JP2001122940A - Method for producing flexible polyurethane foam for automotive cushion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a flexible polyurethane foam for automotive cushions having a high strength and a high impact resilience. SOLUTION: This method for producing a flexible polyurethane foam is characterized as reacting the following polyisocyanate composition with a polyol composition in the presence of a foam stabilizer, a catalyst and a foaming agent. (a) a diphenylmethane diisocyanate having >=15 mass % total content of the 2,2'-isomer and the 2,4'-isomer, (b) a tri- or a polyfunctional diphenylmethane diisocyanate-based condensate, (c) tolylene diisocyanate, (d) a polyoxyalkylene polyol having 5-15 mass % content of oxyethylene groups and (e) a polyoxyalkylene polyol having 60-90 mass % content of the oxyethylene groups, with the proviso that the mass ratio of the (a) to (b) is (a)/(b)= (50/50) to (90/10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a flexible polyurethane foam for an automobile seat cushion. More specifically, the present invention relates to a method for producing a flexible polyurethane foam for an automobile seat cushion which is lightweight and has excellent physical properties.

[0002]

2. Description of the Related Art Conventionally, flexible polyurethane foam has been used for automobile cushion,
It is widely used for headrests, furniture, etc., and the required performance varies depending on the purpose, use site, and the like. As isocyanates for flexible polyurethane foams, tolylene diisocyanate (hereinafter abbreviated as TDI) and T
Isocyanate (hereinafter abbreviated as NCO) group-terminated prepolymers using DI have been used.

In recent years, diphenylmethane diisocyanate (hereinafter referred to as MDI) has been used as an isocyanate component.
), A mixture of MDI and an MDI-based condensate having 3 or more functional groups (hereinafter abbreviated as polymeric MDI), and NCO-terminated prepolymers obtained by reacting these with polyols are widely used as isocyanates for flexible polyurethane foams. It is used.

In NCO-terminated prepolymers which also use isocyanates for flexible polyurethane foams, polyether polyols, polyester polyols, polymer polyols and the like are used as polyols used as so-called modifiers.

For example, Japanese Patent Application Laid-Open No. 7-330850 discloses that a mixture of MDI and polymeric MDI and a compound having two or more active hydrogen atoms are used as an initiator and a compound having 3 carbon atoms.
A method for producing a flexible polyurethane foam using a polyisocyanate composition comprising an NCO-terminated prepolymer obtained by reacting the above-mentioned polyether polyol containing an alkylene oxide as an essential component and TDI is disclosed. Also, JP-A-8-157554 discloses that
A process for producing a flexible polyurethane foam using a polyisocyanate composition comprising an NCO-terminated prepolymer obtained by reacting a mixture of MDI, polymeric MDI and TDI with a polyoxyalkylene polyol having a nominal number of functional groups of 2 to 3 is disclosed. ing.

[0006]

In recent years, from the viewpoint of improving fuel efficiency for automobiles, it has been required to reduce the weight of vehicles. Along with this, the weight of the vehicle cushion has been required to be reduced without decreasing the strength and the like. Further, in order to improve ride comfort, a polyurethane foam having a large rebound resilience is required. Conventionally, a high-strength flexible polyurethane foam has a low rebound resilience, and a high-rebound resilience has a low strength. That is, none of the flexible polyurethane foams obtained by the conventional formulas satisfy such required performance.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies and studies to solve the above problems, and as a result, have found that N
The present inventors have found that a method for producing a flexible polyurethane foam using a polyisocyanate containing a CO group-terminated prepolymer can solve the above problems, and have completed the present invention.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS That is, the present invention provides the following (1) to
(4). (1) An isocyanate group-terminated prepolymer obtained by reacting (a) a polyisocyanate comprising (a) to (c) shown below and a (b) modifying agent comprising (d) and (e) shown below. (A) a polyisocyanate composition and (B) a polyol composition, (C) a foam stabilizer,
(D) A method for producing a flexible polyurethane foam for an automobile seat cushion which is reacted in the presence of a catalyst and (E) a foaming agent, wherein the flexible polyurethane foam has a core density of 40 kg / m ³ or less and a rebound resilience of 65%. The above-mentioned manufacturing method characterized by the above. (A) Diphenylmethane diisocyanate having a total content of 2,2'-isomer and 2,4'-isomer of 15% by mass or more (b) Triphenyl- or more functional diphenylmethane diisocyanate condensate (c) Tolylene diisocyanate ( D) Polyoxyalkylene polyol having an oxyethylene group content of 5 to 15% by mass. (E) Polyoxyalkylene polyol having an oxyethylene group content of 60 to 90% by mass. However, the mass ratio of (a) and (b) is (b) / (b) = 50
/ 50 to 90/10, and the content of (C) in (A) is 15 to 45% by mass.

