cannot be realized. When the number average molecular weight is larger than 1600, the low-temperature storage stability of the isocyanate is significantly lowered. Examples of available products include PEG-600, PEG-1000, and PEG-1540 manufactured by Sanyo Chemical Industries.

The diphenylmethane diisocyanate (B-1) content according to the present invention is preferably in the range of 65 to 90% by mass. When the diphenylmethane diisocyanate (B-1) content exceeds 90% by mass, the polyisocyanate composition obtained has low storage stability at low temperatures and the durability and hardness of the resulting flexible foam. On the other hand, if it is less than 65% by mass, the crosslinking density becomes too high, the foam becomes hard to the extent that it is not suitable for a seat cushion, the elongation at break of the foam is reduced, and the foam strength sufficient for a soft foam for vehicle seats May not be available.

Furthermore, the sum of the content of 2,2′-diphenylmethane diisocyanate (hereinafter 2,2′-MDI) and the content of 2,4′-diphenylmethane diisocyanate (hereinafter 2,4′-MDI) with respect to the total amount of diphenylmethane diisocyanate (hereinafter, “lower”) The isomer content) is preferably 10 to 50% by mass, and more preferably 20 to 45% by mass.

If the content of 2,2′-MDI and 2,4′-MDI is less than 10% by mass based on the total amount of MDI according to the present invention, the storage stability at low temperatures of the resulting polyisocyanate composition is impaired, In addition to constant heating inside the piping and foam molding machine, the molding stability of the flexible foam is impaired and foam collapse occurs during foaming. On the other hand, if it exceeds 50% by mass, the foam hardness is lowered, and sufficient hardness cannot be secured as a seat cushion, seat back or saddle, the reactivity is lowered, the molding cycle is extended, and the foam has a high foam rate. In some cases, the hysteresis loss rate increases.

The amine catalyst (C) used in the present invention is a reactive amine catalyst having a hydroxy group capable of reacting with polyisocyanate in the molecule, and the amount added is a polyol (A-1) containing a polyol component (A-1). ) The range is 0.01 to 5% by mass with respect to 100% by mass. If it is less than 0.01% by mass, the effect of the catalyst may not be obtained. On the other hand, if it exceeds 5% by mass, not only the effect of increasing the catalyst cannot be obtained, but also the physical properties, particularly the durability, of the polyurethane foam may deteriorate.

In the production of a flexible polyurethane foam, it is important to appropriately maintain a balance between the resinification reaction and the foaming reaction. Therefore, as an amine catalyst used in the present invention, a hydroxyl group capable of reacting with polyisocyanate in the molecule or the first group. A reactive catalyst having a secondary and secondary amino group can be used alone or in combination. Such reactive catalysts include 2-hydroxymethyltriethylenediamine, hydroxytriethylenediamine, hydroxymethyltriethylenediamine, hydroxyethyltriethylenediamine, N, N, N′-trimethyl-N′-hydroxyethyl-bisaminoethyl ether, N, N, N′-trimethylaminoethylethanolamine and N, N-dimethylaminoethoxyethanol can be used, among which 2-hydroxymethyltriethylenediamine and N, N, N′-trimethyl-N′-hydroxy Preference is given to using ethyl-bisaminoethyl ether. Specific examples include R-ZETA manufactured by Tosoh Corporation and JEFFCAT ZF-10 manufactured by Huntsman Corporation.

In the present invention, the amine catalyst used in advance may be added during the reaction or may be added simultaneously during the reaction. Moreover, when mixing them, it can also be melt | dissolved and used for a solvent. Although it does not specifically limit as a solvent, For example, alcohol, such as ethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, butanediol, and 2-methyl-1,3-propanediol, toluene, xylene, mineral terpene, Hydrocarbons such as mineral spirits, esters such as ethyl acetate, butyl acetate, methyl glycol acetate and cellosolve acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide Examples include solvable organic solvents such as amides, β-diketones such as acetylacetone and fluorinated substituents thereof, chelating solvents such as ketoesters such as methyl acetoacetate and ethyl acetoacetate, and water. .

