JP6536001B2 - Soft polyurethane foam molding composition - Google Patents

Description

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

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

It is known to use various metal compounds and tertiary amine compounds as catalysts to control the reaction rate in the production of polyurethane foams. In the production of flexible polyurethane foams, metal compounds are often used in combination with tertiary amines in most cases, for example, because the productivity and moldability are reduced, and the use of metal compounds alone is scarce. Further, some metal catalysts contain heavy metals such as lead, tin and mercury, and there are also problems with toxicity and the environment. Examples of tertiary amine compounds include, for example, conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ′ ′, N ′ ′-pentamethyldiethylene triamine, N-methyl morpholine, N-ethyl morpholine, N, N-dimethyl ethanolamine and the like.

The above-mentioned tertiary amine catalyst is gradually released to the atmosphere as a volatile organic compound (VOC) from a polyurethane product, and causes problems of odor, discoloration of polyvinyl chloride surface, fogging and the like in automobile interior materials and the like. In addition, since tertiary amine catalysts generally have strong odor and the working environment at the time of polyurethane resin production is significantly deteriorated, reduction of VOC volatilized from polyurethane products is required. In contrast to these volatile tertiary amine catalysts, reactive amine catalysts having hydroxyl groups and primary and secondary amino groups that can react with polyisocyanate in the molecule are proposed as a method to solve this problem. (For example, refer patent documents 1-3). However, reactive amine catalysts generally have low catalytic activity, and the amount of catalyst used tends to increase. An increase in the amount of the catalyst used has a problem that the physical properties and the durability of the polyurethane resin are deteriorated because the amount of the catalyst remaining in the urethane resin or combined with the isocyanate and taken in the skeleton of the urethane resin increases.

On the other hand, flexible polyurethane foams for seat cushions of automobiles are required to have high durability so as not to change the driver's point of view due to the shape change caused by long-time riding from the viewpoint of safety. In particular, in the recent seat cushions, it is required to reduce the density of the flexible foam as much as possible from the viewpoint of cost reduction and fuel efficiency improvement. Since reduction of foam density has a significant adverse effect on durability, it is required to establish a technique for maintaining sufficient durability even when the density is reduced. Until now, flexible foams for car seat cushions have been known which suppress odor derived from amine catalysts and have sufficient durability in the low density region.

Japanese Patent Laid-Open No. 46-4846 Japanese Examined Patent Publication No. 61-31727 Japanese Examined Patent Publication No. 57-14762

The present invention has been made in view of the above background art, and the object of the present invention is to obtain a flexible foam without causing odor problems, toxicity and environmental problems, and reducing the density to less than 55 kg / m 3. To provide a vehicle seat cushion, a seat back and a saddle that maintain good durability and achieve both good ride quality and high safety.

  That is, the present invention relates to a composition for molding a flexible polyurethane foam produced using a specific polyol component, a polyisocyanate component and an amine catalyst constituting the flexible polyurethane foam, and the following (1) to (4) It is shown.

(1) the polyol component (A), the polyisocyanate component (B), amine catalyst (C), foam stabilizer (D), and the flexible polyurethane foam obtained from the foaming agent (E), as the polyol (A-1) as a catalyst was prepared using a double metal cyanide complex catalyst or a phosphazene catalyst or an imino group-containing phosphazenium salt, a hydroxyl value 18~50mgKOH / g, a total unsaturation degree 0.001～0.03Meq. / Using g of polyoxyalkylene polyol, using a urethane modified modified polyphenylene polymethylene polyisocyanate in polyethylene glycol (F) as the polyisocyanate component (B), at least reactive amine catalysts as amine catalyst (C), polyol The flexible polyurethane foam characterized by using 0.01-5 mass% with respect to 100 mass% of polyol components (A) containing (A-1).
(2) The polyol (A-1) is characterized in that the primary hydroxylation ratio of the terminal hydroxyl group is 60 to 90%, and the polyol (A-1) contains at least 30% by mass or more with respect to the polyol component (A). Flexible polyurethane foam .
(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% 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 (1) Or the flexible polyurethane foam as described in any one of (2).
(4) Apparent density is less than 55 kg / m 3 and 25% compression hardness of the skinned foam test piece is 100 to 400 N / 314 cm 2, hysteresis loss ratio is less than 30%, and wet heat compression strain is less than 12% The flexible polyurethane foam as described in any one of (1)-(3) characterized by these.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have low odor and excellent durability by using a specific polyol component, a polyisocyanate component and an amine catalyst for producing a flexible foam. It has been found that a flexible foam satisfying the comfort and economy can be obtained.