(2) (a) a polyisocyanate comprising (a) and (b) shown below, and (d) and
Isocyanate group-terminated prepolymer obtained by reacting (b) a modifying agent comprising (e), and (A) a polyisocyanate composition containing (c) and (B) a polyol composition, In the method for producing a flexible polyurethane foam for an automobile seat cushion, which is reacted in the presence of a foam stabilizer, a catalyst (D) and a foaming agent (E), the flexible polyurethane foam has a core density of 40 kg / m ³ or less and a rebound resilience. Characterized in that the rate is 65% or more,
The manufacturing method. (A) Diphenylmethane diisocyanate having a total content of 2,2'-isomer and 2,4'-isomer of 15% by mass or more (b) Triphenyl- or more functional diphenylmethane diisocyanate condensate (c) Tolylene diisocyanate ( D) Polyoxyalkylene polyol having an oxyethylene group content of 5 to 15% by mass. (E) Polyoxyalkylene polyol having an oxyethylene group content of 60 to 90% by mass. However, the mass ratio of (a) and (b) is (b) / (b) = 50
/ 50 to 90/10, and the content of (C) in (A) is 15 to 45% by mass.

(3) an isocyanate group-terminated prepolymer obtained by reacting (a) shown below, and (b) a modifier consisting of (d) and (e) shown below, and (a)
(B) a polyisocyanate composition containing (C) and (B) a polyol composition, (C) a foam stabilizer,
(D) A method for producing a flexible polyurethane foam for an automobile seat cushion which is reacted in the presence of a catalyst and (E) a foaming agent, wherein the flexible polyurethane foam has a core density of 40 kg / m ³ or less and a rebound resilience of 65%. The above-mentioned manufacturing method characterized by the above. (A) Diphenylmethane diisocyanate having a total content of 2,2'-isomer and 2,4'-isomer of 15% by mass or more (b) Triphenyl- or more functional diphenylmethane diisocyanate condensate (c) Tolylene diisocyanate ( D) Polyoxyalkylene polyol having an oxyethylene group content of 5 to 15% by mass. (E) Polyoxyalkylene polyol having an oxyethylene group content of 60 to 90% by mass. However, the mass ratio of (a) and (b) is (b) / (b) = 50
/ 50 to 90/10, and the content of (C) in (A) is 15 to 45% by mass.

(4) The method for producing a flexible polyurethane foam according to any one of the above (1) to (3), wherein the polyol composition (B) comprises the following (f) to (h): . (F) Nominal number of functional groups = 2 to 6, hydroxyl value = 15 to 45 m
Polyoxyalkylene polyol having gKOH / g, oxyethylene group content = 10 to 20% by mass, and total unsaturation = 0.06 mmol / g or less. (G) Nominal number of functional groups = 2 to 6, hydroxyl value = 15 to 45 m
gKOH / g, oxyethylene group content = 10 to 20% by mass, total unsaturation = 0.06 mmol / g or less in a polyoxyalkylene polyol. A polymer polyol containing 30% by mass. (H) Nominal number of functional groups = 2-6, hydroxyl value = 30-70 m
gKOH / g, polyoxyalkylene polyol having an oxyethylene group content of 50 to 80% by mass.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The present invention relates to (A) a polyisocyanate composition, and (B)
A method for producing a flexible polyurethane foam, comprising reacting a polyol composition with a foam stabilizer (C), a catalyst (D) and a foaming agent (E). Hereinafter, each raw material used in the present invention will be described.

The polyisocyanate composition (A) comprises the following components (a) to (e). (A) MDI has two NCO groups and two benzene rings in one molecule, and is called a binuclear body.
(B) MDI is 2,2'-MDI, 2,4'-MD
There are three isomers, I and 4,4'-MDI. 2,2'-MDI of (A) MDI in the present invention
The total content of 2,2'-MDI and 2,4'-MDI is at least 15% by mass, preferably at least 16% by mass. 2,2'-MDI and 2,4'-
When the total of the MDI is less than the lower limit, the stability at the time of foaming tends to be lacked during foam production.

(B) MDI condensates having three or more functional groups are
It has three or more NCO groups and three or more benzene rings in the molecule, and is called a polynuclear. The MDI-based condensate usually exists as a mixture with (A) MDI.