As the foam stabilizer (D) used in the present invention, a normal surfactant is used, and an organosilicon surfactant can be suitably used. For example, SZ-1327, SZ-1325, SZ-1336, SZ-3601 manufactured by Toray Dow Corning, Y-10366, L-5309 manufactured by Momentive, B-8724LF2, B-8715LF2, manufactured by Evonik, Shin-Etsu Chemical Examples include F-122 manufactured by the company. The amount of these foam stabilizers is preferably 0.1 to 3% by mass with respect to 100% by mass of the polyol (A) containing the polyol component (A-1).

As the foaming agent (E) used in the present invention, water is mainly used. Water generates carbon dioxide gas by reaction with the isocyanate group, which causes foaming. Moreover, you may use arbitrary foaming agents in addition to water. For example, a small amount of a low-boiling organic compound such as cyclopentane or isopentane may be used in combination, or air, nitrogen gas, or liquefied carbon dioxide may be mixed and dissolved in the stock solution using a gas loading device and foamed. The amount of foaming agent added depends on the set density of the resulting product. Usually, it is 0.5 to 10% by mass with respect to 100% by mass of the polyol (A) containing the polyol component (A-1), but 2 to 6% by mass when considered as a vehicle seat cushion application. It is preferable. If the upper limit is exceeded, foaming may become difficult to stabilize, and if it is less than the lower limit, foaming may not be effective.

In addition, a crosslinking agent such as diethanolamine or triethanolamine can be added to the present invention for the purpose of improving molding stability and adjusting foam hardness. A preferable addition amount of the crosslinking agent is up to 5% by mass with respect to 100% by mass of the polyol (A) containing the polyol component (A-1). When the crosslinking agent is added more than necessary, strong foaming properties may be produced, or the mechanical strength may deteriorate due to an increase in the crosslinking density.

In the production of the flexible polyurethane foam in the present invention, an anti-aging agent such as an antioxidant and an ultraviolet absorber, a filler such as calcium carbonate and barium sulfate, a flame retardant, a plasticizer, a colorant, and an antifungal agent. Various known additives and auxiliaries such as can be used as necessary.

Next, the manufacturing method of a flexible foam is demonstrated. The flexible foam is characterized in that the apparent density is less than 55 kg / m3, the 25% compression hardness of the foamed test piece with skin is 100 to 400 N / 314 cm2, the hysteresis loss rate is less than 30%, and the wet heat compression strain is less than 12%. The polyol component (A), polyisocyanate component (B), amine catalyst (C), foam stabilizer (D), and foaming agent (E) of the present invention are produced by reaction foaming.

The apparent density is the method described in JIS K6400, the 25% compression hardness of the test piece foam with skin is the method B described in JIS K6400, the hysteresis loss rate is the method B described in JIS K6400, and the wet heat compression strain is The value measured by the method described in JIS K6400.

    The molar ratio (NCO group / active hydrogen group) at the time of mixed foaming of all isocyanate groups in the polyisocyanate composition of the present invention and all active hydrogen groups in the active hydrogen group-containing compound containing water is 0.7 to 1. .4 (isocyanate index (NCO INDEX) = 70 to 140), and 0.8 to 1.3 (isocyanate index (NCO INDEX) = 80 to 130 as a good range of the durability and molding cycle of the foam. ) Is more preferable.

If the isocyanate index is less than 70, the durability is lowered and the foam is excessively increased. If it is higher than 140, the unreacted isocyanate remains for a long time, the molding cycle is extended, and the foaming is delayed due to the high molecular weight. Cell collapse may occur.

As a method for producing a flexible foam, a foaming stock solution of a mixed solution of the polyol component (A), the polyisocyanate component (B), the amine catalyst (C), the foam stabilizer (D), and the foaming agent (E) is used as a mold. A method for producing a flexible polyurethane mold foam (hereinafter referred to as “soft mold foam”) can be used, which is injected into the inside and then foam-cured.

The mold temperature when the foaming stock solution is poured into the mold is usually 30 to 80 ° C, preferably 45 to 65 ° C. When the mold temperature at the time of pouring the foaming stock solution into the mold is less than 30 ° C., it leads to the extension of the production cycle due to a decrease in the reaction rate. On the other hand, when the temperature is higher than 80 ° C., the reaction between the polyol and the isocyanate When the reaction between water and isocyanate is excessively promoted, the foam may collapse in the course of foaming, or durability and foam feel may deteriorate due to a local increase in urea bonds.