The polyol component (A) in the present invention is polyaddition with diisocyanate to form a polyurethane, and a bifunctional to tetrafunctional short molecule 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-octacosan 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 and pentaerythritol; low molecular weight such as aniline, ethylene diamine, propylene diamine, toluene diamine, metaphenylene diamine, diphenylmethane diamine and xylylene diamine Amines; low molecular weight amino alcohols such as monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine and the like; That. Among these, ethylene glycol, diethylene glycol, glycerin, trimethylolpropane and pentaerythritol are preferable because they are versatile because they are inexpensive and the supply stability is also good.

Examples of the alkylene oxide to be subjected to 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 or 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. The alkylene oxides may be used alone or in combination of two or more. When two or more alkylene oxides are used in combination, a combination of propylene oxide and ethylene oxide is particularly preferable.

The polyol (A-1) in the present invention is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of an alkylene oxide with an initiator in the presence of a ring-opening addition polymerization catalyst. In the present invention, a hydroxyl number of 18 to 50 mg KOH / g and a total unsaturation degree of 0.001 to 0.03 meq. Use a polyalkylene polyol of not more than 1 / g. When the hydroxyl value of the polyol (A-1) is less than 18 mg KOH / g, the hardness of the polyurethane foam obtained is too soft as a flexible foam for a seat of a vehicle, and poor mixing and deterioration of flowability due to high viscosity. It is easy to occur. On the other hand, if it exceeds 50 mg KOH / g, the hardness of the polyurethane foam may be too high, and the flexibility may be reduced.

An increase in the total degree of unsaturation of the polyol (A-1) means that the monool component having an unsaturated group at the end is increased, and the total degree of unsaturation is 0.03 meq. When it is larger than 1 g, the durability decreases with the decrease in the crosslink density of the foam. Also, 0.001 meq. When it is smaller than / g, it is difficult to industrially produce.

Although a KOH catalyst is generally known as a ring-opening addition polymerization catalyst for polyoxyalkylene polyol, in the present invention, it is preferable to use a complex metal cyanide complex catalyst or a phosphazene catalyst or an imino group-containing phosphazenium salt. When a polyoxyalkylene polyol is produced using a KOH catalyst, it is known that a monool having an unsaturated group at the end is by-produced as the molecular weight of the polyoxyalkylene polyol increases, and the monool is contained in a large amount. When polyoxyalkylene polyol is used as a polyurethane raw material, the obtained polyurethane may have low hardness and durability.

The primary hydroxylation ratio of the terminal hydroxyl group of the polyol (A-1) is preferably 60 to 90%, more preferably 70 to 90%. If the primary hydroxylation ratio of the terminal hydroxyl groups is lower than 60%, the molding stability of the molded flexible polyurethane foam may be reduced, and disintegration or sinking may occur. On the other hand, if the primary hydroxylation ratio of the terminal hydroxyl group is higher than 90%, the closed cell foamability (single foamability) of the foam may be increased, which may cause molding shrinkage. Here, the primary conversion ratio is a ratio at which the terminal hydroxyl group is primary, and can be represented by [(number of primary hydroxyl groups / number of total hydroxyl groups) × 100 (%)].

