KR100186703B1 - Polyurethane foam and method for manufacturing thereof - Google Patents

Abstract

Polyurethane foams and methods of making the same are disclosed. A diol and a diisocyanate are reacted using a polyol as a solvent to prepare a urethane diol polyol mixture. The urethane diol polyol mixture is used to prepare the main diisocyanate prepolymer, and the urethane diol polyol mixture is used to prepare a polyol composition which is a curing agent. The urethane diol polyol mixture is prepared by mixing 70-130 wt% of the main ingredient with respect to 100 wt% of the curing agent. Polyurethane foam can be effectively used for shoe soles because the specific gravity is very low, the demoulding time is shortened to 2 to 5 minutes and the surface properties and physical properties are improved.

Description

Polyurethane Foam and Method of Making the Same

The present invention relates to a polyurethane foam and a method for manufacturing the same, and more particularly, to a polyurethane foam prepared by using a urethane diol polyol mixture, a specific gravity is low, the demold time is shortened, and surface properties and physical properties are improved, and a method for manufacturing the same. It is about.

In general, urethane foam is used in automobile interiors, helmets, children's toys, furniture, building materials, etc. and is particularly widely used for shoe soles.

The main goal of product development in the production of footwear is to reduce the proportion and shorten the demolding time while maintaining the general properties. This is because lowering the weight ratio can reduce raw material costs and reduce the weight of the shoes, and can reduce the demolding time to enable the automated process, thereby improving productivity and reducing labor costs.

As a representative example, a conventional polyurethane foam for a middle sole is prepared by adding a polyol in ester or ether form to diphenylmethane diisocyanate (p-MD1), toluene diisocyanate (TDI) or modified diphenylmethane diisocyanate. It is prepared by mixing the obtained diisocyanate prepolymer (hereinafter referred to as 'subject') and the polyol composition (hereinafter referred to as 'curing agent') containing a blowing agent, a chain extender, an antioxidant, a flame retardant, an antibacterial agent, a silicone catalyst, and a zinc catalyst. . When the ether form is used as the polyol, a mold foaming product having a specific gravity of 0.32 to 0.38 and a demolding time of 4 to 6 minutes can be obtained. When the ester form is used as a polyol, the specific gravity is 0.43 to 0.42 and a demolding time of 6 to 8 minutes. Molded foams can be obtained. However, by using these compositions, but reducing the amount of raw materials used for cost reduction, lowering the specific gravity to 0.3 or less, and to obtain a molded product with a demolding time of 5 minutes or less to shorten the processing time, the surface pore content increases and As the thickness becomes thinner, the appearance quality is deteriorated and the solvent resistance to the colored enamel solvent is reduced, so that the surface is eroded by the solvent, resulting in surface defects, and the deformation of the molded product occurs due to unreacted reaction. There is no problem.

A method of using polymeric polyols to solve this problem is disclosed in US Pat. No. 4,390,645 and European Patent Publication No. 162588. In addition, a method of using a polyether polyol obtained by polymerizing styrene, acrylate, vinyl chloride monomer and the like as a polyol in the presence of a dispersant is disclosed in US Patent No. 4,032,485 and European Patent Publication No. 91036, and a polyester polyol is used as a polyol. Methods are disclosed in Spanish Patents 555780 and 555890. However, these methods have a problem of producing or purchasing new polymeric polyols, and in particular, the polymeric polyols require complicated manufacturing processes, require high manufacturing techniques, and are expensive, causing high costs. There is a problem that the processing characteristics are lowered due to the viscosity and phase separation phenomenon.

On the other hand, the manufacturing method of urethane polyol is widely known. Processes for preparing polyester urethane polyols, which are high solid coating systems with good adhesion to elastomers and metals, are described in US Pat. Nos. 4,485,228, 4,540,766, 4,540,771, 4,605,724, 4,548,998 and the like.

In addition, a method for preparing a modified polyester urethane polyol containing OH groups by introducing at least 5% by weight of triol is disclosed in US Pat. Nos. 4,524,192, 4,530,976, 4,533,703, 4,533,704, and the like.