The curing time when the foaming stock solution is foam-cured is 10 minutes or less, preferably 7 minutes or less in consideration of production cycles of general vehicle seat pads, saddles, and the like.

When producing a flexible mold foam, each component can be mixed using a high-pressure foaming machine, a low-pressure foaming machine, or the like, as in the case of a normal flexible mold foam.
The polyisocyanate component and the polyol component are preferably mixed immediately before foaming. The other components can be mixed in advance with the polyisocyanate component or the polyol component in such a range that does not affect the storage stability of the raw materials and the change with time of the reactivity. These mixtures may be used immediately after mixing or may be used in appropriate amounts after storage. In the case of a foaming apparatus having a structure capable of simultaneously introducing more than two components into the mixing part, polyols, foaming agents, polyisocyanates, catalysts, foam stabilizers, additives and the like can be individually introduced into the mixing part.
The mixing method may be either dynamic mixing in which mixing is performed in the machine head mixing chamber of the foaming machine or static mixing in which mixing is performed in the liquid feeding pipe, or both may be used in combination. Mixing of a gaseous component such as a physical foaming agent and a liquid component is often performed by static mixing, and mixing of components that can be stably stored as a liquid is often performed by dynamic mixing. The foaming apparatus used in the present invention is preferably a high-pressure foaming apparatus that does not require solvent cleaning of the mixing part.

The liquid mixture obtained by such mixing is discharged into a mold (mold), foamed and cured, and then demolded. In order to perform the demolding smoothly, it is also preferable to apply a release agent to the mold in advance. As the release agent to be used, a release agent usually used in the field of molding processing may be used.

Although the product after demolding can be used as it is, it is preferable to stabilize the appearance and dimensions of the product thereafter by destroying the cell membrane of the foam under compression or reduced pressure by a conventionally known method.

The preferred flexible foam obtained by the present invention has an apparent density measured by the method of JIS K6400 of less than 55 kg / m3 and the 25% compression hardness of the foamed test piece with skin measured by the method B of JIS K6400. 100 to 400 N / 314 cm 2, wherein the hysteresis loss rate according to the method B described in JIS K6400 is less than 30%, and the wet heat compression strain described in JIS K6400 is less than 12%.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. Unless otherwise specified, “part” and “%” in the text are based on mass.

-Preparation of polyol premix Charge a polyol component (A), an amine catalyst (C), a foam stabilizer (D), and water (E) as a foaming agent into a 100 L mixer equipped with a stirrer, and uniformly Mixed.