The polyol (A-1) is desirably contained in an amount of at least 30% by mass or more based on the total amount of the polyol component (A) used. When the amount is less than 30% by mass, the amount of monool having unsaturated groups at the end relatively increases, 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, a polymer polyol produced by polymerizing a vinyl monomer in a polyol by a usual method can be used in combination for the purpose of adjusting the hardness. As such a polymer polyol, those obtained by polymerizing and stably dispersing a vinyl monomer in the presence of a radical initiator in the same polyalkylene polyol as the above-mentioned polyol (A-1) can be mentioned. Further, examples of the vinyl-based monomer include acrylonitrile, styrene, vinylidene chloride, hydroxyalkyl, methacrylate, and alkyl methacrylate. Among these, acrylonitrile and styrene are preferable. Specific examples of such polymer polyols include EL-910 and EL-923 manufactured by Asahi Glass Urethane Co., and FA-728R manufactured by Sanyo Chemical Industries, Ltd.

The polyisocyanate component (B) used in the present invention is a modified polyphenylene polymethylene poly urethane-modified with polyethylene glycol (F) using diphenylmethane diisocyanate (B-1) and polyphenylene polymethylene polyisocyanate (B-2) as an isocyanate source. It is characterized by using an isocyanate. When urethane foam modification is carried out with polyethylene glycol (F), when it becomes a flexible foam, electrostatic interaction occurs between the oxyethylene units in the resin, or between the oxyethylene unit and the urethane or urea bond, and a pseudo crosslinked structure By taking this, it is possible to realize a low hysteresis loss rate and high durability even with a low impact resilience foam.

The polyethylene glycol (F) according to the present invention preferably has a number average molecular weight of 600 to 1,600. When the number average molecular weight is less than 600, it is not possible to take a pseudo crosslinked structure sufficiently and low hysteresis loss and high durability can not be realized. When the number average molecular weight is greater than 1600, the low temperature storage stability of the isocyanate is significantly reduced. As an available product, PEG-600, PEG-1000, PEG-1540, etc. by Sanyo Chemical Industries, Ltd. are mentioned.

It is preferable that the diphenylmethane diisocyanate (B-1) content rate concerning this invention is the range of 65-90 mass%. When the content of diphenylmethane diisocyanate (B-1) exceeds 90% by mass, the storage stability at low temperature of the obtained polyisocyanate composition and the durability and hardness of the obtained flexible foam are reduced. On the other hand, if the amount is less than 65% by mass, the crosslink density becomes too high, and the foam becomes hard to the extent that it is not suitable for a seat cushion and the tensile elongation at break of the foam is reduced. You may not be able to get

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 It is preferable that it is 10-50 mass%, and, as for isomer content rate, it is more preferable that it is 20-45 mass%.

If the content of 2,2'-MDI and 2,4'-MDI based on the total amount of MDI according to the present invention is less than 10% by mass, the storage stability at low temperature of the obtained polyisocyanate composition is impaired, and the isocyanate storage location In addition to the need for constant heating in the piping and the foam molding machine, the molding stability of the flexible foam is impaired, and foam collapse or the like occurs during foaming. On the other hand, if it exceeds 50% by mass, the foam hardness is lowered, and sufficient hardness can not be secured as a seat cushion, seat back or saddle, the reactivity is lowered, the molding cycle is extended, and the foam rate is high And the hysteresis loss rate may increase.

Amine catalyst for use in the present invention (C) is a reactive amine catalyst having a hydroxy group capable of reacting with a polyisocyanate in the molecule, the polyol component (A comprising polyol (A-1) as the amount added And 0.01 to 5% by mass with respect to 100% by mass. If the amount 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 can not be obtained, but also the physical properties of the polyurethane foam, in particular, the durability may be deteriorated.

