JP4583918B2 - Production method of polyurethane foam - Google Patents

Description

  The present invention relates to a method for producing a polyurethane foam. More specifically, the present invention relates to a method for producing a polyurethane foam having high mechanical strength and suitable for use in a shoe sole, and a polyester polyol suitable for use in the production method.

  When producing a molded product of polyurethane foam, it is preferable that the density of the polyurethane foam is low because the cost is low. However, if the density is lowered, the amount of resin per unit volume is reduced, so that the mechanical strength is lowered.

  Therefore, in order to improve the mechanical strength of the polyurethane foam, it has been proposed to add a crosslinking agent, a polyfunctional polyol, an aromatic polyol or the like to the polyol (see, for example, paragraph [0003] of Patent Document 1).

However, when a cross-linking agent or a polyfunctional polyol is used, there is a problem of causing gelation. When an aromatic polyol is used, further improvement in fluidity (fillability) and appearance are desired. Yes.
Japanese Patent Laid-Open No. 11-166041

  The present invention provides a polyester polyol that provides a polyurethane foam having a low density, a good appearance, and excellent mechanical strength such as tensile strength, tear strength, and elongation at break, and a method for producing polyurethane foam using the same. The task is to do.

That is, the gist of the present invention is as follows.
(1) (A) a polyester polyol obtained by condensation polymerization of an acid component containing succinic acid and sebacic acid and (B) a polyhydric alcohol, and having a viscosity at 40 ° C. of 10,000 mPa · s or less, and
(2) The present invention relates to a process for producing a polyurethane foam in which a polyisocyanate component and a polyol component containing the polyester polyol are reacted and foamed.

  According to the polyester polyol of the present invention and the production method using the same, a polyurethane foam having a low density, a good appearance, and excellent mechanical strength such as tensile strength, tear strength, and elongation at break is provided. be able to.

  The polyester polyol of the present invention is obtained by polycondensing (A) an acid component containing succinic acid and sebacic acid and (B) a polyhydric alcohol, and is useful as a raw material for polyurethane foam. .

  The molar ratio of succinic acid to sebacic acid (succinic acid / sebacic acid) is preferably 0.15 / 1 or more from the viewpoint of reducing the freezing point and exhibiting a liquid state under molding conditions (molding temperature: about 40 ° C.). The ratio is more preferably 0.6 / 1 or more, and preferably 6/1 or less, more preferably 4/1 or less from the viewpoint of facilitating injection and injection during molding. When this polyester polyol is used as a polyol component when producing a polyurethane foam, succinic acid / sebacic acid is used from the viewpoint of improving moldability such as improving fluidity (fillability) and improving the appearance. The molar ratio is preferably 1/1 or more, more preferably 2.5 / 1 or less.

  The acid component may be composed of succinic acid and sebacic acid, or in addition to succinic acid and sebacic acid, other acid components may be contained within a range that does not impair the object of the present invention.

  Examples of other acid components include oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, nonamethylene dicarboxylic acid, decamethylene dicarboxylic acid, undecamethylene dicarboxylic acid, and dodecamethylene dicarboxylic acid. Saturated aliphatic carboxylic acids such as, aliphatic carboxylic acids such as unsaturated aliphatic carboxylic acids such as maleic acid, fumaric acid and itaconic acid, and aromatic carboxylic acids such as phthalic acid and terephthalic acid. From the viewpoint of reducing the viscosity of the polyurethane foam and improving the appearance of the resulting polyurethane foam, an aliphatic carboxylic acid is preferred to an aromatic carboxylic acid.

  The content of the other acid component in the acid component is usually preferably 10% by weight or less, more preferably 5% by weight or less, and the acid component is further preferably composed of succinic acid and sebacic acid.

  Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6- Examples thereof include polyhydric alcohols having 2 to 10 carbon atoms such as hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, trimethylolpropane, and glycerin. These polyhydric alcohols may be used alone or in combination of two or more.

  Among the polyhydric alcohols, 1,3-propanediol and 1,4-butanediol are preferable from the viewpoint of obtaining a polyurethane foam excellent in physical properties such as tensile strength. These may be used alone or in combination, but 1,3-propanediol is preferably used from the viewpoint of imparting low viscosity and low melting point to the resulting polyester polyol.

  The polyester polyol of the present invention can be obtained by condensation polymerization of an acid component and a polyhydric alcohol.

