KR0185813B1 - Soft urethane foam preparing composition - Google Patents

Abstract

The present invention improves the low temperature stability of MDI isocyanate by mixing and using a polyisocyanate component of a mixture of MDI and TDI isocyanate in a predetermined range of polymethylene polypepolyphenylpolyisocyanate having a functional group of 3 or more, and MDI soft polyurethane The present invention relates to a flexible urethane foam manufacturing composition capable of lowering density without using a CFC-based blowing agent without improving energy saving and production speed, which is a characteristic of elastic foam.

The composition of the present invention has at least two hydroxyl groups, at least 13 mol% of a polyol component having a molecular weight of 2000 to 8000 having a primary hydroxyl group and a polyisocyanate component having at least two isocyanate groups; It is suitable for making flexible polyurethane elastic foams by reacting in the presence of blowing agents, catalysts and other suitable aids.

The composition of the present invention is a mixture of diphenylmethane diisocyanate and toluene diisocyanate or derivative mixtures thereof (a) and polyphenylpolymethylenepolyisocyanate (b) having at least 3 functional groups and the isocyanate component (a + b) 100 It is 19 weight part or less even if there are many (b) components with respect to a weight part.

Toluene diisocyanate or derivatives thereof are 20.1-40.0 weight part with respect to 100 weight part of each said polyisocyanate components, and the remainder is the composition for manufacturing flexible polyurethane foam whose diphenylmethane diisocyanate or derivatives thereof.

Description

Compositions for the production of flexible urethane foam

The present invention relates to a composition for producing a flexible urethane foam having sufficient rebound elasticity by foaming sufficiently without using a chlorofluorocarbon-based blowing agent.

Polyurethane foam can be largely divided into slabstock foam and mold foam according to its physical properties. Slabstock foam is generally used for carpets, furniture, bedding, etc., and has high load bearing properties. Mold foam is used in automobile industry as mold sheet, shock absorbing plate, etc., and has high resiliency characteristics.

Slab foam is manufactured by cutting block foam to the required size, and mold foam is produced by molding into a mold by a hot cure method or a cold cure method.

Polyurethane is manufactured by polymerization reaction containing isocyanate and polyol as the main component.Polyurethane foam is also manufactured by One Shot method of mixing and foaming isocyanate, polyol, water and additives simultaneously. It is also prepared by a prepolymer method by reacting to form a prepolymer and mixing and foaming a catalyst blowing agent and an additive thereto.

Polyurethane foam is an isocyanate in any case, and typical isocyanate compounds include toluenedeiisocyanate (hereinafter referred to as TDI) and diphenylmethanediisocyanate (hereinafter referred to as MDI).

TDI is a mixture isomer of 2,4-TDI and 2,6-TDI. TDI and MDI have some similar properties and also have specific physicochemical properties. Therefore, TDI or MDI is selected depending on the purpose of the polyurethane foam. Sometimes used as a mixture or used in combination with their derivatives.

For example, TDI can be foamed with low density even if only water is used as a blowing agent, so it can maintain excellent rebound elasticity, which is advantageous in terms of production cost, but has a volatile and irritating odor, which provides a source of environmental pollution to the working environment. There is this.

In addition, MDI has a fast curing time (MDI is 50 ~ 100% faster than TDI), but it is not enough to foam with water alone, so many additional foaming agents are needed to obtain the desired degree of foaming. As blowing agents in this field, chlorofluorocarbon (CFC) -based blowing agents are widely used.

However, CFC compounds have the property of destroying the stratospheric ozone layer, which has already been decided to restrict their use internationally in accordance with the International Convention for the Protection of the Global Environment (Vienna Convention for the Protection of the Ozone Layer). The use of this blowing agent is inevitably limited.

Conventionally, TDI compounds (2.4-TDI or 2.6-TDI) have been mainly used as isocyanate compounds for preparing urethane foams, but recently MDI isocyanate compounds (2.4'-MDI or 4.4'-MDI) are mass-produced and at a low price. In order to reduce manufacturing costs, improve productivity and environmental protection, research on a method of producing flexible urethane foam using MDI isocyanate is being actively conducted.

However, since MDI isocyanates such as diphenylmethane isocyanate have a melting point of about 40 ° C. and are solid at room temperature, they are inconvenient to handle and easily solidified when used as a raw material for flexible polyurethane elastic foams. have.

