CN1986594A - Method for producing polyurethane foam - Google Patents

Abstract

The present invention relates to a method for producing polyurethane foam, the density of the polyurethane foam is above 0.1g/cm ³ , the production method comprises the step of reacting polyol component and polyisocyanate component, and the polyol component comprises: Alcohol A, which is a polyester polyol having a hydroxyl value of 45 to 115 mgKOH/g formed by polycondensation of a polyhydric alcohol component containing a polyhydric alcohol having a side chain, and a polybasic acid component; and polyol B, which is a functional group number 3 and a polyether polyol with a hydroxyl value of 15-40 mgKOH/g; and the weight ratio of polyol A to polyol B is 1.2-3. The polyurethane foam obtained by the production method of the present invention is suitably used as, for example, shoe soles, and as cushioning materials used in automobiles or other means of transportation, furniture, bedding, and the like.

Description

How to make polyurethane foam

technical field

The present invention relates to a method for producing polyurethane foam. More specifically, it relates to a method for producing a polyurethane foam that can be suitably used as, for example, shoe soles, and cushioning materials used in automobiles or other means of transportation, furniture, bedding, etc.; a polyurethane foam obtained by the production method; The polyurethane foam sole; and shoes with the sole.

Background technique

Polyurethane foam is mostly used in various applications such as heat insulating materials, cushioning pads, and shoe soles. Among polyurethane foams, especially in the field of semi-rigid polyurethane foams used for shoe soles and the like, polyurethane foams having strength for securing functions as shoe soles and the like and having low resiliency are desired. In addition, from the viewpoint of fatigue reduction, polyurethane foams that are lighter in weight and have the above-mentioned characteristics are desired.

Conventionally, in order to achieve both low resiliency and strength of polyurethane foam, there is known a method of using polyols with 2-3 functional groups (polyol) at a specific mixing ratio (for example, refer to JP-A-2004-161987).

However, as the above-mentioned method, since the orientation of the resin is lowered, it is required to further increase the strength in terms of weight reduction of the polyurethane foam.

In addition, in the field of flexible polyurethane foam, there is known a method of using polyester polyol and polyether polyol in combination (for example, refer to Japanese Patent Application Laid-Open No. 07-025974 ), and the use of polyols having side chains on the main chain. A method in which polyhydric alcohol polyester polyols and polyether polyols are used in combination (for example, refer to JP-A-02-232218).

However, these flexible polyurethane foams are soft low-hardness foams that generally use toluene diisocyanate as the main component as the polyisocyanate component. Since their molded density is lower than 0.1 g/cm ³ , they are classified as C under JIS K7312. Type hardness tester cannot measure. Therefore, these flexible polyurethane foams do not have the mechanical strength which is the object of the present invention.

Therefore, in recent years, it is desired to develop a polyurethane foam having a molded density of 0.1 g/cm ³ or less, a hardness measurable with a C-type durometer specified in JIS K7312, high foam strength, and excellent elongation.

Contents of the invention

The present invention relates to a method for producing polyurethane foam having a density of 0.1 g/cm ³ or more, the method including the step of reacting the following polyol component and polyisocyanate component. The polyol component includes: polyol A, which is a polyester polyol with a hydroxyl value of 45-115 mgKOH/g formed by polycondensation of a polyhydric alcohol component containing a polyhydric alcohol with a side chain and a polyacid component; and Polyol B is a polyether polyol with 3 functional groups and a hydroxyl value of 15-40 mgKOH/g; and the weight ratio of polyol A to polyol B is 1.2-3.

Detailed ways

The present invention relates to a method for the manufacture of polyurethane foams having high foam strength and low resilience.

According to the method for producing a polyurethane foam of the present invention, a polyurethane foam excellent in high foam strength and low resilience can be obtained.

These and other advantages of the invention will become apparent from the following description.

The polyol component contains polyol A and polyol B.

The polyol A is a polyester polyol having a hydroxyl value of 45 to 115 mgKOH/g formed by polycondensing a polyhydric alcohol component containing a polyhydric alcohol having a side chain, and a polybasic acid component.