Since it is important in the production of flexible polyurethane foams to maintain a proper balance between the resinification reaction and the foaming reaction, hydroxyl groups or primary compounds which can react with polyisocyanate in the molecule as an amine catalyst used in the present invention It is possible to use a reaction type catalyst having a graded and secondary amino group alone or in combination. Such reactive catalysts include 2-hydroxymethyltriethylenediamine, hydroxytriethylenediamine, hydroxymethyltriethylenediamine, hydroxyethyltriethylenediamine, N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether, N, N, N'-trimethylaminoethyl ethanolamine, N, N-dimethylaminoethoxyethanol can be used, among which 2-hydroxymethyltriethylenediamine or N, N, N'-trimethyl-N'-hydroxy It is preferred to use ethyl-bisaminoethyl ether. Specific examples thereof include R-ZETA manufactured by Tosoh Corporation and JEFFCAT ZF-10 manufactured by Huntsman Corporation.

In the present invention, the amine catalyst to be used may be added at the time of reaction, or it may be simultaneously added at the time of reaction. Moreover, when mixing them, it can also be melt | dissolved and used for a solvent. The solvent is not particularly limited, but, for example, alcohols such as ethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, butanediol, 2-methyl-1,3-propanediol, toluene, xylene, mineral terpene, Hydrocarbons such as mineral spirits, esters such as ethyl acetate, butyl acetate, methyl glycol acetate, cellosolve acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide And organic solvents for amides, β-diketones such as acetylacetone and its fluorinated substitution products, chelating solvents such as keto esters such as methyl acetoacetate and ethyl acetoacetate, water, etc. .

As the foam stabilizer (D) used in the present invention, a conventional 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, E-8 BLF made by Evonik, B-8715LF2, Shin-Etsu Chemical Company-made F-122 etc. are mentioned. As for the quantity of these foam stabilizers, 0.1-3 mass% is preferable with respect to 100 mass% of polyol components (A) containing a polyol (A-1).

Water is mainly used as the blowing agent (E) used in the present invention. Water reacts with isocyanate groups to generate carbon dioxide gas, which causes foaming. Also, water and optionally any blowing agent may be used. For example, small amounts of low boiling point organic compounds such as cyclopentane and isopentane may be used in combination, or air or nitrogen gas or liquefied carbon dioxide may be mixed and dissolved in the stock solution using a gas loading device to foam. The amount of blowing agent added depends on the set density of the product obtained. Usually, it is 0.5 to 10% by mass with respect to 100% by mass of the polyol component (A) containing the polyol (A-1), but it is 2 to 6% by mass when considered as a seat cushion application for a vehicle Is preferred. If the upper limit is exceeded, foaming may be difficult to stabilize, and if it is less than the lower limit, foaming may not be effective.

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

And, in the production of the flexible polyurethane foam in the present invention, anti-aging agents such as antioxidants and UV absorbers, fillers such as calcium carbonate and barium sulfate, flame retardants, plasticizers, coloring agents, anti-mold agents And the like, known various additives and assistants can be used as required.

Next, a method of producing a flexible foam will be described. The flexible foam is characterized by an apparent density of less than 55 kg / m 3, a 25% compression hardness of 100 to 400 N / 314 cm 2, a hysteresis loss ratio of less than 30%, and a wet heat compression strain of less than 12%. It is produced by reacting and foaming a mixture of the polyol component (A), the polyisocyanate component (B), the amine catalyst (C), the foam stabilizer (D), and the foaming agent (E) of the present invention.

The apparent density is the method described in JIS K 6400, the 25% compression hardness of the test piece foam with skin is the B method described in JIS K 6400, the hysteresis loss rate is the B method described in JIS K 6400, and the wet heat compression strain is It refers to the value measured by the method described in JIS K6400.

    The molar ratio (NCO group / active hydrogen group) in 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), preferably 0.8 to 1.3 (isocyanate index (NCO INDEX) = 80 to 130 as a good range of foam durability and molding cycle Is more preferred.