・ Raw material <Polyol component A>
Polyol A-1-1: Two types of polyoxyalkylene polyols produced using an imino group-containing phosphazenium salt as a catalyst were blended, hydroxyl value = 104 (mg KOH / g), total unsaturation degree 0.03 meq./ g, The terminal hydroxyl group was adjusted so that the primary ratio was 58%.
Polyol A-1-2: Two types of polyoxyalkylene polyols produced using an imino group-containing phosphazenium salt as a catalyst were blended, hydroxyl value = 98 (mg KOH / g), total unsaturation degree 0.03 meq./ g, The terminal hydroxyl group was adjusted so that the primary ratio was 60%.
Polyol A-1-3: Two types of polyoxyalkylene polyols produced using an imino group-containing phosphazenium salt as a catalyst were blended, hydroxyl value = 38 (mgKOH / g), total unsaturation degree 0.03 meq./ g, The terminal hydroxyl group was adjusted so that the primary ratio was 80%.
Polyol A-1-4: Two types of polyoxyalkylene polyols produced using an imino group-containing phosphazenium salt as a catalyst were blended, hydroxyl value = 38 (mgKOH / g), total unsaturation degree 0.03 meq./ g, The terminal hydroxyl group was adjusted so that the primary ratio was 90%.
Polyol A-1-5: Two types of polyoxyalkylene polyols produced using an imino group-containing phosphazenium salt as a catalyst were blended, hydroxyl value = 17 (mg KOH / g), total unsaturation degree 0.03 meq./ g, The terminal hydroxyl group was adjusted so that the primary ratio was 88%.
Polyol A-1-6: Two kinds of polyoxyalkylene polyols produced using an imino group-containing phosphazenium salt as a catalyst were blended, hydroxyl value = 20 (mg KOH / g), total unsaturation degree 0.03 meq./ g, The terminal hydroxyl group was adjusted so that the primary ratio was 87%.
Polyol A-1-7: Two types of polyoxyalkylene polyols produced using an imino group-containing phosphazenium salt as a catalyst were blended, hydroxyl value = 38 (mg KOH / g), total unsaturation degree 0.03 meq./ g, The terminal hydroxyl group was adjusted so that the primary ratio was 81%.
Polyol A-1-8: Two types of polyoxyalkylene polyols produced using an imino group-containing phosphazenium salt as a catalyst were blended, hydroxyl value = 48 (mg KOH / g), total unsaturation degree 0.03 meq./ g, The terminal hydroxyl group was adjusted so that the primary ratio was 78%.
Polyol A-1-9: Two types of polyoxyalkylene polyols produced using an imino group-containing phosphazenium salt as a catalyst were blended, hydroxyl value = 52 (mg KOH / g), total unsaturation degree 0.03 meq./ g, The terminal hydroxyl group was adjusted so that the primary ratio was 76%.
Polyol A-1-10: Two types of polyoxyalkylene polyols produced using an imino group-containing phosphazenium salt as a catalyst were blended, hydroxyl value = 47 (mg KOH / g), total unsaturation 0.009 meq./ g, The terminal hydroxyl group was adjusted so that the primary ratio was 87%.
Polyol A-1-11: Two types of polyoxyalkylene polyols produced using an imino group-containing phosphazenium salt as a catalyst were blended, hydroxyl value = 24 (mg KOH / g), total unsaturation degree 0.03 meq./ g, The terminal hydroxyl group was adjusted so that the primary ratio was 85%.
Polyol A-1-12: Two kinds of polyoxyalkylene polyols produced using imino group-containing phosphazenium salt and KOH as a catalyst were blended, hydroxyl value = 28 (mg KOH / g), total unsaturation degree 0.05 meq ./g, and the terminal hydroxyl group was converted to a primary ratio of 87%.
Polyol A-2: a polymer polyol produced using KOH as a catalyst with an average number of functional groups = 3.0 and a hydroxyl value = 28 (mgKOH / g).
Polyol A-3: Polyoxyethylene polyoxypropylene polyol produced by using KOH as a catalyst with a polymerization initiator average functional group number = 3.0 and hydroxyl value = 48 (mgKOH / g).

<Isocyanate component B>
・ Isocyanate I-1:
Capacity with stirrer, thermometer, condenser and nitrogen gas inlet tube: 1 L reactor, 2,2′-diphenylmethane diisocyanate (2,2′-MDI): 1.4%, 2,4′-diphenylmethane Diisocyanate (2,4′-MDI): Diphenylmethane diisocyanate (MDI) containing 43.4%: 658.1 g was charged and heated to 75 ° C., then polyol F-1 (average functional group number 2 number average molecular weight 1, 000, ethylene oxide unit content 100%, PEG-1000 manufactured by Sanyo Chemical Industries, Ltd.) was charged, and urethanization reaction was performed for 2 hours while uniformly mixing with a stirring blade while maintaining the temperature. Subsequently, 316.4 g of polyphenylene polymethylene polyisocyanate (Poly-MDI) having an MDI of 39% and a content of 2,2′-MDI and 2,4′-MDI in MDI of 2.5% was charged for 30 minutes. After stirring, the mixture was cooled to room temperature to obtain an isocyanate group-terminated prepolymer “I-1” (NCO content 31.6%). The composition of Poly-MDI, which is the sum of MDI charged before the reaction with PEG-1000 and Poly-MDI charged after the reaction, is 80.2% MDI content, 2,2′-MDI in MDI and 2 , 4′-MDI was 38.1% in total.
Isocyanate I-2:
Capacity with stirrer, thermometer, condenser and nitrogen gas inlet tube: 1 L reactor, 2,2′-diphenylmethane diisocyanate (2,2′-MDI): 1.4%, 2,4′-diphenylmethane Diisocyanate (2,4′-MDI): Diphenylmethane diisocyanate (MDI) containing 43.4%: 658.1 g was charged and heated to 75 ° C., then polyol F-2 (average functional group number 2 number average molecular weight 1, 000, ethylene oxide unit content 0%, PP-1000 manufactured by Sanyo Chemical Industries Co., Ltd.), and urethanation reaction was performed for 2 hours while uniformly mixing with a stirring blade while maintaining the temperature. Subsequently, 316.4 g of polyphenylene polymethylene polyisocyanate (Poly-MDI) having an MDI of 39% and a content of 2,2′-MDI and 2,4′-MDI in MDI of 2.5% was charged for 30 minutes. After stirring, the mixture was cooled to room temperature to obtain an isocyanate group-terminated prepolymer “I-2” (NCO content 31.6%). The composition of Poly-MDI, which is the sum of the MDI charged before the reaction with PP-1000 and the Poly-MDI charged after the reaction, was 80.2% MDI content, 2,2′-MDI in MDI and 2 , 4′-MDI was 38.1% in total.
・ Isocyanate I-3:
Isocyanate obtained by blending isocyanate I-1 and isocyanate I-2 in a ratio of 1: 1. The MDI content is 80.2%, and the total content of 2,2′-MDI and 2,4′-MDI in MDI is 38.1%.

