KR100971521B1 - Composition of polyurethane foam containing amino resin - Google Patents

Abstract

The present invention relates to a polyurethane resin composition for shoe soles containing an amino resin, and more particularly, to a polyurethane resin composition prepared from a polyol mixture composed of a polyol, water, a chain extender, and the like, and a prepolymer containing a diisocyanate compound. It is about.

The present invention provides an excellent polyurethane resin composition for shoe midsoles having improved hardness and mechanical properties at a specific gravity of 0.2 to 0.3, by combining the excellent mechanical properties and stability of the amino resin with a polyurethane foam. can do.

Polyurethane, shoe midsole, amino resin, low specific gravity

Description

Polyurethane resin composition for foam containing amino resin TECHNICAL FIELD

The present invention relates to a polyurethane resin composition for shoe soles containing an amino resin, and more particularly, a polyurethane resin prepared from a prepolymer containing a polyol mixture composed of a polyol, water, a chain extender, and the like, and a diisocyanate compound. It relates to a composition.

BACKGROUND OF THE INVENTION In the manufacture of soles, especially midsoles, polyurethane foams having excellent mechanical strength, performance, and moldability have been applied. However, since the specific gravity is greater than that of a foam based on a copolymer of ethylene vinyl acetate, in consideration of the recent trend of lighter weight of shoes, low specific gravity of urethane foam for shoe midsole is required.

Low specific gravity is possible by increasing the amount of water, a chemical foaming agent, and cyclopentane, a physical foam, by increasing the foaming ratio by the method of pursuing low specific gravity of the midsole, but the mechanical properties are lowered due to the increased cell size of the foam. Will lose its performance. Therefore, there is a need to develop a polyurethane resin that can maintain mechanical properties while having a low specific gravity.

Accordingly, the present inventors have completed the present invention by developing a modified polyurethane resin composition containing an amino resin and having a specific gravity of 0.2 to 0.3 and excellent mechanical properties as a result of research and efforts to solve the above problems.

The present invention relates to a polyurethane resin composition prepared by mixing a polyol mixture and a prepolymer, the polyol mixture comprising a polyol, water, and a curing agent in a predetermined ratio, and a polyol and a diisocyanate compound prepared in a prepolymer comprising a predetermined ratio of foam specific gravity It is characterized by the polyurethane resin composition in this 0.2-0.3 range. At this time, an amino resin is necessarily contained in either composition at the time of mixing a polyol mixture or a prepolymer.

The present invention provides an excellent shoe midsole with improved hardness and mechanical properties at a specific gravity of 0.2 to 0.3, which is strong and lighter by incorporating the superior advantages of amino resins, namely the excellent mechanical properties and stability of amino resins into polyurethane foams. Polyurethane resin composition for can be provided.

The present invention is characterized by a polyurethane resin composition for a foam including the amino resin foam specific gravity is adjusted to 0.2 ~ 0.3 range.

In addition, the present invention is a method for producing a polyurethane resin composition by mixing a polyol mixture and a prepolymer, the polyol mixture (R liquid), polyol, diisocyanate compound containing a polyol, water, a curing agent, a foam stabilizer in a predetermined ratio The manufacturing method of the said polyurethane resin composition which mixes the prepolymer (P liquid) contained in a fixed ratio is characterized by the above-mentioned. At this time, an amino resin is necessarily contained in either composition at the time of mixing a polyol mixture or a prepolymer.

Hereinafter, the present invention will be described in detail.

In order to maintain the specific gravity of the foam to 0.2 ~ 0.3, the amount of water used was increased, and in order to maintain the mechanical properties as in the high specific gravity foam, the structure of the polyol was partially different from the conventional one.

The polyol is used alone of the polyester polyol or a mixture of polyester polyols and polyether polyols is used.

The polyester polyols have a weight average molecular weight of 500 to 5000 and use at least 50% by weight of the total polyol mixture. When used within 50% by weight, mechanical properties such as tensile strength, hardness, etc. of the resulting foam are lowered, thereby losing the function of the elastic foam.

The polyester polyol is at least one polyhydric alcohol selected from ethylene glycol, 1,4-butanediol, 1,5-pentanediol, methylpentanediol, 1,6-hexanediol, trimethylolpropane, glycerol, pentaerythritol It may be prepared by the reaction of one or more divalent acids selected from oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, and may also be prepared from polycaprolactonediol, polycarbonate diol.