Most of these systems have been reported to cause unwanted low molecular weight chain extension reactions due to molecular weight control of polyesterurethanes and modified polyesterurethanes, and a method for improving such problems is disclosed in US Pat. No. 5,155,201. However, although most of these systems are used as high solid coating systems, there are many problems in actual use in foam compositions. In particular, due to the high molecular weight of the urethane polyol, there is a problem that the most important curing time (deformation time) is delayed in the manufacture of foams, which causes deterioration in processability.On the contrary, when only the low molecular weight is produced, most solid phases are formed and dissolved again. Problems that must be used occur.

In view of the above problems, the object of the present invention is that the production method is simple and no special apparatus is required, and by using the urethane diol polyol mixture which can be continuously manufactured in one reactor, the specific gravity is low and the demolding time is about 2 to 5 minutes. It is within a while to improve the surface properties, and to provide a new method for producing a low specific gravity polyurethane foam for midsole that can be applied to an automated process.

Another object of the present invention is to provide a polyurethane foam produced according to the above method.

Another object of the present invention is to provide a molded article produced using the polyurethane foam described above.

In order to achieve the above object of the present invention, 0.5 to 30% by weight of a diol monomer and a diisocyanate monomer using 100% by weight of a polyol composition selected from the group consisting of polyester polyols, polyether polyols and mixtures thereof as a solvent The urethane diol polyol mixture in which urethane diol and polyol are mixed is prepared by addition reaction of 0.5 to 30 wt%. And using this to prepare a polyisocyanate composition of the main diisocyanate prepolymer and the curing agent, to prepare a polyurethane foam mixed with the main 70 to 130% by weight based on 100% by weight of the curing agent. The main diisocyanate prepolymer is prepared by adding diisocyanate alone, modified isocyanate and urethane diol polyol mixture, diol, polyol and the like at 70 to 90 ° C., and the polyol composition as a curing agent is a urethane diol polyol mixture 3 based on 100% by weight of polyol. It is prepared by adding -10% by weight, 5 to 13% by weight of a chain extender having a hydroxyl group (-OH) or an amine group (-NH ₂ ), 0.7 to 1.3% by weight of water as an blowing agent and an additive.

Another object of the present invention is achieved by a polyurethane foam produced according to the process described above.

Another object of the present invention is achieved by a molded article produced using the polyurethane foam.

Hereinafter, the present invention will be described in detail.

( Manufacture of urethanediol / polyol mixture)

100% by weight of a polyol selected from the group consisting of polyether polyols, polyester polyols, and mixtures thereof as solvents, reacting urethane by reacting 0.5-30% by weight of diol monomers and 0.5-30% by weight of diisocyanate monomers at a constant temperature. To prepare a urethane diol polyol mixture of diol and polyol.

The polyester polyol may be one having an average molecular weight of 500 to 4000 produced by condensation reaction between polycarboxylic acid and polyhydric alcohol. In particular, as the polyester polyol produced by this method, SE-1714, SE-1541, SE-2014, etc. produced by Samsung Polymer Co., Ltd. can be preferably used. The polycarboxylic acid may be oxalic acid, malonic acid, rosinic acid, glutaric acid, adipic acid, pimelic acid, subvertic acid, azelaic acid, sebacic acid, brasilic acid, tafic acid, maleic acid, fumaric acid, glutamic acid. Cornic Acid, -Hydromuconic acid, β-hydromuconic acid, isophthalic acid, terephthalic acid, hemimeltic acid, 1,4-cyclohexanedicarbonyl acid, or the like can be used.

Polyhydric alcohols include 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,6-hexanediol , 1,7-heptanediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, 1,1,1-trimethyllopropane, 1,1-triethylethane, hexane-1,2,6-tri All, -Methyl glucoside, pentaerythritol, sorbitol and the like are preferably used.

The polyether polyol is preferably a polyoxyalkylene polyol containing 2 to 3 hydroxyl groups and a mixture thereof, and preferably a molecular weight of 500 to 4000. Mixtures thereof are prepared according to known methods for condensation of alkylene oxides or alkylene oxide mixtures with polyhydric initiators or polyhydric initiator mixtures to be prepared by random or stepwise addition. Alkylene oxides in the process include ethylene oxide, propylene oxide, butylene oxide, amylene oxide, aralkylene oxides such as styrene oxide, halogenated alkylene oxides such as chlorobutylene oxide, tetrahydrofuran, epichlorohydrin Etc. are included. In particular, the polyether polyol prepared by the above method is PP-750, PP-950, PP-1000, PP-2000, PP-3000, PP-4000, GP-400, GP-280, GP-1000 , GP-3000, GP-4000, GL-3000 and the like are preferably used.