In the present invention, the mass ratio of (a) to (b) is (a) / (b) = 50/50 to 90/10, preferably (a) / (b) = 55/45 to 85. / 15.
If (a) is less than the lower limit, shrinkage (shrinkage) occurs during the production of a flexible polyurethane foam, and problems such as dimensional change of a molded product are likely to occur, and elongation is liable to be significantly reduced. If (b) exceeds the upper limit, the resilience tends to decrease.

(C) TDI is 2,4-TDI and 2,6
-Contains two isomers of TDI. In the present invention, the isomer composition ratio of (c) is preferably such that 2,4-TDI is 65% by mass or more. When the content of 2,4-TDI is less than 65% by mass, the curability tends to be remarkably reduced.

In the present invention, the content of (c) in (A) is 15 to 45% by mass, preferably 20 to 45% by mass.
40% by mass. When (c) is less than the lower limit, the resilience tends to decrease. If the upper limit is exceeded, molding with different hardness becomes difficult.

(D) and (e) are so-called (b) modifiers.

The polyoxyalkylene polyol (d) is obtained by subjecting an alkylene oxide to an addition reaction by a known method using a low molecular weight compound having an active hydrogen group as an initiator, and having an oxyethylene group content of 5 to 5. 15% by mass,
Preferably it is 7-13 mass%. Further, the number of nominal functional groups is preferably 2 to 6, and more preferably 3 to 5. The hydroxyl value is preferably from 15 to 45 mgKOH / g, and more preferably from 17 to 43 mgKOH / g. In the present invention, the “nominal number of functional groups” is the number of active hydrogens contained in one molecule of the initiator.

As a preferred embodiment of (d), after adding propylene oxide to the low molecular polyol described below,
The end is capped with ethylene oxide.

The polyoxyalkylene polyol (e) is obtained by subjecting an alkylene oxide to an addition reaction by a known method using a low-molecular-weight compound having an active hydrogen group as an initiator, and having an oxyethylene group content of 60 to 60. 90 mass%
And preferably 63 to 87% by mass. The nominal number of functional groups is preferably 2 to 6, and more preferably 3 to 5. The hydroxyl value is preferably 20 to 70 mgKOH / g,
Furthermore, 23 to 67 mgKOH / g is more preferable.

A preferred embodiment of (e) is a low molecular polyol described below to which a mixture of propylene oxide and ethylene oxide is added.

In any of (d) and (e), when the oxyethylene group content is less than the lower limit, the foam tends to collapse during foaming. If you exceed the limit,
The strength of the foam tends to decrease.

When the nominal number of functional groups is less than the lower limit,
It becomes difficult to obtain a flexible polyurethane foam having sufficient physical properties. If it exceeds the upper limit, the polyurethane foam using this polyisocyanate tends to have low rebound resilience. When the hydroxyl value exceeds the upper limit, the polyurethane foam using the polyisocyanate tends to have low rebound resilience. When it is less than the lower limit, the viscosity of the obtained polyisocyanate composition becomes too high, so that workability and productivity are apt to be reduced.

Examples of the low molecular weight active hydrogen group-containing compound used in the initiators (d) and (e) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,2-butanediol. , 1,3-butanediol, 1,4-butanediol, diethylene glycol,
Dipropylene glycol, 1,5-pentanediol,
1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, cyclohexane-1,4-diol, cyclohexane-1,4-
Low molecular weight polyols such as sugar alcohols such as dimethanol, bisphenol A, hydrogenated bisphenol A, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, glucose, fructose, ammonia, ethylamine, butylamine, ethylenediamine, propylenediamine And low-molecular-weight polyamines such as hexamethylenediamine, diethylenetriamine, aniline, toluenediamine, metaphenylenediamine, diphenylmethanediamine, and xylylenediamine, and low-molecular-weight amino alcohols such as monoethanolamine, diethanolamine, monopropanolamine, and dipropanolamine. .

In addition, if necessary, (b) the modifying agent may include:
Active hydrogen group-containing compounds other than (d) and (e) can be used, and specifically, the compounds (excluding ammonia) used as the initiators of (d) and (e), polyester polyols, Polyether polyols and polycarbonate polyols other than (d) and (e) are exemplified.

In the present invention, the preferred mass ratio between (d) and (e) is (d) / (e) = 50/50 to 90/10.
And more preferably (d) / (e) = 55/45
85/15. When (d) is too small, the hardness and strength of the foam tend to be insufficient. If the amount of (d) is too large, the resilience tends to be insufficient.