Flexible polyurethane elastic foam using MDI isocyanate has the effect of saving air volume and improving production speed in the manufacturing process, while it has low resilience compared to cold cure soft polyurethane foam by TDI isocyanate. This has the disadvantage of falling. In addition, since the density of foam is not low enough when only water is used as a blowing agent, the cost of the product is high, so the foam density is equivalent to that of a cold cure flexible polyurethane elastic foam by TDI, and its use is limited internationally. There is a significant drawback to the use of CFC-based blowing agents. Therefore, it is a new technology that uses MDI isocyanate which can save energy and improve productivity when manufacturing flexible polyurethane elastic foam, and has high rebound elasticity like TDI isocyanate and does not impair ride comfort and does not use CFC foaming agent at all. Development is required.

The present inventors have studied in various ways to solve the above problems, MDI isocyanate by mixing a polymethylene polyphenyl polyisocyanate having a functional group of 3 or more in a predetermined range in a mixture of MDI and TDI isocyanate as a polyisocyanate component Improved low temperature stability and improved resilience without compromising energy saving and production speed, which is characteristic of MDI soft polyurethane elastic foam, and it was confirmed that the density can be reduced without using CFC-based foaming agent. To complete.

The composition of the present invention has at least two hydroxyl groups, at least 13 mol% of a polyol component having a molecular weight of 2000 to 8000 having a primary hydroxyl group and a polyisocyanate component having at least two isocyanate groups; It is suitable for making flexible polyurethane elastic foams by reacting in the presence of blowing agents, catalysts and other suitable aids.

The composition of the present invention is a mixture of diphenylmethane diisocyanate and toluene diisocyanate or derivative mixtures thereof (a) and polyphenylpolymethylenepolyisocyanate (b) having a functional group of 3 or more. 100 wt% of the isocyanate component (a + b) Even if there are many (b) components with respect to a part, it is 19 weight part or less.

It is a composition for manufacturing flexible polyurethane foam, wherein the total amount of toluene diisocyanate or derivatives thereof is 20.1 to 40.0 parts by weight based on 100 parts by weight of each of the corresponding polyisocyanate components, and the remainder is diphenylmethane diisocyanate or derivatives thereof.

Also included is a composition for producing a flexible polyurethane having an isocyanate group content of 41.0 to 20.0%, which is a mixture of diphenylmethane diisocyanate and toluene diisocyanate or derivatives thereof.

Toluene diisocyanate and diphenylmethane diisocyanate used in this invention are 4,4'- methylene bisphenyl isocyanate or 4,4'- methylene bisphenyl including 2.4'- methylene bisphenyl isocyanate (2,4'-MDI). 2,4-toluene diisocyanate (2,4-TDI) or 2,4-toluene diisocyanate including isocyanate (4,4'-MDI) and 2,6-toluene diisocyanate (2,6-TDI) A mixture containing at least a portion of a modified product of TDI or MDI, including a urtonimine group, a carbodiimide group, a urethane group, an allophanate group, a biuret group, for example MDI And mixtures of MDI and TDI isocyanates and mixtures of MDI and TDI isocyanates.

In addition, polyphenylpolymethylenepolyisocyanate having functional group 3 or more has a residual ratio obtained by taking a part of 4,4-MDI through distillation to the prepared MDI obtained by condensation reaction of aniline and formaldehyde to form phosgene. It refers to a polynuclear oligoma [the compound of following structural formula (1)]. This residue polyisocyanate (hereinafter referred to as polymer MDI-Polymeric MDI) contains 40 to 60% by weight of polyphenylpolymethylenepolyisocyanate having 3 or more functional groups. [Example Kumho Mitsui Toatsu MDI M-200]

The ratio of the polyphenyl polymethylene polyisocyanate component having 3 or more functional groups to 100 parts by weight of the polyisocyanate component is 19 parts by weight or less. When the ratio of the polyphenylpolymethylenepolyisocyanate component having a functional group of 3 or more is more than 19 parts by weight, the effect of improving resilience is not obtained, and at the same time, the tear strength and elongation of the foam are lowered and the performance required as a seat cushion cannot be obtained. .