In addition, diols used for urethanediol synthesis are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,4-pentanediol , 1,6-hexanediol, 1,7-heptopdiol, diethylene glycol, triethylene glycol and the like are preferable.

Diisocyanate is diphenylmethane diisocyanate (MDI), 2,4- / 2,6-toluene diisocyanate, 2,4 '-/ 4,4'-diphenylmethane diisocyanate, cyclohexane diisocyanate, isophorone Aliphatic and aromatic diiocyanates such as diisocyanate, hydrogenated diphenylmethane diisocyanate and 1,6-hexamethylene diisocyanate are preferred.

In addition, the reaction molar ratio of diol and diisocyanate is preferably 2: 1 to 2: 0.1, more preferably 2: 1 to 2: 0.5, and their reaction temperature or 70 to 90 ° C is preferable.

If the total amount of diol monomer and diisocyanate monomer is used in an amount of less than 1% by weight based on 100% by weight of polyol, the physical properties represented by the urethane diol polyol mixture may not be obtained. It is preferable to use within the range of 1% by weight to 60% by weight since difficulty occurs.

In particular, the method for preparing a urethane diol polyol mixture is 0.5 to 30% by weight of a diol monomer and 0.5 to 30 diisocyanate monomer, using 100% by weight of a polyol selected from the group consisting of polyester polyols, polyether polyols and mixtures thereof as a solvent. It is preferable to prepare the urethane diol polyol mixture in which 1% by weight to 60% by weight of urethane diol is dissolved in 100% by weight of the polyol by addition reaction at 70 to 90 ° C.

( Production of Polyurethane Foam Using Urethane Diol Polyol Mixture)

Polyurethane foam having a specific gravity of 0.23 to 0.28, demolding time of about 2 to 5 minutes, and improved surface properties and physical properties by using a urethane diol polyol mixture is preferably 70% of a diisocyanate prepolymer based on 100% by weight of the polyol composition as a curing agent. It prepares by mixing -130 weight%.

1) manufacture of subjects

First, the subject is prepared by addition reaction of one diisocyanate selected from the group consisting of diisocyanate alone, modified isocyanate alone and mixtures thereof, the urethane diol polyol mixture, diol and polyol in the temperature range of 70 ~ 90 ℃ To include 15 to 22% by weight of isocyanate. If the addition reaction temperature is lower than 70 ℃ the reaction does not proceed completely, if it is higher than 90 ℃ because the side reactions are not produced to obtain the desired subject to react in the above temperature range.

Diisocyanate homopolymers are aliphatic, aromatic diisocyanates, especially 2,4- / 2.6-toluene diiocyanate (TDI), 2,4 '-/ 4,4'-diphenylmethane diisocyanate (MDI), their Analogs and the like are used, and modified isocyanate homogeneous materials include trade names COSMONATE LL, COSMONATE LK, and COSMONATE LT manufactured by Kumho Mitsui Toatsu Corporation.

As the diisocyanate, a diisocyanate prepolymer composition using a polyisocyanate prepoly or a urethane diol polyol mixture may also be used, which is synthesized by adding a polyol or urethane diol polyol mixture to an aliphatic or aromatic diisocyanate, Isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,6-hexanemethylene diisocyanate, etc. are preferable. Aromatic diisocyanates are also 2,4- / 2,6-toluene diisocyanate (TDI), 2,4 '-/ 4.4'-diphenylmethane diisocyanate (MDI), analogs or isomers thereof, m- Phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethoxy-4,4'- diphenyl diisocyanate are preferable.

The polyol is preferably a polyester polyol, a polyether polyol, a urethane diol polyol mixture, a copolymer of a polyester polyol and a polyether polyol or a polyol mixed with the polyol. In this case, in the case of the copolymer or mixed polyol, the ratio of the polyether polyol to the polyester polyol is preferably 1:10 to 10: 1.