The polyisocyanate composition (A) used in the present invention is obtained by the following (1) to (3). (1) A polyisocyanate composition containing an isocyanate group-terminated prepolymer obtained by reacting (a) a polyisocyanate comprising (a) to (c) and (b) a modifier comprising (d) and (e). object. (2) an isocyanate group-terminated prepolymer obtained by reacting (a) a polyisocyanate composed of (a) and (b), and (b) a modifier composed of (d) and (e), and (c) Polyisocyanate composition containing (3) (b) consisting of (a) and (d) and (e)
A polyisocyanate composition containing an isocyanate group-terminated prepolymer reacted with a modifier, and (b) and (c).

As for the reaction order of the modifiers (d) and (e) in the above (1) to (3), (d) and (e) may be simultaneous or one of them may be reacted first. . Also,
The temperature in the production method of (1) to (3) is 15 to 15
The temperature is 0 ° C, preferably 40 to 100 ° C, and a catalyst described later may be added during the reaction.

It should be noted that (1) to (3)
At any stage in the described production method, the number of NCO groups and the number of hydroxyl groups are such that the number of NCO groups is always larger than the number of hydroxyl groups. The molar ratio (R value) of NCO group / hydroxyl group during the reaction is from 2 to 500, preferably from 50 to 450. When the R value is less than the lower limit, the viscosity of the NCO-terminated prepolymer tends to increase, and the flowability of the liquid decreases, so that the workability tends to be poor. When the R value exceeds the upper limit, the viscosity of the polyisocyanate liquid becomes low, and when the liquid after mixing the polyisocyanate liquid and the polyol liquid is poured into the mold, splash is likely to occur. The NCO-terminated prepolymer thus obtained has an NCO content of 20 to
It is 40% by mass, preferably 22 to 38% by mass. The viscosity is 25 m in consideration of the fluidity of the liquid obtained by mixing the polyisocyanate and the polyol, particularly, the splash.
Pa · s or more is preferable.

The thus obtained (A) polyisocyanate composition and (B) polyol composition are
By reacting in the presence of (C) a foaming agent, (D) a catalyst, and (E) a foam stabilizer, a highly resilient and high-strength flexible polyretan foam can be obtained. At this time, the core density of the foam is 40 kg / m ³ or less. Further, the total density of the foam is preferably ³⁰ to 50 kg / m ³ , particularly preferably 35 to 45 kg / m ³ .

(B) The polyol composition generally has a nominal average number of functional groups of 2 to 8 and a hydroxyl value of 10 to 200 mg.
A KOH / g polyether polyol is used, preferably having a nominal average number of functional groups of 2 to 6, and a hydroxyl value of 10 to 10.
It is a polyether polyol of 150 mgKOH / g. In the present invention, a polyol composition comprising the following (f) to (h) is more preferable.

The polyol (f) is obtained by subjecting an alkylene oxide to an addition reaction by a known method using a low-molecular-weight compound having an active hydrogen group as an initiator, and has a nominal number of functional groups of 2 to 6, and a hydroxyl value. = 15-45 mgKOH /
g, oxyethylene group content = 10 to 20% by mass, total unsaturation = 0.06 mmol / g or less, preferably a nominal number of functional groups = 2 to 5 (particularly preferably 3), and a hydroxyl value = 17. ４３43 mgKOH / g, oxyethylene group content = 12-18 mass%, total unsaturation = 0.05 mm
ol / g or less.

As a preferred embodiment of (f), after adding propylene oxide to the low molecular polyol described below,
The end is capped with ethylene oxide.

The polyol (g) is obtained by subjecting an alkylene oxide to an addition reaction by a known method using a low-molecular-weight compound having an active hydrogen group as an initiator, and has a nominal number of functional groups of 2 to 6, and a hydroxyl value. = 15-45 mgKOH /
g, oxyethylene group content = 10 to 20% by mass, total unsaturation = 0.06 mmol / g or less, preferably a nominal number of functional groups = 2 to 5 (particularly preferably 3), and a hydroxyl value = 17. ４３43 mgKOH / g, oxyethylene group content = 12-18 mass%, total unsaturation = 0.05 mm
ol / g or less of the polyoxyalkylene polyol,
It is a polymer polyol containing 10 to 30% by mass, preferably 12 to 28% by mass of polymer fine particles obtained by polymerizing a vinyl monomer.

The polyol (h) is obtained by subjecting an alkylene oxide to an addition reaction by a known method using a low-molecular-weight compound having an active hydrogen group as an initiator. The polyol has a nominal number of functional groups of 2 to 6, and a hydroxyl value. = 30-70 mgKOH /
g, oxyethylene group content = 50-80% by mass, and preferably, a mixture of propylene oxide and ethylene oxide is subjected to an addition reaction, and the number of nominal functional groups = 2-5.
(Particularly preferably 3), hydroxyl value = 33-67 mg KO
It is a polyoxyalkylene polyol having H / g and an oxyethylene group content of 53 to 77% by mass.