  Regarding the ratio between the acid component and the polyhydric alcohol, the reaction between the acid component and the polyhydric alcohol is a polycondensation reaction. The equivalent ratio (COOH group / OH group) between the group (COOH group) and the hydroxyl group (OH group) of the polyhydric alcohol is preferably smaller than 1.

  The method for polycondensation of the acid component and the polyhydric alcohol is not particularly limited as long as it is a method generally employed for producing a polyester by polycondensation of the acid component and the polyhydric alcohol. Typical examples of the method for polycondensation of an acid component and a polyhydric alcohol include the methods described in “Guenter Oertel” edited by “Polyurethane Handbook” Hansar, 2nd edition (1994), p65-72. It is done.

  As the polyester polyol, a polyester polyol having a viscosity at 40 ° C. of 10,000 mPa · s or less is used.

  In a generally used automatic mixing type injection foaming machine, since the management temperature of the raw material tank and the raw material during the circulation of the raw material is around 40 ° C., the viscosity of the polyester polyol is regulated at 40 ° C.

  The viscosity at 40 ° C. of the polyester polyol is 10000 mPa · s or less, preferably 8000 mPa · s or less, more preferably 7000 mPa · s, from the viewpoint of improving injection moldability when molding polyurethane foam and performing stable ejection. It is as follows. The viscosity is a value when measured at a temperature of 40 ° C. after the measurement system is stabilized by a B-type (Brookfield) viscometer which is a kind of rotational viscometer.

  The acid value of the polyester polyol is 1 mgKOH / g or less, preferably 0.7 mgKOH / g or less, more preferably 0.5 mgKOH / g, from the viewpoint of improving mechanical properties of the polyurethane foam and preventing hydrolysis due to autocatalysis. The following is desirable.

  The hydroxyl value of the polyester polyol is preferably 28.1 to 224 mgKOH / g, preferably 32.1 to 224 mgKOH / g, more preferably 44.9 to 112 mgKOH / g in consideration of the viscosity, melting point and the like of the polyester polyol.

  Here, the acid value and hydroxyl value of the polyester polyol are values measured according to JIS K0070.

The number average molecular weight of the polyester polyol is desirably 500 to 4000, preferably 500 to 3,500, more preferably 500 to 3000, and still more preferably 1000 to 2500 in consideration of the viscosity, melting point and the like of the polyester polyol. The number average molecular weight of the polyester polyol is expressed by the formula:
[Number average molecular weight of polyester polyol]
= (56108 × average number of functional groups) / hydroxyl value (wherein 56108 is the mass (mg) of 1 mole of potassium hydroxide, the average functional group number is the average functional group number of the polyester polyol, and the hydroxyl value is the hydroxyl value of the polyester polyol) To do)
It is a value when calculated based on.

  The polyester polyol thus obtained can be suitably used as a polyol component when producing a polyurethane foam.

  The polyol component contains the polyester polyol and is a liquid having a low viscosity at 40 ° C. Accordingly, since the polyol component can be injected even at a low pressure, a polyurethane foam can be easily produced by reacting with the polyisocyanate component.

  The method for producing a polyurethane foam according to the present invention is greatly characterized in that the polyester polyol is used. In the production method of the present invention, since the polyester polyol is used, the resulting polyurethane foam has excellent mechanical strength.

In the production method of polyurethane foam using the polyester polyol, mainly,
(1) When a polyurethane foam is produced by reacting and foaming a polyisocyanate component and a polyol component, a method using a polyol component containing the polyester polyol as the polyol component (hereinafter referred to as production method I), and
(2) A polyol component used as a raw material for an isocyanate prepolymer when a polyurethane foam is produced by reacting and foaming an isocyanate prepolymer obtained by reacting a polyisocyanate component and a polyol component with the polyol component. As a method using a polyol component containing the polyester polyol (hereinafter referred to as production method II)
There is.

First, the manufacturing method I is demonstrated.
In the manufacturing method I, the polyol component containing the said polyester polyol is used as a polyol component used when making a polyurethane foam react by making a polyol component and a polyisocyanate component react and foam.

  The polyol component can contain other polyester polyols in addition to the polyester polyol. Other polyester polyols include, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, methylpentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol. Polycondensation of one or more polyhydric alcohols such as diglycerin, dextrose, sorbitol and one or more dibasic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, dimer acid, etc. Polyester polyols obtained by the following, polyether glycols such as polypropylene glycol and polyoxytetramethylene glycol, polycaprolactone polyols, polycarbonate polyols, and the like, and these may be used alone, They may be mixed and used more species.