The polyisocyanate prepolymer so produced is preferably comprised between 15 and 22% by weight of isocyanate relative to 100% by weight of polyisocyanate prepolymer.

2) Preparation of Curing Agent

Next, the curing agent has a molecular weight of 750 to 3000 and an average functionality of 1.5 to 4, and is prepared by adding a urethane diol polyol mixture, a polyol, a chain extender, an additive, and the like. The addition amount is 3 to 10% by weight of the urethane diol polyol mixture, 5 to 13% by weight of a chain extender having a hydroxy group or an amine group and 0.7 to 1.3% by weight of water, which is a blowing agent, based on 100% by weight of the polyol. If the amount of the urethane diol polyol mixture is less than 3% by weight relative to 100% by weight of polyol, the desired physical properties cannot be obtained. If the amount of the urethanediol polyol mixture is more than 10% by weight, the workability is lowered to obtain the desired curing agent. do.

The polyol is intended to use one selected from the group consisting of polyester polyols, polyether polyols, urethanediol polyol mixtures, copolymers of polyester polyols and polyether polyols, and mixtures thereof.

Polyester polyols are synthesized by reacting polycarboxylic acids with polyhydric alcohols. The polycarboxylic acid may be oxalic acid, malonic acid, rosinic acid, glutaric acid, adipic acid, pimelic acid, subvertic acid, azelaic acid, sebacic acid, brasilic acid, tafic acid, maleic acid, fumaric acid, glutamic acid. Cornic Acid, Hydromuconic acid, -Hydromuconic acid, isophthalic acid, terephthalic acid, hemimeltic acid or 1,4-cyclohexanedicarbonyl acid, and polyhydric alcohols are 1,4-butanediol, 1,3-butanediol, 1,2 Butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,6-hexanediol, 1,7-heptanediol, diethylene glycol, triethylene glycol, dipropylene glycol, Glycerol, 1,1,1-trimethyllopropane, 1,1-triethylethane, hexane-1,2,6-triol, -Methyl glucoside, pentaerythritol or sorbitol is preferable.

As the polyether polyol, trade names GP-3000, PP-3000 or PP-2000 produced by Korea Polyol Co., Ltd. are particularly preferable.

In addition, it is preferable to use a copolymer of polyester polyol or polyether polyol or a polyol mixed with them by copolymerizing or mixing the ratio of polyether polyol to polyester polyol in a range of 1:10 to 10: 1 depending on the scope of application. .

Chain extenders for increasing the hardness of urethane foams are ethylene glycol, diethylene glycol , Alkylene glycol, 1,3-propylene glycol, butanediol, triethylene glycol, dipropylene glycol, tripropylene glycol, diethyltoluenediamine, methylenedianiline, methylene bis ( -Chloroaniline) and the like, and they have a lower molecular weight of 31 to 200 than the polyol and have a reactive hydroxyl group or an amine group. Such chain extenders add 5 to 13 weight percent with respect to 100 weight percent of the polyol. If the amount thereof is less than 5% by weight, the hardness is too low. If the amount is more than 13% by weight, the hardness is too high, so it is added within the above range.

As other additives, amine catalysts, antioxidants, silicones, antibacterial agents, flame retardants and the like are mixed, preferably 1 to 6% by weight based on 100% by weight of polyol.

The amine catalyst is N, N-dimethylaminoethanol, N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N, N-pentamethyldipropylenetriamine, N , N'`-dimethylethylamine, diaminobicyclooctane (DABCO), N-methylmorpholine, methylene-bis-dimethylcyclohexylamine, N, N, N ', N', N-pentamethyldiethylenetri Amine, N, N-diethylpiperazine, N, N, N'-trimethylaminoethylethanolamine, 1- (2-hydroxypropyl) imidazole, 1,4-bis (2-hydroxypropyl) -2 -Methyl piperazine and the like are preferable.

Water, the foam, is to be added 0.7 to 1.3% by weight relative to 100% by weight of the polyol composition. If the amount thereof is less than 0.7% by weight, the specific gravity is high, and if the amount is more than 1.3% by weight, the workability is lowered, so that the blowing agent is added within the above range.

3) Preparation of Polyurethane Foam

Thus, the main body and the hardening | curing agent are manufactured, and the main body 70-130 weight% is mixed with respect to 100 weight% of hardening agents, and the polyurethane foam which concerns on this invention is obtained.