As a preferred embodiment of (h), a low molecular polyol described below is added with a mixture of propylene oxide and ethylene oxide.

In any of the cases (f) to (h), when the nominal number of functional groups is less than the lower limit, it becomes difficult to obtain a flexible polyurethane foam having sufficient physical properties. When the nominal number of functional groups exceeds the upper limit, the polyurethane foam using this polyisocyanate tends to be too hard. When the hydroxyl value exceeds the upper limit, the polyurethane foam using this polyisocyanate tends to have low rebound resilience. When it is less than the lower limit, the viscosity of the obtained polyisocyanate composition becomes too high, and the workability tends to be reduced. When the oxyethylene group content is less than the lower limit, the foam tends to collapse during foaming. If it exceeds the upper limit, the strength of the foam tends to decrease. In (g), when the polymer content is less than the lower limit, the strength of the foam tends to decrease, and when it exceeds the upper limit, the rebound resilience tends to decrease.

The initiators used in (f) to (h) include:
Low molecular polyol used in the above (d) and (e),
Examples of the initiator include low molecular weight polyamines and low molecular weight amino alcohols.

In the present invention, (g) in (B)
Is preferably 30 to 50% by mass, more preferably 35 to 50% by mass.
-45 mass% is more preferable. In addition, (h) in (B)
Is preferably 3 to 20% by mass, more preferably 5 to 1% by mass.
5 mass% is more preferable.

In addition, the polyol composition (B) may contain, if necessary, polyols such as polyether polyols, polymer polyols and polyester polyols other than (f) to (h), and initiators for the above-mentioned polyethers. The low molecular polyol, low molecular polyamine and low molecular amino alcohol used may be used.

As the blowing agent (C), water is used. Foaming is carried out with carbon dioxide gas generated by the reaction between the isocyanate group and water. For the purpose of lowering the density, a method of mixing carbon dioxide in a liquid form and vaporizing and foaming at the time of foaming can also be used in combination. The amount of water is preferably 2 to 20% by mass based on the organic polyisocyanate (A). When liquefied carbon dioxide is used in combination, the amount is preferably 0.5 to 6% by mass based on (A) the organic polyisocyanate.

As the catalyst (D), various urethanization catalysts and trimerization catalysts known in the art can be used. Representative examples include triethylamine, tripropylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, dimethylbenzylamine, N, N, N ',
N'-tetramethylhexamethylenediamine, N, N,
N ', N', N "-pentamethyldiethylenetriamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, 1,8-diaza-bicyclo (5,
(0,0) Reactive tertiary amines such as tertiary amines such as undecene-7, dimethylethanolamine, N-trioxyethylene-N, N-dimethylamine, N, N-dimethyl-N-hexanolamine and the like; Organic acid salt, 1-methylimidazole, 2-methylimidazole, 1,2-
Imidazole compounds such as dimethylimidazole, 2,4-dimethylimidazole and 1-butyl-2-methylimidazole; organometallic compounds such as stannas octoate, dibutyltin dilaurate and zinc naphthenate;
4,6-tris (dimethylaminomethyl) phenol,
A trimerization catalyst such as 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine, potassium acetate, and potassium 2-ethylhexanoate is exemplified. The amount of the catalyst was 0.1% based on (A) the organic polyisocyanate.
-10% by mass is preferred.

The foam stabilizer (E) is an organic silicon-based surfactant known in the art, for example, L-5 manufactured by Nippon Unicar Co., Ltd.
20, L-540, L-5309, L-5366, SZ
-1306, SH-19 manufactured by Toray Dow Corning
0, SH-192, SH-193, SH-194, SR
X-274C, SF-2962, SF-2964, B-4113 and B-8680 manufactured by Goldschmidt, DC-2584, DC-504 manufactured by Air Products
3, DC-5169 and the like. The amount of these foam stabilizers is 0.1 to 3 with respect to (A) the organic polyisocyanate.
The use of% by weight is preferred.

In the present invention, a cross-linking agent can be used for the purpose of stabilizing the cell, for example, diethanolamine,
Triethanolamine and the like. The preferable addition amount is 0.1% based on (b) the modifier component ((d) + (e)).
5 to 2% by mass.