  For each content of the polyester polyol and other polyester polyol in the polyol component, from the viewpoint of producing a polyurethane foam excellent in mechanical strength, making the polyol component liquid at 40 ° C., maintaining an appropriate viscosity. The content of the polyester polyol is preferably 10 to 95% by weight, more preferably 20 to 90% by weight, still more preferably 40 to 90% by weight, and the content of the other polyester polyol is preferably 5 to 90% by weight. %, More preferably 10 to 80% by weight, still more preferably 10 to 60% by weight.

  The polyol component may contain an appropriate amount of, for example, a chain extender, a foaming agent, a urethanization catalyst, a foam stabilizer, a stabilizer, a pigment, and the like as appropriate.

  As the chain extender, a compound having a low molecular weight and having two or more active hydrogens in the molecule can be used. Representative examples of chain extenders include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, methylpentanediol, 1,6- Hexanediol, trimethylolpropane, glycerol, pentaerythritol, diglycerol, dextrose, sorbitol and other polyhydric alcohols, ethylenediamine, hexamethylenediamine and other aliphatic polyamines, aromatic polyamines, diethanolamine, triethanolamine, di Examples thereof include alkanolamines such as isopropanolamine, and these may be used alone or in admixture of two or more.

  Examples of the foaming agent include water and fluorocarbons. These may be used alone or in combination of two or more.

  Examples of the urethanization catalyst include triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, tertiary amines such as 1,2-dimethylimidazole, tin (II) octoate, dibutyltin dilaurate These may be used alone, or may be used alone or in admixture of two or more.

  Examples of the foam stabilizer include silicone surfactants such as dimethylpolysiloxane, polyoxyalkylene polyol-modified dimethylpolysiloxane, and alkylene glycol-modified dimethylpolysiloxane, fatty acid salts, sulfate ester salts, phosphate ester salts, and sulfonate salts. And the like, and these may be used alone or in admixture of two or more.

  Examples of the stabilizer include dibutylhydroxytoluene, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], isooctyl-3- (3,5-di-t -Hindered phenol radical scavengers such as butyl-4-hydroxyphenyl) propionate; antioxidants such as phosphorous compounds such as phosphorous acid, triphenyl phosphite, triethyl phosphite, triphenyl phosphine; (5-Methyl-2-hydroxyphenyl) benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] condensate of propionate and polyethylene glycol These may be used alone or in combination of two or more.

  Examples of the pigment include inorganic pigments typified by transition metal salts, organic pigments typified by azo compounds, carbon powder, and the like. These pigments may be used alone or in combination of two or more. May be used.

  Typical examples of the polyisocyanate component used in production method I include isocyanate prepolymers.

  The isocyanate prepolymer can be obtained by stirring and reacting a polyisocyanate monomer and a polyol in a conventional manner in the presence of an excess of the polyisocyanate monomer.

  Specific examples of the polyisocyanate monomer include tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate, 3, 3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, etc. These polyisocyanate compounds and their modified products, for example, carbodiimide modified products, may be used, and these may be used alone or in admixture of two or more. Among these, it is preferable to use 4,4′-diphenylmethane diisocyanate alone or to use 4,4′-diphenylmethane diisocyanate in combination with a modified carbodiimide.

  Examples of the polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, methylpentanediol, 1,6-hexanediol, One or more polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, diglycerin, dextrose, sorbitol and one or more two kinds of oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, dimer acid, etc. Polyester polyols obtained by polycondensation with a basic acid, polyether polyols such as polypropylene glycol and polyoxytetramethylene glycol, polycaprolactone polyols, polycarbonate polyols, and the like, and these may be used alone, They may be mixed and used more species.

  Further, an isocyanate prepolymer can be prepared using the polyester polyol. As will be described later, this isocyanate prepolymer can be suitably used as an isocyanate component in producing a polyurethane foam.

  In addition, when preparing an isocyanate prepolymer, you may add an additive as needed.

  Examples of additives include additives used as necessary when preparing polyester polyols, acidic gases such as hydrogen chloride gas and sulfurous acid gas, acetyl chloride to prevent the isocyanate prepolymer from self-polymerizing. An isocyanate self-polymerization inhibitor such as acid chlorides such as benzoyl chloride and isosuccinic acid chloride, and phosphoric acid compounds such as phosphoric acid, monoethyl phosphate, and diethyl phosphate can be used. These additives may be used alone or in combination of two or more.