The polyether polyol has a weight average molecular weight of 500 to 4000, and 1 to 40 parts by weight based on 100 parts by weight of the polyester polyol. Since polyether polyols have -O- bonds that are freely rotatable in the molecule, they provide flexibility to the molecules and thus have excellent low temperature properties, but the mechanical properties thereof are not higher than those of polyester polyols. Therefore, when 40 weight part or more is used, there exists a problem that the tensile strength and hardness of the obtained foam become low.

The polyether polyol is obtained by polymerization of a polyhydric alcohol and an alkylene oxide, and typical examples thereof include polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, and polytetramethylene ether glycol prepared from tetrahydrofuran. Can be used.

Water reacts with the functional groups at the end of the isocyanate as a chemical blowing agent to generate carbon dioxide, and carbon dioxide may act as a foaming gas to obtain a foam, and control specific gravity. The amount of water to be used is preferably 0.5 to 2.5% by weight of the liquid R. When the amount of water to be used is 0.5% by weight or less, the foaming ratio is lowered, so that the specific gravity is increased. At 2.5% by weight or more, the size of the cells constituting the foam is uneven. This is because mechanical properties such as hardness and tensile strength are lowered.

As the curing agent, it is preferable to use diols (diol) which can simultaneously serve as a chain extender, and such diols include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, Neopentane glycol may be used. Such a curing agent is preferably 5 to 15% by weight of the liquid R, because the hardness and mechanical properties are lowered at 5% by weight or less, and the performance of the foam is lowered, and at 15% by weight or more, the obtained foam exhibits excessively high hardness.

In addition, the R liquid may include other additives, and may include a weathering stabilizer, a fungicide for preventing bacterial growth such as mold, a foam stabilizer for controlling the size and shape of a cell, a pigment for color and design diversity, and the like. Can be. It is preferable to use 0.5 to 2% by weight of the stabilizer, 0.1 to 1% by weight of the antibacterial agent, 0.5 to 2.5% by weight of the foam stabilizer.

The isocyanate reactor terminal prepolymer (P liquid) used in the present invention is prepared by reacting organic diisocyanates with compounds having an active hydrogen (polyol). The polyol is a polyester polyol alone, or a polyester polyol and a polyether polyol. Mixtures can be used. When the polyether polyol is mixed, 1 to 40 parts by weight is used based on 100 parts by weight of the polyester polyol. The polyol accounts for 20 to 50% by weight of the total prepolymer, and the organic diisocyanates account for 50 to 80% by weight. The prepolymer may also contain amino resins. It is preferable that the prepared prepolymer has an NCO content of 15 to 25%. If the NCO content is less than 15%, there is a problem that the reaction with the R liquid is slow, at 25% or more it becomes difficult to control the reaction rate and difficult to demould the produced foam.

The equivalent ratio of the reactive group (-OH) of the polyol and the reactive group (-NCO) of the diisocyanate compound is preferably 1: 0.9 to 1.5. When the equivalent ratio of the diisocyanate compound is 0.9 or less, surface stickiness and a decrease in mechanical properties due to the unreacted polyol are exhibited, and when 1.5 or more, the foam is hard and brittle.

Examples of the organic diisocyanates include 4,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, carbodiimide Modified diisocyanates or mixtures thereof can be used. The diisocyanate containing an aromatic ring has a disadvantage in that it is easy to cause yellowing by forming chromophore by benzene structure, but the mechanical property is superior to aliphatic diisocyanate, so 4,4′-diphenylmethane diisocyanate, 2,4-toluene Diisocyanate, 2,6-toluene diisocyanate and the like act advantageously to improve and maintain the mechanical properties of the foam, among which 4,4'- diphenylmethane diisocyanate has a linear structure and contains an aromatic ring The mechanical properties of the foams are excellent and are advantageous for the present invention.

The mixed polyols used in the R liquid, which is a polyol mixture, and the compounds having active hydrogens used in the synthesis of the P liquid may be the same, and polyester polyols and polyether polyols are used individually or in combination.

In the polyurethane resin composition of the present invention, the amino resin is an amino resin having an amino equivalent of 150 to 4500, and must be used in the P liquid or the R liquid. Preferably, 0.1 to 40% by weight when added to the liquid R, 0.1 to 20% by weight when added to the liquid P, and the total composition is used in the range of 0.05 to 20% by weight.