In the present invention, if necessary, additives can be used. For example, trichloroethyl phosphate, trichloropropyl phosphate, a phosphorus-halogen type liquid flame retardant represented by a condensation type thereof,
Uses solid flame retardant represented by melamine powder, conductive carbon represented by Ketjen Black, plasticizer such as dioctyl phthalate, antioxidant, ultraviolet absorber, coloring agent, internal release agent, and other auxiliaries be able to. These flame retardants are usually used by adding to polyols. However, auxiliary agents having no active hydrogen capable of reacting with isocyanate can be mixed in advance with organic isocyanate.

The equivalent ratio of NCO group / hydroxyl group during production of the flexible polyurethane foam is from 0.5 to 1.5, particularly preferably from 0.6 to 1.2.

As the production apparatus in the present invention, a mixing head having a low-pressure mechanical stirring device, an injection head having a high-pressure collision mixing mechanism, a spray head, and the like can be used for mixing raw materials. When the foam is colored, it is preferable to use an apparatus capable of directly supplying the mixing head from the viewpoint of color change and economy. Then, the mixture is injected into the mold from the head. In addition,
Examples of the method of injecting the mixture include mold open injection and mold close injection from an injection port. When a surface decoration material is used, it can be integrally molded into the skin if it is set in a mold frame in advance. In this case, in order to make the curing uniform, it is preferable that the temperature of the mold (and the surface decoration material) is adjusted to a constant temperature in the range of 20 to 70 ° C.

[0049]

The flexible polyurethane foam for automobile seat cushions obtained according to the present invention has excellent elasticity, strength, durability and the like. In addition, the flexible polyurethane foam obtained by the present invention may be used in addition to an automobile seat cushion, for example, a cushion material for furniture such as a sofa, a clothing material, a cushion material for a railway vehicle, a car interior material, a mattress, a futon, a bedding such as a pillow. It is also useful for materials, sound-absorbing materials, sound-insulating materials, household electrical appliances, electronic components, industrial sealing materials, packing materials, daily necessities, and the like.

[0050]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “%” means “% by mass”.
Is shown.

Synthesis Example 1 A capacity equipped with a stirrer, a cooling pipe, a nitrogen introducing pipe, and a thermometer:
347.2 k of MDI (1) was placed in a 1000 kg reactor.
g, 302.8 kg of P-MDI (1), TDI (1)
Was charged and heated to 40 ° C. while stirring. Next, 48.2 kg of the polyol (1) and 18.8 kg of the polyol (2) were charged and stirred at 80 ° C.
For 4 hours to obtain polyisocyanate P-1. The NCO content of P-1 was 34.4%.

Synthesis Examples 2-3, 10-12 Polyisocyanates P-2, 3, 10-12 were obtained from the starting materials shown in Tables 1 and 3 by the same reaction procedure as in Synthesis Example 1.

Synthesis Example 4 In a reactor similar to that of Synthesis Example 1, MDI (1) was added to 347.2.
kg and 302.8 kg of P-MDI (1) were charged and heated to 40 ° C. while stirring. Then, polyol (1)
Was charged and 48.8 kg of polyol (2) were charged, and reacted at 80 ° C. for 4 hours with stirring. Thereafter, 383.0 kg of TDI (2) was charged and heated to 50 ° C. with stirring to obtain polyisocyanate P-4. The NCO content of P-4 was 34.4%.

Synthesis Examples 5, 6, 13 to 15 Polyisocyanates P-5, 6, 13 to 15 were obtained from the raw materials shown in Tables 1 to 4 by the same reaction procedure as in Synthesis Example 4.

Synthesis Example 7 In a reactor similar to Synthesis Example 1, MDI (1) was added to 347.2.
kg and heated to 40 ° C. while stirring. Then
48.2 kg of polyol (1) and 18.8 kg of polyol (2) were charged and reacted at 80 ° C. for 4 hours with stirring. After that, the P-MDI (1) is
g, TDI (1) were charged in an amount of 283.0 kg, and the mixture was heated to 50 ° C. while stirring to obtain polyisocyanate P-3. The NCO content of P-3 was 34.4%.