In the present invention, the toluene diisocyanate compound refers to TDI including TDI modified foam containing TDI or urethane group, uretonimine group, carbodiimide group, alloponate group, and butyrate group.

The ratio of toluene diisocyanate and / or derivative is 20.1-40.0 weight part with respect to 100 weight part of said polyisocyanate components. When the ratio of toluene diisocyanate and / or its derivatives is lower than 10 parts by weight, the rebound elasticity does not improve. Or the low temperature storage stability of this polyisocyanate falls remarkably. Moreover, the density of the foam cannot be lowered sufficiently. When the ratio of toluene diisocyanate and / or its derivatives exceeds 50 weight part, when the polyol component and the isocyanate component are mixed and reacted, the curing rate is slow and productivity is lowered.

The isocyanate group content, which is a mixture of diphenylmethane diisocyanate and toluene diisocyanate or derivatives thereof, is 41.0 to 20.0%. When the isocyanate group content is 20% by weight or less, the effect of improving repulsive elasticity and reducing the density of the foam cannot be obtained.

The polyols used in the present invention are water, polyhydric hydroxyl group compounds (for example, ethylene glycol, propylene glycol diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol, 1,3- and 1,4-butanol, 1,5-pentadiol, 1,2-hexylene glycol, 1,10-decanediol, 1,2-cyclohexanediol, 2-butene-1,4-diol, 3-cyclohexane-1, 1 Dimethanol, 4-methyl-3-cyclohexane-1,1-dimethanol, 5-pentanediol, 2-propanediol, glycerin, 1,2,6-hexanetriol, 1,1,1-trimethyl Oleethane, 1,1,1-trimethylolpropane, 2-propanediol, lactose) polyamines (e.g. ethylenediamine, diethylenetriamine, triethylenetetraamine, methyleneolsocroaniline, 4,4'-diphenyl Methanediamine, 2,4-toluenediamine, 2,6-toluenediamine) or alkylolamines (e.g., triethanolamine, diethanolamine) to ethylene oxide, propylene oxide, butylene oxide, styrene It is polyether polyol or polytetramethylene ether glycol obtained by adding 1 type, or 2 or more types, such as dehydration.

Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3 and 1,4-butanediol, trimethylene glycol, neobenzol glycol, hexamethylene glycol, decamethylene glycol, glycerin , One or two or more kinds of compounds having at least two hydroxyl groups, such as trimethylolpropane and sorbitol, and at least two kinds, such as malonic acid, maleic acid, adipic acid, acetic acid, butyric acid, terephthalic acid, and trimellitic acid Ring-opening polymers of cyclic esters, such as a compound having three carboxyl groups or polycaprolactam, may also be used. Furthermore, polymapolyol compositions obtained by graft polymerization of ethylenically unsaturated compounds in polyetherpolyols and / or polyesterpolyols can be used. Suitable ethylenically unsaturated compounds for preparing such compositions include acrylonitrile, styrene and the like. Furthermore, 1,2-polymerbutadienepolyol (1,2-Polymerbutadienpolyol) and 1,4-polymerbutadienepolyol (1,4-Polymerbutadienpolyol) may also be used.

The molecular weight of the various polyols described above is usually 2000-8000.

Moreover, the suitable range of the hydroxyl group of these polyols is 20-140 mg KOH / g, Especially good thing is 24-56 mg KOH / g. In the present invention, a crosslinking agent and a chain extender containing a reactive, active hydrogen atom obtained by reacting at least two isocyanates with a mixture are used.

These crosslinking agents and / or chain extenders include monomeric polyols such as ethylene glycol, propylene glycol, trimethylene glycol and 1,4-butanol, alkylolamines such as triethanol amine and diethanolamine, ethylene amines, diethylene triamine and triethylene. In addition to aromatic polyamines, such as aliphatic polyamines, such as tetraamine, methyleneol to chloramine, 4, 4- diphenylmethane amine, aniline, 2, 4- toluenediamine, and 2, 6- toluenediamine, and these activated hydrogen compounds, It is a compound whose hydroxyl group obtained is 200 mmg KOH / g or more.