The amino resin is a monomolecular or low molecular weight condensate of an amino group or a component containing an amido group, a so-called aminoplast former and a carbonyl compound. A thermoset resin obtained by reacting an amino compound with an aldehyde to produce a compound having a hydroxyalkyl group, with an average of at least one reactor per molecule. The reactor is -NHR or -OH to -OH. The R substituents of the -NHR group are typically hydrogen atoms or hydrocarbons, wherein the hydrocarbons are substituted or unsubstituted, and if substituted the substituents must be those which do not inhibit or interfere with the polymerization. Representative examples of R substituents are methyl, alkyl such as ethyl, aryl such as phenyl, alkoxy and carbonyl. Representative examples of amino resins are urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, toluenesulfonamide-formaldehyde, acrylamide-formaldehyde and ethyleneurea-formaldehyde. Among amino resins, melamine-formaldehyde resins and urea-formaldehyde resins are of industrial importance. The amino resin is thermoset and crosslinks to form an insoluble and insoluble resinous network that is high in strength, robust, structurally stable and heat resistant.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

Polymer resin Combined Of prepolymer (P liquid)  Produce

4,4′-diphenylmethane diisocyanate, polyol, amino resin were added to the 10L reactor in the same composition as in Tables 1 to 3, and the temperature was raised to 80 ° C. while stirring at 200 rpm. When the NCO content of the prepolymer (P liquid) was titrated to maintain 20%, the reaction was terminated, and the prepared prepolymer (P liquid) was kept at a temperature of 45 ± 1 ° C. and stored.

Having active hydrogen groups Polyol  Mixture (R solution) preparation

Each raw material was added to the 10L reactor in the same composition as in Tables 1 to 3, and then stirred at 100 rpm for 30 minutes to ensure sufficient mixing and storage at 45 ± 1 ° C.

Foam  Manufacturing and Characterization

The polyurethane resin composition was prepared using the prepolymer (P liquid) and the polyol mixture (R liquid) prepared above.

Stock solution temperature: 45 ± 1 ℃

R liquid and catalyst stirring speed and time: 4000 rpm, 20 seconds

Stirring speed and mixing time of P liquid and R liquid: 4000 rpm, 5 seconds

Mold Used: 100mm X 200mm X 10mm

Mold temperature: 55 ± 3 ℃

Demold time: 10 minutes

Evaluation of Physical Properties: After demolding, the samples were aged for more than 24 hours, and the specimens were prepared by using a knife to measure their properties.

Example  1 to 4 and Comparative example  1 to 4

Examples 1 to 4 prepared foams using R liquid prepared by mixing amino resins, and the compositions and mechanical properties of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 1.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 R amount Polyol-a 83.27 83.27 79.66 79.66 87.59 80.23 83.27 80.23 Polyol-b 0 0 4.98 4.98 0 6.02 0 6.02 Ethylene glycol 8.41 8.41 7.04 7.04 8.41 9.75 8.41 9.75 Amino resin 4.32 4.32 4.32 4.32 0 0 0 0 water One One One One One One 0.5 0.5 Foam stabilizer 2 2 2 2 2 2 2 2 stabilizator 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Antiseptic 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 catalyst 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 P amount Polyol-c 34.77 28.61 34.77 28.61 34.77 34.77 34.77 34.77 Polyol-d 0 5.03 0 5.03 0 0 0 0 Isocyanate 65.73 66.36 65.73 66.36 65.73 65.73 65.73 65.73 NCO Content (%) 20 20 20 20 20 20 20 20 OH / NCO equivalence ratio 1: 1.2 1: 1.2 1: 1.3 1: 1.4 1: 1.1 1: 1.2 1: 1.1 1: 1.2 Foam state Good Good Good Good Good Good Good Good importance 0.25 0.25 0.25 0.25 0.25 0.26 0.33 0.33 Hardness (C type) 59 57 60 59 48 47 58 56 Tensile strength (kgf / cm ² ) 25 23 22 20 15 14 23 21 Elongation (%) 300 300 300 300 300 310 330 310 Tear strength (kgf / cm) 12 13 13 13 9 9 12 12 Split Tier (kgf / cm) 2.7 2.5 2.5 2.3 1.5 1.6 2.5 2.5 Permanent Compression Shrinkage (%) 11 10 12 10 20 18 10 10

※ Polyol-a: Polyester polyol (molecular weight 1000), DT-1046 (large polymer)

   Polyol-b: polyether polyol (molecular weight 1000), PP-1000 (Korean polyol)

   Polyol-c: polyester polyol (molecular weight 2000), DT-2014 (large polymer)

   Polyol-d: polyether polyol (molecular weight 2000), PP-2000 (Korean polyol)

   Defoamer: DC-193 (Air Product)

   Catalyst: Dabco-EG (Air Product)

   Amino Resin: Cymel 1116 (Cytec Industries)

   Unit: weight%

As can be seen from the foam properties of Table 1 Examples 1 to 4 in which the amino resin is included in the R liquid, although the specific gravity is lower than Comparative Examples 1 to 4 it can be seen that the mechanical properties are excellent.