Synthesis Examples 8, 9, 16-18 Polyisocyanates P-8, 9, 16-18 were obtained from the raw materials shown in Tables 2 and 4 in the same reactor as in Synthesis Example 7.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

[Table 4]

In Synthesis Examples 1 to 18 and Tables 1 to 4, MDI (1): an isomer mixture of MDI isomer content other than 4,4'-isomer = 19% MDI (2): isomer of MDI Mixture isomer content other than 4,4'-isomer = 1% MDI (3): isomer mixture of MDI isomer content other than 4,4'-isomer = 27% P-MDI (1): Polymeric MDI MDI content = 37% Isomeric content other than 4,4′-isomer in MDI = 27
% NCO content = 30.3% P-MDI (2): Polymeric MDI MDI content = 40% Isomer content other than 4,4′-isomer in MDI = 27
% NCO content = 31.0% TDI (1): 2,4-TDI: 2,6-TDI =
TDI that is 80:20 TDI (2): 2,4-TDI: 2,6-TDI =
99: 1 TDI Polyol (1): Polyoxypropylene polyol with ethylene oxide added to its terminal Nominal number of functional groups = 4 Hydroxyl value = 32 mgKOH / g Oxyethylene group content = 12% Polyol (2): Poly Oxypropylene polyol Nominal number of functional groups = 3 Hydroxyl value = 56 mg KOH / g Oxyethylene group content = 0% Polyol (3): Polyoxyalkylene polyol into which oxyethylene groups / oxypropylene groups are randomly introduced Nominal number of functional groups = 4 hydroxyl groups Value = 28 mgKOH / g Oxyethylene group content = 80% Polyol (4): Polyoxyethylene polyol No. of functional groups = 2 Hydroxyl value = 56 mgKOH / g Oxyethylene group content = 100%

[Preparation of Polyol Premix] Volume:
A polyol premix was prepared by blending a polyol, a foam stabilizer, a catalyst and water in the following ratio in a 1000 kg container. Polyol (A) 580 kg Polyol (B) 400 kg Polyol (C) 10 kg Foam stabilizer (A) 4 kg Foam stabilizer (B) 0.75 kg Catalyst (A) 10 kg Catalyst (B) 5 kg Water 50 kg Polyol (A): Polyoxy Propylene polyol with ethylene oxide added to the terminal Nominal number of functional groups = 3 Hydroxyl value = 24 mgKOH / g Oxyethylene group content = 16% Total unsaturation = 0.03 mmol / g Polyol (B): Polyol (A) Polyol containing vinyl polymer in vinyl polymer: Polyacrylonitrile polymer Polymer content = 20% Total unsaturation = 0.03 mmol / g Polyol (C): Oxyethylene group / oxypropylene group is random Polyoxyalkylene polyol introduced into the product Nominal No. of active groups = 3 Hydroxyl value = 48 mg KOH / g Oxyethylene group content = 67% Foam stabilizer (A): F-122 (silicone foam stabilizer, manufactured by Toray Dow Corning) Foam stabilizer (B): L-5309 (Silicone foam stabilizer,
Catalyst (A): TEDA L-33 (amine catalyst, manufactured by Tosoh) Catalyst (B): Toyocat-ET (amine catalyst, manufactured by Tosoh)

[Production of Flexible Polyurethane Foam] Example 1 Using P-1 and a polyol premix shown below,
After water foaming the flexible polyurethane foam in the mold,
It was removed from the mold and immediately subjected to roller crushing.
After that, the molded product after crushing is left for one day and night, and JI
Various physical properties of the foam were measured according to SK-6401.

[Foaming conditions] Mold shape: 400 mm × 400 mm × 100 mm Mold material: Aluminum Mold temperature: 60 ± 2 ° C. Mixing method: High pressure machine mixing Isocyanate index: 100 Raw material temperature: 25 ± 2 ° C. Cure condition: 60 ± 2 ° C, 6 minutes Crushing conditions: 5-stage roller 90% compression

Examples 2 to 9 and Comparative Examples 1 to 9 P-1 in Example 1 was replaced with P-2 to 18,
Various foams were produced in the same manner, and the physical properties were measured. Tables 5 and 6 show the measurement results of the foam properties.

[0066]

[Table 5]

[0067]

[Table 6]

As shown in Table 5, each of the flexible polyurethane foams obtained by the production method of the present invention has a core density of 40 kg / m ³ or less, an elongation of 100% or more,
The rebound resilience was 65% or more, showing excellent physical properties, and no splash was observed. On the other hand, in the comparative example,
In Comparative Example 2, the foam collapsed, and Comparative Examples 3, 5,
In 6, 8, and 9, splash was observed. In Comparative Example 4, the foam was not filled in the entire mold due to insufficient expansion ratio, and thus, physical properties were not measured. Comparative Example 1 had a small elongation. Comparative Example 7 was small in elongation and rebound resilience.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08G 101: 00) C08G 101: 00) C08L 75:04 C08L 75:04 F term (Reference) 3B084 CA00 4J034 BA03 BA07 DA01 DB03 DB08 DC50 DG02 DG03 DG09 HA02 HA07 HC11 HC12 HC22 HC46 HC64 HC67 QC01 RA12