<Amine catalyst C>
Catalyst C-1: 33% dipropylene glycol solution of triethylenediamine, TEDA-L33 manufactured by Tosoh Corporation
Catalyst C-2: 70% dipropylene glycol solution of bis (2-dimethylaminoethyl) ether, TOYOCAT-ET manufactured by Tosoh Corporation
Catalyst C-3: 2-hydroxymethyltriethylenediamine, R-ZETA manufactured by Tosoh Corporation
Catalyst C-4: N, N, N′-trimethyl-N′-hydroxyethyl-bisaminoethyl ether, JEFFCAT ZF-10 manufactured by Huntsman

<Foam stabilizer D>
Foam stabilizer D-1: Silicone foam stabilizer, L-5309 manufactured by Momentive

・ Form molding [foaming conditions]
Mold temperature: 55-60 ° C
Mold shape: 100 × 300 × 300mm
Mold material: Aluminum cure Conditions: 55-60 ° C x 4 minutes

Method for measuring physical properties of polyurethane foam The apparent density and wet heat compression residual strain are the methods described in JIS K6400, and the 25% compression hardness (ILD) of the test piece foam with skin is the B method described in JIS K6400. The rate was measured by the method B described in JIS K6400, and the wet heat residual strain was measured by the method described in JIS K6400. The odor was evaluated using an odor sensor COSMOXP-329 manufactured by Shin Cosmos Electric Co., Ltd. The odor of the foam sample was measured over time under the conditions of 20 ° C. and 55% RH, and the time until the odor decreased to the numerical value of the measurement environment level was measured. “O” indicates that the odor falls to the measurement environment level within 10 hours, “△” indicates that the odor falls to the measurement environment level within 24 hours, and “No” indicates that the sample does not fall to the measurement environment level after 100 hours. × ”.

-Foam moldability evaluation The state of the flexible polyurethane foam immediately after molding was confirmed.
Collapse: Phenomenon that sinks greatly after the molded foam reaches its maximum height

Examples 1 to 3 and Comparative Example 1 of flexible foam molded products

Examples 4 to 5 and Comparative Examples 2 to 3 of flexible foam molded products

Examples 6 to 8 of flexible foam molded article, Comparative examples 4 to 5

Examples 9 to 10 of flexible foam molded article, Comparative examples 6 to 8

As is apparent from the results shown in Table 1, Example 1 is a reactive amine catalyst having a hydroxy group capable of reacting with polyisocyanate in the molecule, 2-hydroxymethyltriethylenediamine and N, N, N′—. The composition was a combination of trimethyl-N′-hydroxyethyl-bisaminoethyl ether, and it was confirmed that there was little odor. It was also confirmed that a foam having good foam hysteresis loss and durability could be obtained even in a low density region by combining the specific polyol component and polyisocyanate component described in the present application. On the other hand, in Comparative Example 1, the odor derived from the amine catalyst remains in the foam for a long time, which may cause odor problems and environmental problems.