Example  5 to 8

Examples 5 to 8 synthesized a P liquid using an amino resin and prepared a foam using the same, and the compositions and mechanical properties of Examples 5 to 8 and Comparative Examples 5 to 6 are shown in Table 2.

division Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 5 Comparative Example 3 Comparative Example 6 R amount Polyol-a 88.31 88.31 79.35 79.35 87.59 87.59 83.27 87.59 Polyol-b 0 0 10.38 10.38 0 0 0 0 Ethylene glycol 7.69 7.69 6.27 6.27 8.41 8.41 8.41 8.41 water One One One One One One 0.5 0.5 Foam stabilizer 2 2 2 2 2 2 2 2 stabilizator 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Antiseptic 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 catalyst 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 P amount Polyol-c 28.34 23.96 28.34 23.96 34.77 26.51 34.77 26.51 Polyol-d 0 8.31 0 8.31 0 7.85 0 7.85 Amino resin 6.73 5.62 6.73 5.62 0 0 0 0 Isocyanate 64.93 62.11 64.93 62.11 65.73 65.64 65.73 65.64 NCO Content (%) 20 20 20 20 20 20 20 20 OH / NCO equivalence ratio 1: 1.2 1: 1.3 1: 1.3 1: 1.3 1: 1.1 1: 1.2 1: 1.1 1: 1.2 Foam state Good Good Good Good Good Good Good Good importance 0.25 0.25 0.25 0.25 0.25 0.26 0.33 0.33 Hardness (C type) 60 59 59 59 48 48 58 55 Tensile strength (kgf / cm ² ) 24 23 23 21 15 13 23 22 Elongation (%) 300 310 300 300 300 320 330 320 Tear strength (kgf / cm) 13 12 13 13 9 8 12 10 Split Tier (kgf / cm) 2.6 2.5 2.4 2.3 1.5 1.5 2.5 2.1 Permanent Compression Shrinkage (%) 12 10 11 12 20 17 10 9

※ Polyol-a: Polyester polyol (molecular weight 1000), DT-1046 (large polymer)

   Polyol-b: polyether polyol (molecular weight 1000), PP-1000 (Korean polyol)

   Polyol-c: polyester polyol (molecular weight 2000), DT-2014 (large polymer)

   Polyol-d: polyether polyol (molecular weight 2000), PP-2000 (Korean polyol)

   Defoamer: DC-193 (Air Product)

   Catalyst: Dabco-EG (Air Product)

   Amino Resin: Cymel 1156 (Cytec Industries)

   Unit: weight%

As shown in Table 2, the foam using the P liquid reacted with the addition of the amino resin is significantly superior in the low specific gravity (0.2 to 0.3) compared to the foam of the comparative example, and has a high specific gravity (0.3 to 0.4) foam of the comparative example. It can be seen that they exhibit comparable mechanical properties.

Example  9 to 12

Examples 9 to 12 prepared foams of R liquid and P liquid containing amino resins, and the compositions and mechanical properties of Examples 9 to 12 and Comparative Examples 7 to 8 are shown in Table 3.