When the mixing amount of the main agent and the curing agent is out of the above range, complete curing is not achieved, and thus, desired physical properties and workability may not be obtained.

Hereinafter, a preferred embodiment of the method for producing a polyurethane foam according to the present invention will be described in detail, but the present invention is not limited thereto.

( Manufacture of urethanediol / polyol mixture)

(Example 1)

A dry nitrogen flow device, a thermometer, and a reflux tube were installed in a four-necked flask, and Samsung Polymer's SE-1714 (1000 g) as a polyol and ethylene glycol (EG, 25 g) as a diol single molecule were used. Diphenyl methane diisocyanate (MDI, 25 g) was added as an isocyanate. While stirring the reactants using a magnetic bar while flowing the dried nitrogen gas these mixtures were slowly heated to raise the temperature to 72 ~ 80 ℃ and reacted for about 2 hours to prepare a urethane diol polyol mixture.

At this time, the completion point of the reaction was confirmed by FT-IR, it was confirmed that the isocyanate peak (2270cm ^-1 ) disappears. Point or Brookfield DV-Ⅱ It was confirmed that the viscosity meter was 1620cps at 40 ° C, and the OH number was 93.0 by reverse titration using acetic anhydride.

(Examples 2 to 5)

After selecting and adding polyol, diol, and diisocyanate as shown in [Table 1], urethanediol polyol mixtures were prepared in the same manner as in (Example 1), and their reaction progress was confirmed and the properties were measured (Example 1). ) And the results are shown in [Table 2].

( Production of diisocyanate prepolymer (topic))

(Examples 6 to 8)

In a four-necked flask, a dry nitrogen flow device, a thermometer, and a reflux tube are installed, and urethanediol polyol mixture and diisocyanate are selected and labeled as shown in [Table 3]. While stirring the reactants using a magnetic bar while flowing dried nitrogen gas, the temperature of these mixtures was gradually raised to 75 ° C. and reacted for about 2 hours to prepare a diisocyanate prepolymer (topic). Their point or Brookfield DV _- II It was confirmed by the viscometer, NCO wt% content was confirmed by the reverse titration method using DBA (Dibutylamine) and the results are shown in [Table 3].

(Comparative Examples 1 and 2)

It was prepared in the same manner as in (Example 6), except that SE-2014 of Samsung Polymer Co., Ltd. was used instead of the urethane diol polyol mixture, and the results are shown in [Table 3].

( Production of polyol composition (curing agent))

(Examples 9-11)

A four-necked flask was equipped with a stirrer, a reflux tube, and a thermometer, and as shown in [Table 4], urethanediol polyol mixture, chain extender, and silicone, yellowing agent, antibacterial agent, and foaming agent as water were added at 30 ° C. at 30 ° C. Mixing for minutes to prepare a polyol composition as a curing agent. Their point or Brookfield DV _- II It was confirmed by a viscometer, OH number was confirmed by reverse titration using acetic anhydride, the results are shown in [Table 4].

(Comparative Examples 3 to 4)

Except for the use of SE-1714 and SE-1541 of Samsung Polymer Co., Ltd. instead of the urethane diol polyol mixture, the preparation was carried out in the same manner as in (Example 9), and the results are shown in [Table 4].

(Polyurethane Foam Composition and Foam Production Using the Same)

(Examples 12 to 17)

The main body and the hardener prepared by the above process were added to the mixer in a weight% as shown in [Table 5], and the mixture mixed for 5 seconds was injected into a mold to prepare a polyurethane mold foam. The resulting foams were measured for physical properties according to ASTM standards and the results are shown in [Table 6]. Here, the foaming machine manufactured a foam using a model of Italian GUSBI company.

(Comparative Examples 5-6)

A foam was prepared in the same manner as in Example 12 using the main agent and the curing agent as shown in Table 5.

(Physical measurement and analysis)

The physical properties of the foams were measured by molding mill or ASTM D-729 method, and tensile strength, tear steel, or tensile steel or ASTM D-412 by HUN-FIELD HTE-5000, according to tear steel or DIN 53507. And wear resistance according to flexural steel or DIN 5354 3, according to DIN 53516. Reactivity was performed according to generally known standards. The above results are shown in [Table 6].