  The NCO% of the isocyanate prepolymer is preferably 15% or more, more preferably 17% or more from the viewpoint of preventing the molding with a low-pressure foaming machine from becoming difficult due to the increase in viscosity. From the viewpoint of avoiding a decrease in the weighing accuracy of the foaming machine, it is preferably 25% or less, more preferably 23% or less, and still more preferably 22% or less.

  Since the isocyanate prepolymer exhibits a liquid state at a temperature of 15 ° C. or higher and can be discharged even at a low pressure, for example, a polyurethane foam can be easily produced even at a molding temperature of 40 to 50 ° C.

  In the manufacturing method I, when making a polyisocyanate component and a polyol component react, it is preferable to adjust both ratio so that an isocyanate index may be set to 95-110.

  In the production method I, a polyurethane foam can be produced by mixing and stirring a polyisocyanate component and a polyol component with a molding machine, injecting the mixture into a mold, and foaming. More specifically, for example, after adjusting the temperature of the polyol component to a temperature of about 40 ° C. using a tank or the like, using a foaming machine such as an automatic mixing injection type foaming machine or an automatic mixing injection type foaming machine. A polyurethane foam can be produced by mixing and reacting a polyol component and a polyisocyanate component.

  Moreover, according to the manufacturing method I, after mixing a polyisocyanate component and a polyol component, a urethane shoe sole can be shape | molded with the foaming machine normally adjusted to about 40-50 degreeC.

  Production method I can also be used for the production of non-foamed elastomers, but when used in the production of shoe soles, the resulting polyurethane foam reduces the amount of resin per unit volume. Regardless, mechanical strength such as tensile strength and tear strength can be sufficiently improved.

Next, Production Method II will be described.
In production method II, the isocyanate prepolymer obtained by reacting the polyisocyanate component and the polyol component and the polyol component are reacted and foamed to produce a polyurethane foam, which is used to prepare the isocyanate prepolymer. As the polyol component to be used, a polyol component containing the polyester polyol is used.

  In the polyester polyol contained in the polyol component used in preparing the isocyanate prepolymer, the molar ratio of succinic acid to sebacic acid (succinic acid / sebacic acid) is preferably from the viewpoint of easy handling of the isocyanate prepolymer. 6/1 or less, more preferably 4/1 or less, from the viewpoint of reducing the viscosity and melting point of the resulting polyester polyol, preferably 0.15 / 1 or more, more preferably 0.6 / 1 or more.

  As a polyisocyanate component which is a manufacturing raw material of an isocyanate prepolymer, the polyisocyanate monomer etc. which are used by manufacturing method I are mentioned, for example.

  As a polyisocyanate monomer, the same thing as the specific example of the polyisocyanate monomer used by the manufacturing method I is illustrated. Among these examples, 4,4′-diphenylmethane diisocyanate alone or a combination of 4,4′-diphenylmethane diisocyanate and a modified carbodiimide thereof is preferable.

  In production method II, by using the polyester polyol, the viscosity of the resulting isocyanate prepolymer can be suitably maintained, so that a polyurethane foam having excellent mechanical strength can be obtained.

  The polyol component can contain other polyester polyols in addition to the polyester polyol. As another polyester polyol component, the same thing as what is used by the manufacturing method I is illustrated, for example.

  The content of the polyester polyol in the polyol component is preferably 10 to 100% by weight, more preferably 50 to 100% by weight, and the content of the other polyester polyol is preferably 0 to 90% by weight, more preferably Is 0 to 50% by weight.

  Further, the ratio of the polyisocyanate component and the polyol component is preferably adjusted so that the equivalent ratio of NCO 3 / OH group is usually about 5 to 30.

  In addition, when preparing an isocyanate prepolymer, you may add additives, such as a self-polymerization inhibitor, antioxidant, and an ultraviolet absorber, as needed.

  Examples of the self-polymerization inhibitor are the same as those that can be added when preparing the isocyanate prepolymer in Production Method I.

  Examples of the antioxidant and the ultraviolet absorber are the same as those that can be added to the polyol component used in Production Method I.

  Next, an isocyanate prepolymer is obtained by mixing a polyisocyanate component, a polyol component and, if necessary, an additive by a conventional method, stirring and reacting.

  The NCO% of the isocyanate prepolymer thus obtained is preferably 12% or more, more preferably 14% or more, from the viewpoint of reducing the viscosity and facilitating molding with a low-pressure foaming machine. From the viewpoint of improving the measuring accuracy of the foaming machine, it is preferably 25% or less, more preferably 23% or less, and still more preferably 22% or less.