If the isocyanate index is less than 70, the durability decreases or the single foam property is excessively increased, and if it is higher than 140, the molding cycle is prolonged due to the long remaining unreacted isocyanate, and foam foaming is delayed due to high molecular weight formation. Cell collapse etc. may occur.

As a method for producing a flexible foam, a foaming stock solution of a mixture 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 of producing a flexible polyurethane molded foam (hereinafter referred to as a flexible molded foam) characterized in that it is injected into the inside and then foamed and cured can be used.

As a mold temperature at the time of pouring the above-mentioned foaming stock solution into a mold, it is usually 30-80 ° C, preferably 45-65 ° C. If the mold temperature at the time of pouring the above-mentioned foaming stock solution into the mold is less than 30 ° C., it leads to the extension of the production cycle due to the decrease in reaction rate, while on the other hand, it is higher than 80 ° C. Excessive acceleration of the reaction between water and isocyanate may cause the foam to collapse during foaming, or may cause deterioration of the durability and foam feel due to the local increase of the urea bond.

The curing time for foaming and curing the foaming stock solution is 10 minutes or less, preferably 7 minutes or less, in consideration of the production cycle of a general vehicle seat pad, saddle, and the like.

When producing a flexible molded foam, the above-mentioned components 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 molded foam.
The polyisocyanate component and the polyol component are preferably mixed immediately before foaming. The other components can be premixed with the polyisocyanate component or the polyol component within the range not affecting the storage stability of the raw material and the change with time of the reactivity. The mixture may be used immediately after mixing or may be used as needed after storage. In the case of a foaming apparatus having a structure capable of simultaneously introducing two or more components into the mixing part, it is also possible to separately introduce a polyol, a blowing agent, a polyisocyanate, a catalyst, a foam stabilizer, an additive and the like into the mixing part.
Further, the mixing method may be either dynamic mixing in which mixing is performed in the machine head mixing chamber of the foaming machine, static mixing in which mixing is performed in the liquid feed pipe, or both may be used in combination. Mixing of gaseous components such as physical blowing agents and liquid components 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 device used in the present invention is preferably a high pressure foaming device which does not require solvent cleaning of the mixing section.

The mixed solution obtained by such mixing is discharged into a mold, and is foamed and cured, and then the mold is removed. It is also preferable to apply a mold release agent to the mold in advance in order to smoothly carry out the above-mentioned demolding. As a 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 destroy the cell membrane of the foam under compression or under reduced pressure by a conventionally known method to stabilize the appearance and dimensions of the subsequent products.

A suitable flexible foam obtained according to the present invention has an apparent density of less than 55 kg / m 3 measured by the method of JIS K 6400, and a 25% compression hardness of the skinned foam test piece measured by the method B according to JIS K 6400. It is 100 to 400 N / 314 cm 2 and is characterized in that the hysteresis loss rate by method B according to JIS K6400 is less than 30%, and the wet heat compression strain according to JIS K 6400 is less than 12%.

Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples. In addition, unless otherwise indicated, "part" and "%" in a sentence are mass references.

Preparation of Polyol Premix A polyol component (A), an amine catalyst (C), a foam stabilizer (D), and water (E) as a foaming agent are separately charged into a 100 L mixer equipped with a stirrer and uniformly mixed. Mixed.