Claims (4)

[Claims] 1. A polyisocyanate (a) comprising (a) to (c) shown below, and (d) shown below:
(B) a polyisocyanate composition containing an isocyanate group-terminated prepolymer obtained by reacting (b) a modifying agent with (b) a modifying agent; and (B) a polyol composition.
(C) A method for producing a flexible polyurethane foam for an automobile seat cushion which is reacted in the presence of a foam stabilizer, a catalyst (D) and a foaming agent (E), wherein the core density of the flexible polyurethane foam is 40 kg / m ³ or less. And a rebound resilience of 65% or more. (A) Diphenylmethane diisocyanate having a total content of 2,2'-isomer and 2,4'-isomer of 15% by mass or more (b) Triphenyl- or more functional diphenylmethane diisocyanate condensate (c) Tolylene diisocyanate ( D) Polyoxyalkylene polyol having an oxyethylene group content of 5 to 15% by mass. (E) Polyoxyalkylene polyol having an oxyethylene group content of 60 to 90% by mass. However, the mass ratio of (a) and (b) is (b) / (b) = 50
/ 50 to 90/10, and the content of (C) in (A) is 15 to 45% by mass. 2. A polyisocyanate (a) comprising (a) and (b) shown below, and (d) shown below:
Isocyanate group-terminated prepolymer obtained by reacting (b) a modifying agent comprising (e), and (A) a polyisocyanate composition containing (c) and (B) a polyol composition, In the method for producing a flexible polyurethane foam for an automobile seat cushion, which is reacted in the presence of a foam stabilizer, a catalyst (D) and a foaming agent (E), the flexible polyurethane foam has a core density of 40 kg / m ³ or less and a rebound resilience. Characterized in that the rate is 65% or more,
The manufacturing method. (A) Diphenylmethane diisocyanate having a total content of 2,2'-isomer and 2,4'-isomer of 15% by mass or more (b) Triphenyl- or more functional diphenylmethane diisocyanate condensate (c) Tolylene diisocyanate ( D) Polyoxyalkylene polyol having an oxyethylene group content of 5 to 15% by mass. (E) Polyoxyalkylene polyol having an oxyethylene group content of 60 to 90% by mass. However, the mass ratio of (a) and (b) is (b) / (b) = 50
/ 50 to 90/10, and the content of (C) in (A) is 15 to 45% by mass. 3. An isocyanate group-terminated prepolymer obtained by reacting (a) shown below, and a modifier (b) consisting of (d) and (e) shown below, and (a):
(B) a polyisocyanate composition containing (C) and (B) a polyol composition, (C) a foam stabilizer,
(D) A method for producing a flexible polyurethane foam for an automobile seat cushion which is reacted in the presence of a catalyst and (E) a foaming agent, wherein the flexible polyurethane foam has a core density of 40 kg / m ³ or less and a rebound resilience of 65%. The above-mentioned manufacturing method characterized by the above. (A) Diphenylmethane diisocyanate having a total content of 2,2'-isomer and 2,4'-isomer of 15% by mass or more (b) Triphenyl- or more functional diphenylmethane diisocyanate condensate (c) Tolylene diisocyanate ( D) Polyoxyalkylene polyol having an oxyethylene group content of 5 to 15% by mass. (E) Polyoxyalkylene polyol having an oxyethylene group content of 60 to 90% by mass. However, the mass ratio of (a) and (b) is (b) / (b) = 50
/ 50 to 90/10, and the content of (C) in (A) is 15 to 45% by mass. 4. The method according to claim 1, wherein (B) the polyol composition comprises the following (f) to (h):
The method for producing a flexible polyurethane foam according to any one of items 2 and 3. (F) Nominal number of functional groups = 2 to 6, hydroxyl value = 15 to 45 m
Polyoxyalkylene polyol having gKOH / g, oxyethylene group content = 10 to 20% by mass, and total unsaturation = 0.06 mmol / g or less. (G) Nominal number of functional groups = 2 to 6, hydroxyl value = 15 to 45 m
gKOH / g, oxyethylene group content = 10 to 20% by mass, total unsaturation = 0.06 mmol / g or less in a polyoxyalkylene polyol. A polymer polyol containing 30% by mass. (H) Nominal number of functional groups = 2-6, hydroxyl value = 30-70 m
gKOH / g, polyoxyalkylene polyol having an oxyethylene group content of 50 to 80% by mass.