As the catalyst used in the present invention, it is possible to use those commonly used in polyurethane foam, and there is no particular limitation, but for example, amine-based and urethane catalysts (triethylamine, tripropylamine, triisopropanolamine, tributylamine, tri Ethylamine, hexadimethylamine, N-methylmorpholine, N-octadecylmorpholine, monoethanolamine, diethanolamine, triethanolamine, N-methyl diethanolamine, diethylenetriamine bis (2- (n, n Organometallic compounds such as oxyalkylene adducts of amino groups of primary and secondary amines, dimethylamino) ethyl) ether, N, N-dimethylbenzolamine, crohexylamine, triethylenediamine and other salts Urethane-forming catalysts (tin acetate, octylate tin, oleic acid tin, lauric acid tin, dibutyl tin dilaurate, dibutyl tin chromide, lead octanoate, lead melamine acid, nickel merarate, cobalt carbonate) have. The catalyst is used alone or in combination.

The amount of these used is from 0, 0001 to 10.0% with respect to 100% by weight of the compound having active hydrogen.

In the present invention, water is used as the blowing agent, but as the auxiliary blowing agent, ordinary urethane blowing agents such as trichloroproomethane, methyl chloride, dichlorofluoromethane, and pentane may be used alone or in combination. However, according to the present invention, since foams and foams having a lower density, that is, higher foaming degree, are obtained than conventional MDI mainly used as polyisocyanates, auxiliary blowing agents do not need to be used.

In the present invention, foam stabilizers include organosilicon surfactants commonly used in polyurethane foams. For example, L-5309, L-3600, manufactured by Osuai Co., Ltd., srx274c, SF-2966, PRX- 601, SF-2962, B-4113, B-4900 by Cold Schmidt, etc. are mentioned. The use amount of these foam stabilizers is 0.1 to 5% with respect to 100 weight% of total amounts of an activated hydrogen compound and an organopolyisocyanate compound.

In the present invention, it is possible to use various stabilizers, filler colorants, flame retardants and the like as necessary. In carrying out the present invention, a polyol, a crosslinking agent, a foam stabilizer, and other preparations are mixed to form a resin component.

On the other hand, what mixes predetermined amount of diphenylmethane diisocyanate or its derivative (s), polyphenyl polymethylene polyol isocyanate mixture, and toluene diisocyanate or its derivative (s) is made into polyisocyanate component.

These components are mixed and reacted as a method usually carried out in the production of polyurethane foam.

Each component isocyanate index is made to react 0.1 to 1.50% normally. Isocyanate indexes are often used by those skilled in the art. This is an index for the amount (stoichiometric amount) of isocyanate groups required for the amount of active hydrogen groups (H) obtained by reacting with isocyanate groups (NCO groups) such as polyols and crosslinking agents. For example, the isocyanate index when an isocyanate corresponding to the amount of active hydrogen group is used is 1.00. Isocyanate Index is calculated by the following formula.

The resin premix and the isocyanate composition were adjusted by the operation shown in Examples 13 to 18 and Comparative Example K using the types and amounts described in Table 5, and the resin prepreg by the method indicated in Examples 13 to 18 and comparison. Mix 426.4% and the amount (part) isocyanate composition shown in Table 4 by stirring and mixing. (The total amount of resin premix and isocyanate is 880 g.) The reaction mixture was poured into a 350 x 350 x 100 mm aluminum test mold (mould), which was temperature-controlled to 50 ° C. in advance, and 4 minutes after the start of stirring of the resin premix and the isocyanate composition. The flexible urethane foam expanded and expanded in the mold is taken out. The foam is weighed and the foam weight divided by the volume in the mold is taken as the foam's obaol density. The resilience was evaluated by cutting a 100 mm x 100 mm x 30 mm specimen from the center of the obtained flexible foam. (Evaluation method: according to JIS K-6401)

In the present invention, in the case where the isocyanate index is 0.5 or less, the foamed foamed foam may have many cells of independent bubbles, and the foam shrinkage may occur with a decrease in the foam internal temperature. When the isocyanate index is 1.5 or more, the reaction hardening is slowed due to the unreacted isocyanate in the foam. Moreover, productivity may fall. The resin component and the isocyanate are mixed and added so as to have a compounding ratio of 0.5 to 1.50 in the isocyanate index, and then injected into a mold previously heated and adjusted to 30 to 60 ° C. In other words, after closing the lid and standing at room temperature for 3 to 4 minutes, the molded polyurethane elastic foam is removed from the roll.