  Since the isocyanate prepolymer exhibits a liquid state at a temperature of 15 ° C. or higher and can be discharged even at a low pressure, for example, a polyurethane foam can be satisfactorily produced even at a molding temperature of 40 to 50 ° C.

  Next, the polyurethane foam is obtained by reacting and foaming the isocyanate prepolymer and the polyol component.

  As a polyol component used for reaction with an isocyanate prepolymer, the same thing as other polyols other than the polyester polyol used for a polyol component in the manufacturing method I is illustrated.

  In addition, a chain extender, a foaming agent, a urethanization catalyst, a stabilizer, a pigment, and the like may be appropriately added in an appropriate amount to the polyol component used for the reaction with the isocyanate prepolymer. Examples of these components are the same as those that can be added to the polyol component used in Process I.

  In the production method II, when the polyisocyanate component and the polyol component are reacted, it is preferable to adjust the ratio of the two so that the isocyanate index is 95 to 110.

  In the production method II, a polyurethane foam can be produced by mixing and stirring an isocyanate prepolymer, a polyol component and, if necessary, an additive with a molding machine, injecting the mixture into a mold and foaming. More specifically, for example, the polyol component is usually adjusted to a temperature of about 40 ° C. using a tank or the like, and then the isocyanate is used using a foaming machine such as an automatic mixing injection type foaming machine or an automatic mixing injection type foaming machine. A polyurethane foam can be produced by mixing and reacting with a prepolymer.

  Moreover, according to the manufacturing method II, after mixing an isocyanate prepolymer and a polyol component, a urethane shoe sole can be shape | molded with the foaming machine normally adjusted to about 40-50 degreeC. When production method II is used for the production of shoe soles, the resulting polyurethane foam can sufficiently improve the mechanical strength such as tensile strength and tear strength despite the decrease in the amount of resin per unit volume. it can.

Thus, the density of the molded product of the polyurethane foam obtained by the production method I or the production method II is preferably 0.15 to 1.0 g / cm ³ , more preferably 0.2 to 0.5 from the viewpoint of achieving sufficient mechanical strength and low density. 0.6 g / cm ³ , more preferably 0.2 to 0.4 g / cm ³ .

  Production method II can also be employed when producing a non-foamed elastomer.

In the following, “parts” means “parts by weight”.
Preparation Examples 1 to 5 (Production of polyester polyols A to E)
After charging succinic acid, sebacic acid and 1,3-propanediol in the amounts shown in Table 1 in a four-necked flask, a stirring bar, a dehydrating tube, a nitrogen gas inlet tube and a thermometer were attached to the flask.

  Next, nitrogen gas was introduced into the flask, the generated water was distilled off, and the temperature was raised to 220 ° C. After confirming that the inside of the flask became transparent, the pressure was gradually reduced and water was further distilled off.

  The reaction was continued until the acid value of the reaction solution became 1 mg KOH / g or less, and polyester polyols A to E were obtained.

  As physical properties of each polyester polyol, an acid value, a hydroxyl value, a viscosity at 40 ° C., a liquid property at 40 ° C., and a number average molecular weight were examined. The results are shown in Table 1.

The acid value of each polyester polyol was measured according to JIS K 0070, the hydroxyl value was JIS K 0070, and the viscosity at 40 ° C. was measured according to JIS Z 8803 (B type (Brookfield) viscometer used). The number average molecular weight of each polyester polyol is given by the formula:
[Number average molecular weight of polyester polyol]
= (56108 × average number of functional groups) / hydroxyl value (wherein 56108 is the mass (mg) of 1 mole of potassium hydroxide, the average functional group number is the average functional group number of the polyester polyol, and the hydroxyl value is the hydroxyl value of the polyester polyol) To do)
Calculated according to The liquidity at 40 ° C. was visually observed.

Production Examples 1 to 5 (Production of polyol components A to E)
100 parts of any of polyester polyols A to E obtained in Preparation Examples 1 to 5 shown in Table 2, 11 parts of ethylene glycol as a chain extender, 1.05 parts of water as a foaming agent, 0.8 part of triethylenediamine as a catalyst, and a silicone system 1 part of a foaming agent was mixed, adjusted to 60 ° C., and stirred to obtain polyol components A to E.