division Example 9 Example 10 Example 11 Example 12 Comparative Example 1 Comparative Example 7 Comparative Example 3 Comparative Example 8 R amount Polyol-a 83.27 83.27 79.66 79.66 87.59 80.23 83.27 80.23 Polyol-b 0 0 4.98 4.98 0 6.02 0 6.02 Ethylene glycol 8.41 8.41 7.04 7.04 8.41 9.75 8.41 9.75 Amino resin 4.32 4.32 4.32 4.32 0 0 0 0 water One One One One One One 0.5 0.5 Foam stabilizer 2 2 2 2 2 2 2 2 stabilizator 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Antiseptic 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 catalyst 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 P amount Polyol-c 28.34 23.96 28.34 23.96 34.77 26.51 34.77 26.51 Polyol-d 0 8.31 0 8.31 0 7.85 0 7.85 Amino resin 6.73 5.62 6.73 5.62 0 0 0 0 Isocyanate 64.93 62.11 64.93 62.11 65.73 65.73 65.73 65.73 NCO Content (%) 20 20 20 20 20 20 20 20 OH / NCO equivalence ratio 1: 1.2 1: 1.2 1: 1.3 1: 1.2 1: 1.1 1: 1.2 1: 1.1 1: 1.2 Foam state Good Good Good Good Good Good Good Good importance 0.25 0.25 0.25 0.25 0.25 0.26 0.33 0.33 Hardness (C type) 62 58 59 57 48 45 58 53 Tensile strength (kgf / cm ² ) 25 23 23 21 15 14 23 19 Elongation (%) 300 300 300 300 300 310 330 310 Tear strength (kgf / cm) 13 13 12 13 9 8 12 10 Split Tier (kgf / cm) 2.7 2.5 2.5 2.4 1.5 1.5 2.5 2.4 Permanent Compression Shrinkage (%) 12 13 12 14 20 21 10 13

※ Polyol-a: Polyester polyol (molecular weight 1000), DT-1046 (large polymer)

   Polyol-b: polyether polyol (molecular weight 1000), PP-1000 (Korean polyol)

   Polyol-c: polyester polyol (molecular weight 2000), DT-2014 (large polymer)

   Polyol-d: polyether polyol (molecular weight 2000), PP-2000 (Korean polyol)

   Defoamer: DC-193 (Air Product)

   Catalyst: Dabco-EG (Air Product)

   Amino Resin: Cymel 1130 (Cytec Industries)

   Unit: weight%

As shown in Table 3, even when the amino resin was used in the P liquid and the R liquid at the same time, the foam was successfully molded and the mechanical properties such as hardness and tensile strength were excellent.

Claims (14)