[Table 1] Composition of urethane diol polyol mixture

E.G. Ethylene Glycol

D.E.G: Diethylene Glycol

1,4-BD: 1,4-Butane diol

M.D.I: Diphenylmethane diisocyanate

T.D.I: 2,4- / 2,6-Toluene diisocyanate

IPDI: Isophoron diisocyanate

[Table 2] Urethane Diol Polyol Mixture Properties

[Table 3] Composition and Properties of Diisocyanate Prepolymer (Topic)

Table 4 Composition and Properties of Polyols (Hardeners)

Reference) E.G: Ethylene Glycol

Table 5 Polyurethane Foam Composition (Combination Ratio)

[Table 6] Physical Properties and Reactivity of Polyurethane Foam

In view of the above results, in the present invention, it can be seen that a polyurethane foam having a molding density of 0.3 g / cm 3 or less (generally used for a midsole) which can not be obtained in a comparative example can be obtained. It was confirmed that it does not lag significantly behind. In addition, in the case of polyurethane foam having a molding density of 0.3 g / cm 3 or more (generally used for outsoles), although the molding mill was slightly higher or higher, the physical properties thereof were significantly superior to those of the comparative example.

In particular, the polyurethane foam according to the present invention was found that the demolding time is greatly shortened to about 3 to 4 minutes.

Therefore, according to the present invention, polyurethane foams having low specific gravity and short demolding time can be manufactured while maintaining general physical properties, thereby reducing raw material costs and improving productivity. In addition, the polyurethane foam prepared according to the present invention has a low surface pore content and a low incidence of surface defects due to erosion of a solvent, and thus the molded article manufactured using the same has excellent deformation-free generation. In particular, a shoe window made using the polyurethane foam of the present invention is light and of good quality.

Claims (21)