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

<Isocyanate component B>
· Isocyanate I-1:
In a reactor equipped with a stirrer, a thermometer, a cooler and a nitrogen gas inlet: 1 L of a reactor, 2,2'-diphenylmethane diisocyanate (2,2'-MDI): 1.4%, 2,4'-diphenylmethane Diisocyanate (2,4'-MDI): 658.1 g of diphenylmethane diisocyanate (MDI) containing 43.4% was charged, and after raising the temperature to 75 ° C., Polyol F-1 (average functional group number 2 number average molecular weight 1, 1, 2 25.6 g of an ethylene oxide unit content of 100%, PEG-1000 manufactured by Sanyo Chemical Industries, Ltd. was charged, and the urethane reaction was carried out for 2 hours while uniformly mixing with a stirring blade while maintaining the temperature. Subsequently, 316.4 g of polyphenylenepolymethylene polyisocyanate (Poly-MDI) having an MDI content of 39% and a content ratio of 2,2'-MDI and 2,4'-MDI in MDI of 2.5% was charged, for 30 minutes. After stirring, the reaction solution was cooled to room temperature to obtain isocyanate group-terminated prepolymer "I-1" (NCO content: 31.6%). The composition of Poly-MDI obtained by adding MDI charged before the reaction with PEG-1000 and Poly-MDI charged after the reaction was 80.2% MDI content, 2,2'-MDI in MDI and 2 The total content of 4, 4'-MDI was 38.1%.
Isocyanate I-2:
In a reactor equipped with a stirrer, a thermometer, a cooler and a nitrogen gas inlet: 1 L of a reactor, 2,2'-diphenylmethane diisocyanate (2,2'-MDI): 1.4%, 2,4'-diphenylmethane Diisocyanate (2,4'-MDI): 658.1 g of diphenylmethane diisocyanate (MDI) containing 43.4% is charged, and after raising the temperature to 75 ° C., Polyol F-2 (average functional group number 2 number average molecular weight 1, 1, 2 25.6 g of an ethylene oxide unit content of 0% and PP-1000 manufactured by Sanyo Chemical Industries, Ltd. was charged, and the urethane formation reaction was performed for 2 hours while uniformly mixing with a stirring blade while maintaining the temperature. Subsequently, 316.4 g of polyphenylenepolymethylene polyisocyanate (Poly-MDI) having an MDI content of 39% and a content ratio of 2,2'-MDI and 2,4'-MDI in MDI of 2.5% was charged, for 30 minutes. After stirring, the reaction solution was cooled to room temperature to obtain an isocyanate group-terminated prepolymer "I-2" (NCO content: 31.6%). The composition of Poly-MDI obtained by adding MDI charged before the reaction with PP-1000 and Poly-MDI charged after the reaction was 80.2% MDI content, 2,2'-MDI in MDI and 2 The total content of 4, 4'-MDI was 38.1%.
· Isocyanate I-3:
Isocyanate blended with isocyanate I-1 and isocyanate I-2 in a ratio of 1: 1. MDI content 80.2%, 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, Tosoh TEDA-L33
Catalyst C-2: 70% dipropylene glycol solution of bis (2-dimethylaminoethyl) ether, Tosoh TOYOCAT-ET
Catalyst C-3: 2-hydroxymethyltriethylenediamine, Tosoh Corporation R-ZETA
Catalyst C-4: N, N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether, Huntsman JEFFCAT ZF-10

<Flow control agent D>
Foam control agent D-1: silicone type foam control agent, manufactured by Momentive L-5309

Foam molding [foaming condition]
Mold temperature: 55 to 60 ° C
Mold shape: 100 x 300 x 300 mm
Mold material: Aluminum curing conditions: 55 ~ 60 ° C × 4 minutes

-Measuring method of physical properties of polyurethane foam Apparent density, wet heat compression residual strain is a method described in JIS K 6400, 25% compression hardness (ILD) of a test piece foam with skin is a hysteresis loss by method B according to JIS K 6400 The rate was measured by method B described in JIS K6400, and the moist heat residual strain was measured by the method described in JIS K6400. The odor was evaluated using an odor sensor COSMOXP-329 manufactured by New Cosmos Denki. The odor of the foam sample was measured over time under conditions of 20 ° C. and 55% RH, and the time until the odor dropped to the numerical value of the measurement environmental level was measured. Those with an odor falling to the measurement environment level within 10 hours are "○", those with the odor falling to the measurement environment level within 24 hours "Δ", and the samples not falling to the measurement environment level even after 100 hours have passed X.