50-93% by weight of polyester polyol having a weight average molecular weight of 500-5000, urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, toluenesulfonamide-formaldehyde, acrylamide-formaldehyde and ethyleneurea-form Polyol mixture comprising 0.1 to 40% by weight of amino resin selected from aldehyde, 0.5 to 2.5% by weight of water, 5 to 15% by weight of curing agent, 0.5 to 2.5% by weight of foam stabilizer; And A prepolymer comprising 20 to 50 wt% of a polyester polyol having a weight average molecular weight of 500 to 5000 and 50 to 80 wt% of a diisocyanate compound; To include, the foam specific gravity is a polyurethane resin composition for the foam adjusted to the range 0.2 ~ 0.3. A polyol mixture comprising 80 to 93 wt% of a polyester polyol having a weight average molecular weight of 500 to 5000, 0.5 to 2.5 wt% of water, 5 to 15 wt% of a curing agent, and 0.5 to 2.5 wt% of a foam stabilizer; And 20 to 39% by weight of polyester polyol having a weight average molecular weight of 500 to 5000, 60 to 79% by weight of diisocyanate compound, urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, toluenesulfonamide-formaldehyde, acrylic A prepolymer comprising 0.1 to 20% by weight of an amino resin selected from amide-formaldehyde and ethyleneurea-formaldehyde; To include, the foam specific gravity is a polyurethane resin composition for the foam adjusted to the range 0.2 ~ 0.3. 50-93% by weight of polyester polyol having a weight average molecular weight of 500-5000, urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, toluenesulfonamide-formaldehyde, acrylamide-formaldehyde and ethyleneurea-form Polyol mixture comprising 0.1 to 40% by weight of amino resin selected from aldehyde, 0.5 to 2.5% by weight of water, 5 to 15% by weight of curing agent, 0.5 to 2.5% by weight of foam stabilizer; And 20 to 39% by weight of polyester polyol having a weight average molecular weight of 500 to 5000, 60 to 79% by weight of diisocyanate compound, urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, toluenesulfonamide-formaldehyde, acrylic A prepolymer comprising 0.1 to 20% by weight of an amino resin selected from amide-formaldehyde and ethyleneurea-formaldehyde; To include, the foam specific gravity is a polyurethane resin composition for the foam adjusted to the range 0.2 ~ 0.3. The polyurethane resin composition for foam according to any one of claims 1 to 3, wherein the equivalent ratio of the hydroxyl group of the polyol and the isocyanate group of the diisocyanate compound is in the range of 1: 0.9 to 1.5. The method according to any one of claims 1 to 3, wherein the polyester polyol is ethylene glycol, 1,4-butanediol, 1,5-pentanediol, methylpentanediol, 1,6-hexanediol, trimethylolpropane Prepared by reaction of at least one polyhydric alcohol selected from glycerol and pentaerythritol with at least one dihydric acid selected from oxalic acid, malonic acid, succinic acid, adipic acid and sebacic acid, or polycaprolactonediol, polycarbonate A polyurethane resin composition for a foam, which is prepared from diol. The method according to any one of claims 1 to 3, wherein the polyol mixture further comprises 1 to 40 parts by weight of a polyether polyol having a weight average molecular weight of 500 to 4000 based on 100 parts by weight of the polyester polyol. Polyurethane resin composition for foam. The polyurethane resin composition for a foam according to claim 6, wherein the polyether polyol is polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol and polytetramethylene ether glycol. The diisocyanate compound according to any one of claims 1 to 3, wherein the diisocyanate compound is 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,6 -Hexamethylene diisocyanate, isophorone diisocyanate and carbodiimide modified diisocyanate or mixtures thereof, or a prepolymer thereof. A shoe midsole made by foaming the polyurethane resin composition of any one of claims 1 to 3. In the method for producing a polyurethane resin composition by mixing a polyol mixture and a prepolymer, 50 to 93% by weight of polyester polyol having a weight average molecular weight of 500 to 5000, 60 to 79% by weight of diisocyanate compound, urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, toluenesulfonamide-formaldehyde, acrylic Preparing a polyol mixture comprising 0.1 to 40 wt% of amino resin, 0.5 to 2.5 wt% of water, 5 to 15 wt% of curing agent, and 0.5 to 2.5 wt% of foam stabilizer selected from amide-formaldehyde and ethyleneurea-formaldehyde; Preparing a prepolymer comprising 20 to 50 wt% of a polyester polyol having a weight average molecular weight of 500 to 5000 and 50 to 80 wt% of a diisocyanate compound; Mixing the polyol mixture and prepolymer Method for producing a polyurethane resin composition for foam comprising a. In the method for producing a polyurethane resin composition by mixing a polyol mixture and a prepolymer, Preparing a polyol mixture comprising 80 to 93 wt% of a polyester polyol having a weight average molecular weight of 500 to 5000, 0.5 to 2.5 wt% of water, 5 to 15 wt% of a curing agent, and 0.5 to 2.5 wt% of a foam stabilizer; 20 to 39% by weight of polyester polyol having a weight average molecular weight of 500 to 5000, 60 to 79% by weight of diisocyanate compound, urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, toluenesulfonamide-formaldehyde, acrylic Preparing a prepolymer comprising 0.1 to 20% by weight of an amino resin selected from amide-formaldehyde and ethyleneurea-formaldehyde; Mixing the polyol mixture and prepolymer Method for producing a polyurethane resin composition for foam comprising a. In the method for producing a polyurethane resin composition by mixing a polyol mixture and a prepolymer, 50-93% by weight of polyester polyol having a weight average molecular weight of 500-5000, urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, toluenesulfonamide-formaldehyde, acrylamide-formaldehyde and ethyleneurea-form Preparing a polyol mixture comprising 0.1 to 40% by weight of amino resin selected from aldehyde, 0.5 to 2.5% by weight of water, 5 to 15% by weight of curing agent, and 0.5 to 2.5% by weight of foam stabilizer; 20 to 39% by weight of polyester polyol having a weight average molecular weight of 500 to 5000, 60 to 79% by weight of diisocyanate compound, urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, toluenesulfonamide-formaldehyde, acrylic Preparing a prepolymer comprising 0.1 to 20% by weight of an amino resin selected from amide-formaldehyde and ethyleneurea-formaldehyde; Mixing the polyol mixture and prepolymer Method for producing a polyurethane resin composition for foam comprising a. 13. The foam according to any one of claims 10 to 12, further comprising 1 to 40 parts by weight of a polyether polyol having a weight average molecular weight of 500 to 4000, based on 100 parts by weight of the polyester polyol. Method for producing a polyurethane resin composition. 13. The foam poly according to any one of claims 10 to 12, further comprising 1 to 40 parts by weight of a polyether polyol having a weight average molecular weight of 500 to 4000 in 100 parts by weight of the polyester polyol in the prepolymer. The manufacturing method of a urethane resin composition.