100% by weight of a polyol selected from the group consisting of polyester polyols, polyether polyols and mixtures thereof as solvents is added to react 0.5 to 30% by weight of diol monomers and 0.5 to 30% by weight of diisocyanate monomers to form a urethanediol polyol. Preparing a mixture; One diisocyanate selected from the group consisting of diisocyanate alone, modified isocyanate alone, and mixtures thereof, the urethane, diol polyol mixture, diol and polyol is added and reacted at a temperature of 70 to 90 ° C. to prepare a main diisocyanate prepolymer. step; 3 to 10 weight percent of the urethanediol polyol mixture, 5 to 13 weight percent of a chain extender having a hydroxy group (-OH) or an amine group (-NH ₂ ), and 0.7 to 1.3 weight of water as a blowing agent, based on 100 weight percent of a polyol. Mixing% and additives to prepare a polyol composition that is a curing agent; And Method for producing a polyurethane foam, characterized in that the mixing step of 70 to 130% by weight based on 100% by weight of the curing agent. The method according to claim 1, wherein the polyester polyol in the step of preparing the urethane diol polyol mixture is obtained by condensation reaction of polycarboxylic acid and polyhydric alcohol, the average molecular weight is 500 to 4000 polyurethane Method of making foams. According to claim 2, wherein the polycarboxylic acid is oxalic acid, malonic acid, rosinic acid, glutonic acid, adipic acid, pimelic acid, subvertic acid, azelaic acid, sebacic acid, brasilic acid, tarpric acid, maleic acid , Fumaric acid, glutamic acid, Hydromuconic acid, -A method for producing a polyurethane foam, characterized in that it is one selected from the group consisting of hydromuconic acid, isophthalic acid, terephthalic acid, hemimelitic acid and 1,4-cyclohexanedicarbonyl acid. The method of claim 2, wherein the polyhydric alcohol is 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol , 1,6-hexanediol, 1,7-heptanediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, 1,1,1-trimethyllopropane, 1,1-triethylethane, hexane- 1,2,6-triol, -Method for producing a polyurethane foam, characterized in that one selected from the group consisting of methyl glucoside, pentaerythritol and sorbitol. According to claim 1, wherein the polyether polyol in the step of preparing the urethane diol polyol mixture is a polyoxyalkylene polyol comprising a mixture of 2 to 3 or a mixture thereof, characterized in that the molecular weight of 500 to 4000 Method for producing urethane foams. The method of claim 1, wherein in the step of preparing a mixture of the urethane diol polyol, the monomer is ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1, Preparation of a polyurethane foam, characterized in that one selected from the group consisting of 5-pentanediol, 1,4-pentanediol, 1,6-hexanediol, 1,7-heptanediol, diethylene glycol and triethylene glycol Way. The method of claim 1, wherein the diisocyanate monomer as the polyether polyol in the step of preparing the urethane diol polyol mixture is 2,4- / 2,6-toluene diisocyanate, diphenylmethane diisocyanate 2,4 '-/ Poly, characterized in that one selected from the group consisting of 4,4'-diphenylmethane diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate and 1,6-hexamethylene diisocyanate Method for producing urethane foams. The method of claim 1, wherein the diol monomer and the diisocyanate monomer are reacted in a molar ratio of 2: 1 to 2: 0.1 in the step of preparing the urethane diol polyol mixture. The method of claim 1, wherein the main diisocyanate prepolymer comprises 15-22% by weight of isocyanates. The method of claim 1, wherein the diisocyanate homogenate in preparing the subject is 2,4- / 2,6-toluene diisocyanate (TDI), 2,4 '-/ 4,4'-diphenylmethane di A method for producing a polyurethane foam, characterized in that one is selected from the group consisting of isocyanates (MDI) and analogs thereof. The method of claim 1, wherein in the step of preparing the subject, the diol is 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1, 3-pentanediol, 1,6-hexanediol, 1,7-heptanediol, diethylene glycol triethylene glycol, dipropylene glycol, glycerol, 1,1,1-trimethyllopropane and 1,1-triethylethane Method for producing a polyurethane foam, characterized in that one selected from the group consisting of. The method of claim 1, wherein each of the polyols in the subject and the step of preparing the curing agent is a group consisting of polyester polyols, polyether polyols, urethanediol polyol mixtures, copolymers of polyester polyols and polyether polyols and mixtures thereof Method for producing a polyurethane foam, characterized in that one selected from. The method of claim 12, wherein the copolymerization or mixing of the polyester polyol and the polyether polyol or a mixture thereof such that the ratio of the polyether polyol to the polyester polyol is 1:10 to 10: 1. Process for the preparation of polyurethane foams. According to claim 1, wherein in the step of preparing the curing agent, the chain extender having a molecular weight of 31 to 200 and having a reactive hydroxy group and an amine group, ethylene glycol, diethylene glycol, , Group consisting of alkylene glycol, 1,3-propylene glycol, butanediol, triethylene glycol, dipropylene glycol, tripropylene glycol, diethyl toluenediamine, methylene dianiline, methylene bis (o-chloroaniline) and mixtures thereof Method for producing a polyurethane foam, characterized in that one selected from. The method of claim 1, wherein in the preparing of the curing agent, the additive comprises an amine catalyst, an antioxidant, a silicone, an antibacterial agent, and a flame retardant. The method of claim 15, wherein the amine catalyst is N, N-dimethylaminoethanol, N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N', N-penta Methyldiethylenetriamine, N, N-dimethylethylamine, diaminobicyclo octane (DABCO), N-methylmorpholine, methylene-bis-dimethylcyclohexylamine, N, N, N ', N, N-penta Menyldipropylenetriamine, N, N'-diethylpiperazine, N, N, N'-trimethylaminoethylethanolamine, 1- (2-hydroxypropyl) imidazole, 1,4-bis (2-hydroxy Oxypropyl) -2-methylpiperazine and a mixture thereof, the process for producing a polyurethane foam, characterized in that one. Urethane prepared by adding and reacting 0.5-30% by weight of diol monomer and 0.5-30% by weight of diisocyanate monomer using 100% by weight of one polyol selected from the group consisting of polyester polyol, polyether polyol and mixtures thereof Diolpolyol mixtures. Polyurethane foam prepared according to the method of claim 1. 19. The polyurethane foam according to claim 18, wherein the polyurethane foam is demolded for 2 to 5 minutes. Molded article made using the polyurethane foam prepared according to claim 18. The molded article according to claim 20, wherein the molded article is a shoe sole.