As shown in Comparative Examples 2 and 3, when the terminal hydroxyl group primary rate was low, the molding stability of the foam was insufficient and a good foam could not be obtained.

  In Comparative Example 4, since the set hydroxyl value was low and the viscosity of the polyol was high, the liquid flow was deteriorated and the foam filling property was lowered, so that a good foam could not be obtained.

  In Comparative Example 5, the set hydroxyl value was high, the hardness of the polyurethane foam was too high, and the flexibility was lowered, so that good hysteresis loss could not be obtained.

  In Comparative Example 6, since the set total unsaturation was large and the crosslinking density of the foam was reduced, hysteresis loss and durability were deteriorated.

In Comparative Example 7, since polyethylene glycol was not used as the modifier, the molding stability of the foam was lowered and a good foam could not be obtained. In Comparative Example H-8, the cross-linking effect due to the aggregation of the oxyethylene glycol unit was low, and the hysteresis loss exceeded 30%.

By comparing the above Examples and Comparative Examples, in the present invention, the polyol component (A) and the polyisocyanate component (B) are converted into an amine catalyst (C), a foam stabilizer (D), and a foaming agent ( In the flexible polyurethane foam obtained by reacting in the presence of E), the polyol component (A-1) is produced using a double metal cyanide complex catalyst, phosphazene catalyst or imino group-containing phosphazenium salt as a catalyst, and has a hydroxyl value of 18 To 50 mg KOH / g, total unsaturation 0.001 to 0.03 meq. / G or less polyoxyalkylene polyol, modified polyphenylene polymethylene isocyanate urethane-modified with polyethylene glycol (F) as polyisocyanate component (B), and at least reactive amine catalyst as amine catalyst (C), By using 0.01 to 5% by mass with respect to 100% by mass of the polyol (A) containing the polyol component (A-1), the hysteresis loss and durability of the foam are good even in a low density region, and the odor It is clear that fewer flexible polyurethane foams are obtained, and the significance and significant excellence of the composition of the present invention can be understood.

Claims (4)

In a flexible polyurethane foam obtained by reacting a polyol component (A) and a polyisocyanate component (B) in the presence of an amine catalyst (C), a foam stabilizer (D), and a foaming agent (E), the polyol component (A -1) is produced using a double metal cyanide complex catalyst or a phosphazene catalyst or an imino group-containing phosphazenium salt as a catalyst, having a hydroxyl value of 18 to 50 mg KOH / g and a total unsaturation of 0.001 to 0.03 meq. / G polyoxyalkylene polyol, modified polyphenylene polymethylene isocyanate urethane-modified with polyethylene glycol (F) as polyisocyanate component (B), and at least reactive amine catalyst as amine catalyst (C), polyol A composition for molding flexible polyurethane foam, which is used in an amount of 0.01 to 5% by mass based on 100% by mass of the polyol (A) containing the component (A-1). 2. The flexible polyurethane according to claim 1, wherein the polyol component (A-1) has a terminal hydroxyl group primary conversion ratio of 60 to 90% and is at least 30% by mass or more based on the polyol component (A). Foam molding composition. 2,2′-diphenylmethane diisocyanate and 2,4′-diphenylmethane diisocyanate contained in diphenylmethane diisocyanate (B-1), wherein the polyisocyanate component (B) contains diphenylmethane diisocyanate (B-1) in the range of 65 to 90% by mass. The total amount of is 10 to 50% by mass with respect to the total amount of diphenylmethane diisocyanate (B-1), and the number average molecular weight of polyethylene glycol (F) is 600 to 1600. The flexible polyurethane foam molding composition according to any one of the above items. The apparent density is less than 55 kg / m3, the 25% compression hardness of the foamed test piece with skin is 100 to 400 N / 314 cm2, the hysteresis loss rate is less than 30%, and the wet heat compression strain is less than 12%. The composition for flexible polyurethane foam molding according to any one of claims 1 to 3.