EXAMPLE

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

Examples 1 to 6 and Comparative Examples A to E

Toluene diisocyanate is described as TDI and diphenylmethane diisocyanate is described as MDI. % Is by weight unless there is particular notice.

Examples 1-6 and Comparative Examples A-E The various isocyanate mixtures shown in Table 1 were placed in a 100 cc sealable glass container, sealed in a nitrogen atmosphere, and left for 5 days in a low temperature bath at 5 ° C. to visually evaluate the low temperature storage stability of the contents. It was.

As shown in the Examples and Comparative Examples of Table 1, 2,4'-MDI, uretonimine-modified MDI, urethane-modified MDI regardless of the presence or use amount of TDI 10% or more in the isocyanate composition to use a liquid at 5 ℃ for 5 days However, the TDI amount was less than 10% in the composition of the isocyanate solid or crystallized precipitate was seen.

[Examples 7 to 12 Comparative Examples F to J]

The polyol, H ₂ O, surfactant, catalyst, and crosslinking agent of the resin premix formulations shown in Table 2 are taken into the container in the amounts shown in Table 2 and sufficiently stirred. A blowing agent was mixed with this compound by the amount shown in Table 2 to obtain a resin premix.

In another vessel, a TDI mixture of 80% 2,4-TDI and 20% 2,6-TDI, 4,4'-MDI, 2,4'-MDI, polymeric MDI, uretonimine-modified MDI is shown in Table 2. Take as much as described and mix it to make an isocyanate composition. 432.8 g of a resin premix adjusted to 22 ° C. ± 2 ° C. was added, and the amount of the isocyanate composition adjusted to 22 ° C. ± 2 ° C. was added to the amounts shown in Table 2, followed by vigorous stirring and mixing for 6 seconds, followed by mixing the reaction mixture into a 6 L polyethylene beaker. After cooling for 10 minutes at room temperature, the foam expansion, foamed soft foam was taken out, and the core density was measured by cutting the center of the flexible foam in the size of 100 mm x 100 mm x 50 mm the next day.

The core density of the flexible foam obtained as shown in Table 2 was low as 31-36 Kg / m ³ , using an isocyanate composition using 10 to 50% of TDI regardless of the constant amount of water and blowing agent as the blowing agent. Examples 7-12) and the core density of the thing of less than 10% of TDI usage-amount became high (Comparative Examples F-J) at 39-46 Kg / m <^3> .

The core density of the flexible foam is not significantly affected by the presence or absence of 4.4'-MDI, polymeric MDI, or uretonimine modified substance. When 2,4'-MDI was used, the foam was somewhat lowered (Comparative Examples G and H), but the density was not as low as 10-50% of TDI was used.

[Examples 13 to 18 Comparative Example K]

The polyol-A, polyol-B, H ₂ O, surfactant, catalyst crosslinking agent, and the like of the resin premix formulations shown in Table 3 were taken in containers in the amounts shown in Table 3 and sufficiently stirred to obtain a resin premix.

In another container, 4,4'-MDI, 2,4'-MDI, polymeric MDI, urethane-modified MDI, and urethane-modified TDI of the mixture of TDI isomers were taken in the amounts shown in Table 3 and mixed to obtain an isocyanate composition.

Take 426.4 g of resin premix adjusted to 22 ° C ± 2 ° C, add the amounts shown in Table 3 to the isocyanate composition adjusted to 22 ° C ± 2 ° C, stir and mix for 6 seconds, and add the reaction mixture to a 6-L polyethylene beaker. After standing at room temperature for about 10 minutes, the foamed expanded foamed hard foam was taken out, and the center of the flexible foam was cut to a size of 100 mm x 100 mm x 50 mm the next day, and the core density was measured.

The core density of the flexible foam obtained as shown in Table 3 is 38-45Kg / m ^{3, which is} low using the isocyanate composition using 14-45% of TDI or urethane modified TDI (TDI derivative) regardless of the constant amount of water as the blowing agent. (Examples 13-18) and the core density of less than 10% of TDI usage-amount became high as 60Kg / m <^3> .

The core density of the flexible foam was not significantly affected by the use or the amount of 4.4'-MDI, 2,4'-MDI, polymeric MDI, urethane modified MDI, urethane modified TDI.