-Formability evaluation of foam The state of the flexible polyurethane foam immediately after molding was confirmed.
Collapse: Plunging phenomenon after the molded foam reaches its maximum height

Examples 1 to 3 of flexible foam molded articles, Comparative Example 1

Examples 4 to 5 of flexible foam molded articles, Comparative examples 2 to 3

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

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

As is clear from the results shown in Table 1, Example 1 is 2-hydroxymethyltriethylenediamine which is a reactive amine catalyst having a hydroxy group capable of reacting with polyisocyanate in the molecule, and N, N, N'-. The composition was a combination of trimethyl-N'-hydroxyethyl-bisaminoethyl ether, and it was confirmed that the odor was small. In addition, it has been confirmed that by combining the specific polyol component and the polyisocyanate component described in the present application, it is possible to obtain a foam having good hysteresis loss and durability even in the low density region. 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 primary hydroxylation ratio of the terminal hydroxyl group 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 filling property of the foam was reduced, 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 reduced, so that a good hysteresis loss could not be obtained.

  In Comparative Example 6, since the set total degree of unsaturation was large and the crosslink density of the foam decreased, the hysteresis loss and the durability deteriorated.

In Comparative Example 7, since polyethylene glycol was not used as a modifier, the molding stability of the foam was reduced and a good foam was not obtained. Further, in Comparative Example H-8, the crosslinking effect due to the aggregation of the oxyethylene glycol unit was low, and the result was that the hysteresis loss exceeded 30%.

In the present invention, the polyol component (A) and the polyisocyanate component (B) can be combined with an amine catalyst (C), a foam stabilizer (D), and a foaming agent by comparing the above-described examples and comparative examples. In the flexible polyurethane foam obtained by reacting in the presence of E), the polyol (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 and has a hydroxyl value of 18 to 50 mg KOH / g, total unsaturation degree 0.001 to 0.03 meq. At least a reaction type amine catalyst as an amine catalyst (C), using a modified polyphenylene polymethylene isocyanate urethane-modified with polyethylene glycol (F) as a polyisocyanate component (B) using a polyoxyalkylene polyol of not more than 1 g / g By using 0.01 to 5% by mass with respect to 100% by mass of the polyol component (A) containing the polyol (A-1), the hysteresis loss and durability of the foam are good even in the low density region, and the odor is It is clear that less flexible polyurethane foams can be obtained, and one can understand the significance and remarkable excellence of the composition of the present invention.

Claims (4)

The polyol component (A), the polyisocyanate component (B), amine catalyst (C), foam stabilizer (D), and the process for producing a flexible polyurethane foam obtained from the foaming agent (E), as the polyol (A-1) as a catalyst was prepared using a double metal cyanide complex catalyst or a phosphazene catalyst or an imino group-containing phosphazenium salt, a hydroxyl value 18~50mgKOH / g, a total unsaturation degree 0.001～0.03Meq. / Using g of polyoxyalkylene polyol, using a urethane modified modified polyphenylene polymethylene polyisocyanate in polyethylene glycol (F) as the polyisocyanate component (B), at least reactive amine catalysts as amine catalyst (C), polyol 0.01-5 mass% is used with respect to 100 mass% of polyol components (A) containing (A-1), The manufacturing method of the flexible polyurethane foam characterized by the above-mentioned. The flexible polyurethane foam according to claim 1, wherein the polyol (A-1) has a primary conversion ratio of terminal hydroxyl groups of 60 to 90% and contains at least 30% by mass or more based on the polyol component (A). Manufacturing method . 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'-diphenylmethane diisocyanate contained in diphenylmethane diisocyanate (B-1) The total amount of (C) 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 manufacturing method of the flexible polyurethane foam as described in any one. Apparent density less than 55 kg / m ³ , and 25% compression hardness of skinned foam test piece is 100 to 400 N / 314 cm ² , hysteresis loss ratio is less than 30%, wet heat compression strain is less than 12% The manufacturing method of the flexible polyurethane foam of any one of Claims 1-3 characterized by the above-mentioned.