  As physical properties of the obtained polyol components A to E, the acid value and the hydroxyl value were examined in the same manner as in Preparation Example 1. The results are shown in Table 2.

Production Example 6 (Production of polyol component F)
Polyester polyol F (adipate having a molar ratio of ethylene glycol to 1,4-butanediol of 1.00, acid value 0.42 mg KOH / g, hydroxyl value 56.6 mg KOH / g, number average molecular weight 1982, viscosity at 40 ° C. 3925 mPa · s ) 100 parts, 11 parts of ethylene glycol as a chain extender, 1.05 parts of water as a blowing agent, 0.8 parts of triethylenediamine as a catalyst and 1 part of a silicone foam stabilizer, adjusted to 60 ° C., stirred, and polyol component F Got.

  The physical properties of the obtained polyol component F were examined in the same manner as in Production Example 1. The results are shown in Table 2.

Examples 1-3 and Comparative Examples 1-2
Any one of the polyol components A to D and F obtained in Production Examples 1 to 4 and 6 and an isocyanate prepolymer (trade name: Edifice B-2009, NCO%: 18.5%, manufactured by Kao Corporation) are automatically used. A polyurethane foam sheet of 10 mm × 100 mm × 300 mm was prepared by charging into a mixed injection foaming machine (manufactured by Polyurethane Engineering, Model MU-203S, Model No. 6-018) and foaming under the following molding conditions. The polyol components used in each example are shown in Table 3.

〔Molding condition〕
・ Isocyanate index: 100-103
・ Mixing temperature: Adjust the temperature of isocyanate prepolymer and polyol component to 35-45 ° C ・ Reaction: Cream time 5-10 seconds, Silk time 15-25 seconds, Rise time 35-60 seconds, Tack-free time 30- 55 seconds - demold time 4.5-5.5 minutes mold: mold temperature 45 to 55 ° C., the release agent silicone and wax density: free foam density 0.12~0.32g / cm ^3, the molded body density 0.35 g / cm ³
・ Aging condition: 1 week at room temperature

  Next, as physical properties of the obtained sheet, hardness, tensile strength (tensile strength), tear strength, and elongation at break were measured according to the following methods. The results are shown in Table 3.

[Physical properties of sheet]
Hardness (Asker C): Measured according to SRIS 0101 Tensile strength: Measured according to JIS K 6301 using JIS No. 1 dumbbells Tear strength: Measured according to JIS K 7311 Elongation at break: Measured according to JIS K 6301 using JIS No. 1 dumbbells : The sheet was visually observed, and the case where the entire surface of the sheet was uniform and glossy and there were almost no defects due to bubbles was judged as ◯, and the case where it was not judged as x.

  From the results shown in Table 3, the polyurethane foam sheet obtained in Comparative Example 1 was poor in appearance because the viscosity of the polyol component was very high, whereas the polyurethane foam obtained in Examples 1 to 3 It can be seen that the sheet is excellent in appearance. Further, the polyurethane foam sheets obtained in Examples 1 to 3 are remarkably increased in tensile strength and elongation at break while having the same compact density as the polyurethane foam sheet obtained in Comparative Example 2. It turns out that it is excellent.

Comparative Example 3
The polyol component F obtained in Production Example 5 and an isocyanate prepolymer (manufactured by Kao Corporation, trade name: Edifico Form B-2009, NCO%: 18.5%) are automatically mixed type injection foaming machine (manufactured by Polyurethane Engineering Co., Ltd.) , Model MU-203S, model number 6-018).

  However, since the polyol component was solidified in the tank, it could not be injected into the foaming machine and a polyurethane foam could not be obtained.

  The polyurethane foam obtained by the production method of the present invention can be suitably used as, for example, a shoe sole.

Claims (5)

(A) an acid component containing succinic acid and sebacic acid and (B) a polyhydric alcohol will by polycondensing, Ri viscosity der less 10000 mPa · s at 40 ° C., and a number average molecular weight of 500 to 4,000 A polyester polyol.   The polyester polyol according to claim 1, wherein the molar ratio of succinic acid to sebacic acid (succinic acid / sebacic acid) is 0.15 / 1 to 6/1.   The polyester polyol according to claim 1 or 2, wherein the polyhydric alcohol is a polyhydric alcohol having 2 to 10 carbon atoms. The manufacturing method of the polyurethane foam which foams a polyisocyanate component and the polyol component containing the polyester polyol in any one of Claims 1-3 with an injection-type foaming machine . A polyurethane foam obtained by the production method according to claim 4.