[Examples 19-24 Comparative Examples L-P]

432.8 g of resin premix and the amount (%) described by the method shown in Examples 7-12 and Comparative Examples F-J using the resin premix and the isocyanate composition shown in Table 4 Isocyanate composition was stirred and mixed (800 g in the total amount of resin premix and isocyanate).

The reaction mixture was poured into a 350 × 350 × 100 mm aluminum test mold previously adjusted to 50 ° C., and the resin premix and the isocyanate composition were taken out of the foamed expanded urethane foam in the mold 4 minutes after the start of stirring, and the curable test sample was touched. By. The foam is weighed and the value divided by the foam weight from the volume of the mold is taken as the foam's obaol density. The resulting soft foam was cut the following day, cut out a 100 × 100 × 30 mm specimen from the center of the foam, and evaluated the resilience (based on jis k-6401).

Although it is generally thought that ride comfort can be evaluated by the repulsion property, rebound elasticity is used as a measure of the panel feel of the seat cushion.

The four minute curability of the flexible foams made using the isocyanate composition using 10% to 50% TDI in the isocyanate composition is almost good or good.

Repulsive elasticity is excellent in the panel feeling which displays 60 to 69%. (Examples 19 to 24)

On the other hand, as shown in Comparative Examples (L, M, N, O), a flexible foam obtained by using an isocyanate composition having a TDI content of less than 10% in the isocyanate composition is used when 2,4'-MDI is used a lot (comparative example) Except for the good curia, but the rebound elasticity is low 51 ~ 54% and the panel feels poor.

In addition, as shown in Comparative Example P, when a large amount of TDI is used at 50% in the isocyanate composition, the rebound elasticity is good at 67%, but the curability is greatly deteriorated and the mold is difficult to be deformed. Decreases.

[Examples 25-30 and Comparative Example Q]

The resin premix and the isocyanate composition were adjusted by the operation shown in Examples 13 to 18 and Comparative Example K using the types and amounts of the bases described in Table 5, and Examples 13 to 18. By the method shown in the comparative example K, 426.4% of resin premix and the amount (%) of isocyanate composition of Table 4 are stirred and mixed. (The total amount of resin premix and isocyanate is 880 g.) The reaction mixture was poured into a test mold made of 350 x 350 x 100 mm aluminum, which was previously temperature-controlled at 50 ° C, and 4 minutes after the start of stirring of the resin premix and the isocyanate composition. The flexible urethane foam which expanded and expanded inside is taken out. The foam is weighed and the foam weight divided by the volume in the mold is taken as the foam's obaol density. The obtained soft foam cut | disconnected the 100 mm x 100 mm x 30 mm specimen from the center part of the foam cut on the next day, and evaluated the repulsive coal phase (based on JIS K-6401).

As shown in Examples 25 to 30 and Comparative Example Q, when 14 to 45% of TDI or urethane-modified TDI (TDI derivative) in the isocyanate composition was used, the resilience showed a high value of 60% to 67% and excellent ride comfort. Give it a soft foam. If the TDI usage is less than 10%, only a low value of 55% repulsive elasticity is obtained.

# 1) 80% 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI)

20% Mixture NCO% 48.3% Korea Fine Chemicals Co., Ltd.

# 2) 4,4'-diphenylmethane diisocyanate NCO% 33.6%, Kumho Mitsui Totsu Co., Ltd. (brand name: MDI-PH)

# 3) 2,4'-diphenylmethane diisocyanate NCO% 33.6%, Kumho Mitsui Totsu Co., Ltd.

# 4) Polymeric MDI, polyphenylpolymethylene polyisocyanate NCO% 31.0%, Kumho Mitsui Totsu Co., Ltd. (brand name: MDI LK)

# 5) Ureitonimine modified diphenylmethane diisocyanate NCO% 28.0%, Kumho Mitsui Toatsu Co., Ltd. (brand name: MDI M-200)

# 6) Diphenylmethane diisocyanate NCO% 22.5% urethane-modified with tripropylene glycol

# 1) A mixture of 80% 2,4-toluene diisocyanate and 20% 2,6-toluene diisocyanate (TDI) NCO 48.3%, manufactured by Fine Chemicals Co., Ltd.

# 2) 4,4'-diphenylmethane diisocyanate NCO% 33.6%, Kumho Mitsui Toatsu Co., Ltd. (brand name: MDI-PH)

# 3) 2,4'-diphenylmethane diisocyanate NCO% 33.6%, Kumho Mitsui Totsu Co., Ltd.

# 4) Polymatic MDI, polyphenylpolymethylpolyisocyanate NCO% 31.0%, Kumho Mitsui Toatsu Co., Ltd. (brand name: MDI M-200)

# 5) Uretonimine-modified diphenylmethane diisocyanate NCO% 28.0% Commercial item made by Kumho Mitsui Toatsu Corporation (brand name: MDI-LK)

# 6) Polyether polyol obtained by addition polymerization of propylene oxide and ethyl oxide as glycerin as initiator, OHV 28mg KOH / g

# 7) distilled or ion-exchanged water

# 8) Silicone surfactant, commercial product of Gold Schmidt

# 9) Amine catalyst, commercial product made by Air Prod

# 10) Amine catalyst, commercial product made by OSI Corporation

# 11) Crosslinking agent diethanolamine, commercial product made by Korea Polyol Co., Ltd.

# 12) Foaming agent CFC 11 DuPont Chemicals commercial item

# 13) Core density at pre-foaming

# 1) A mixture of 80% 2,4-toluene diisocyanate and 20% 2,6-toluene diisocyanate (TDI) NCO% 48.3%, manufactured by Fine Chemicals Co., Ltd.

# 2) 4,4'-diphenylmethane diisocyanate NCO% 33.6%, Kumho Mitsui Toatsu Co., Ltd. (brand name: MDI-PH)

# 3) 2,4'-diphenylmethane diisocyanate NCO% 33.6%, Kumho Mitsui Totsu Co., Ltd.

# 4) Polymatic MDI, polyphenylpolymethylenepolyisocyanate NCO% 31.0%, Kumho Mitsui Toatsu Co., Ltd. (brand name: MDI M-200)

# 5) Obtained by reacting polyol A with 4,4'-MDI. NCO% 23.5% preforma

# 6) Obtained by reacting polyol A with TDI 80/20. NCO% 23.5% preforma

# 7) Polyether polyol obtained by addition polymerization of propylene oxide and ethylene oxide with glycerin as initiator, OHV 28mg KOH / g

# 8) OHV 28 mg KOH / g polymapolyol obtained by radical polymerization of styrene and acrylonitrile in a polyether polyol obtained by addition polymerization of propylene oxide and ethylene oxide with glycerine as an initiator and OHV 34 mg KOH / g polyol

# 9) distilled or ion-exchanged water

# 10) Silicone surfactant, commercial product of Gold Schmidt

# 11) Amine catalyst, commercial product made by Air Prod

# 12) Amine catalyst, commercial product made by OSI Corporation

# 13) Crosslinking agent diethanolamine, commercial product made by Korea Polyol Co., Ltd.

# 14) Cross-linking agent Triethanolamine, commercial product made by Korea Polyol Co., Ltd.

# 15) Core density at pre-foaming

# 1) A mixture of 80% 2,4-toluene diisocyanate and 20% 2,6-toluene diisocyanate (TDI) NCO% 48.3%, manufactured by Fine Chemicals Co., Ltd.

# 2) 4,4'-diphenylmethane diisocyanate NCO% 33.6%, Kumho Mitsui Totsu Co., Ltd. (brand name: MDI-PH)

# 3) 2,4'-diphenylmethane diisocyanate NCO% 33.6%, Kumho Mitsui Totsu Co., Ltd.

# 4) Polymatic MDI, polyphenylpolymethylene polyisocyanate NCO% 31.0%, Kumho Mitsui Totsu Corporation (trade name: MDI M-200)

# 5) Uretonimine modified diphenylmethane diisocyanate NCO% 28.0% A commercial item made by Kumho Mitsui Toatsu Corporation (brand name: MDI-LK)

# 6) Polyether polyol obtained by addition polymerization of propylene oxide and ethylene oxide with glycerin as initiator, OHV 28mg KOH / g

# 7) distilled or ion-exchanged water

# 8) Silicone surfactant, commercial product of Gold Schmidt

# 9) Amine catalyst, commercial product made by Air Prod

# 10) Amine catalyst, commercial product made by OSI Corporation

# 11) Crosslinking agent diethanolamine, commercial product made by Korea Polyol Co., Ltd.

# 12) Foaming agent CFC 11 DuPont Chemicals commercial item

# 13) Overall Density in Mold Foaming

# 14) The time from the start of stirring to demolding is 4 minutes, and it is determined whether demolding is possible.

# 15) Measure with 100mm × 100mm × 30mm specimen.

# 1) A mixture of 80% 2,4-toluene diisocyanate and 20% 2,6-toluene diisocyanate (TDI) NCO% 48.3%, manufactured by Fine Chemicals Co., Ltd.

# 2) 4,4'-diphenylmethane diisocyanate NCO% 33.6%, Kumho Mitsui Totsu Co., Ltd. (brand name: MDI-PH)

# 3) 2,4'-diphenylmethane diisocyanate NCO% 33.6%, Kumho Mitsui Totsu Co., Ltd.

# 4) Polymeric MDI, polyphenylpolymethylenepolyisocyanate NCO% 31.0%, Kumho Mitsui Toatsu Co., Ltd. (brand name: MDI M-200)

# 5) Obtained by reacting polyol A with 4,4'-MDI. NCO% 23.5% prepolymer

# 6) Obtained by reacting polyol A with TDI 80/20. NCO% 23.5% prepolymer

# 7) Polyether polyol obtained by addition polymerization of propylene oxide and ethylene oxide with glycerin as initiator, OHV 28mg KOH / g

# 8) OHV 28 mg KOH / g polymapolyol obtained by radical polymerization of styrene and acrylonitrile in a polyether polyol obtained by addition polymerization of propylene oxide and ethylene oxide with glycerine as an initiator and OHV 34 mg KOH / g polyol

# 9) distilled or ion-exchanged water

# 10) Silicone surfactant, commercial product of Gold Schmidt

# 11) Amine catalyst, commercial product made by Air Prod

# 12) Amine catalyst, commercial product made by OSI Corporation

# 13) Crosslinking agent diethanolamine, commercial product made by Korea Polyol Co., Ltd.

# 14) Cross-linking agent Triethanolamine, commercial product made by Korea Polyol Co., Ltd.

# 15) Ovalol Density in Mold Foaming

# 16) Measure with 100mm × 100mm × 50mm specimen.

According to the present invention, it is possible to obtain a foam having improved resilience while maintaining high elasticity in MDI-based flexible urethane foam production. In addition to a free core density as compared to conventional MDI-based flexible polyurethane elastic foam of the same water (water) the amount of water (blowing agent) 45Kg / m ³ or less (for example, 15~45Kg / m ³⁾ of the body is low-density foam can be obtained Since there is no CFC-based blowing agent it is possible not to use. The composition of the isocyanate used as a raw material for the present invention has good low temperature storage stability of the liquid even at a low temperature.

In addition, the compositions of the present invention can be used both in a short-shot method and in a prepolymer method.

Claims (3)

A polyisocyanate having at least two hydroxyl groups, at least 13 mol% of which is a primary hydroxyl group having a molecular weight of 2000 to 8000 polyol (Ployol) and at least two isocyanate groups, In the composition for producing a flexible polyurethane foam composed of water, a catalyst and an additive, the isocyanate component is a mixture of diphenylmethanediisocyanate and toluendeiisocyanatc or a derivative mixture thereof (a) Functional group Is a polyisocyanate (b) obtained from polyphenylpolymethylenepolyisocyanate of 3 or more and is 19 parts by weight or less with respect to 100 parts by weight of the isocyanate component (a + b) and no more than 19 parts by weight and 100 parts by weight of the isocyanate component. About Toruendi Isocane Agent and or weight of the total amount of the derivative 20.1 to 40.0 parts and the remaining amount is diphenylmethane diisocyanate or or a flexible polyurethane foam composition for preparing a derivative thereof. The composition for producing a flexible polyurethane foam according to claim 1, wherein the isocyanate group content of the mixture of diphenylmethane diisocyanate or these derivatives is 50.0 to 15.0%. The soft urethane according to claim 1, wherein the diphenylmethane diisocyanate and toluene diisocyanate derivatives are diphenylmethane diisocyanate derivatives or toluene diisocyanate derivatives modified with uretonimine, carbodiimide, urethane, aluperate, butate. Foam preparation composition.