From the viewpoint of improving the dimensional stability of the polyurethane foam and increasing the foam strength, the hydroxyl value of the polyol A is 45 to 115 mgKOH/g, preferably 50 to 100 mgKOHg, more preferably 70 to 90 mgKOH/g, and even more preferably 71 to 86 mgKOH /g, more preferably 71 to 77 mgKOH/g. In addition, the hydroxyl value is a value measured based on JIS K0070.

The "polyhydric alcohol having a side chain" is a compound containing only a primary hydroxyl group as a hydroxyl group and an alkyl group as a side chain. The number of carbon atoms of the alkyl group in the side chain is preferably 1-4, and more preferably 1-2, from the viewpoint of improving foam strength.

Specific examples of polyhydric alcohols having side chains include 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,4 -Butanediol, neopentyl glycol, 2,2-dimethyl-1,4-butanediol, 2,3-dimethyl-1,4-butanediol, 3-methyl-1,5 -pentanediol, 2,3-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 3-ethyl-1,5-pentanediol, 2-methyl-1,6-hexanediol, 3-methyl-1,6-hexanediol, 2,3,4-trimethyl-1,5-pentanediol, 3,3-dimethyl Base-1,6-hexanediol, 3,3-diethyl-1,5-pentanediol, 3,3-diethyl-1,6-hexanediol, etc., these substances can be used alone or Mix two or more. Among these, 3-methyl-1,5-pentanediol is preferable from the viewpoint of achieving both foam strength and impact absorbability.

From the viewpoint of hydrolysis resistance, the content of polyhydric alcohols having side chains in the polyhydric alcohol component is preferably 70 to 100% by weight, more preferably 90 to 100% by weight, and even more preferably 95 to 100% by weight. More preferably, it is 100% by weight.

Although the polyhydric alcohol component contains the polyhydric alcohol which has a side chain, it may contain polyhydric alcohol other than the polyhydric alcohol which has a side chain. The content of the polyhydric alcohols other than the polyhydric alcohol which has a side chain differs with the kind, Therefore It cannot be determined uniformly, Usually, what is necessary is just the range which does not hinder the object of this invention. The content of polyhydric alcohols other than polyhydric alcohols having side chains in the polyhydric alcohol component is usually preferably 10% by weight or less.

Examples of polybasic acid components include polybasic acid components containing aromatic carboxylic acids, aliphatic carboxylic acids, etc., for example: aliphatic carboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, and maleic acid ; Aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalene dicarboxylic acid; and their anhydrides or derivatives. These can be used individually or in mixture of 2 or more types, respectively. Among them, polybasic acid components containing an aromatic carboxylic acid are preferable from the viewpoint of improving foam strength, and among them, polybasic acid components containing terephthalic acid are more preferable. In addition, from the viewpoint of the foam strength of the obtained polyurethane foam and the reactivity with the polyhydric alcohol component, as the polybasic acid component, a polybasic acid component containing an aromatic carboxylic acid and/or an aliphatic carboxylic acid or the like is preferable, for example, It is preferable to use adipic acid and terephthalic acid in combination.

From the viewpoint of compatibility with the polyhydric alcohol component, the molar ratio (aromatic carboxylic acid/aliphatic carboxylic acid) of the aromatic carboxylic acid to the aliphatic carboxylic acid is preferably 0 to 0.25, more preferably 0.1 to 0.2, and furthermore Preferably it is 0.12 to 0.16.

Since the polycondensation of the polyhydric alcohol component and the polybasic acid component is polycondensation of the hydroxyl group of the polyhydric alcohol component and the carboxyl group of the polybasic acid component, the reaction of both proceeds stoichiometrically. The polycondensation of the polyhydric alcohol component and the polybasic acid component can be performed by a usual polycondensation reaction, and the present invention is not limited to this method.

Polyol B is a polyether polyol having 3 functional groups and a hydroxyl value of 15 to 40 mgKOH/g.

The term "polyol B having three functional groups" refers to a polyol obtained by addition-polymerizing a polyhydric alcohol having three functional groups as a polymerization initiator with an alkylene oxide. The number of functional groups of polyol B is three from the viewpoint of foam strength and dimensional stability.

From the viewpoint of improving the dimensional stability of the polyurethane foam and increasing the foam strength, the hydroxyl value of the polyol B is 15 to 40 mgKOH/g, preferably 24 to 37 mgKOH/g, more preferably 24 to 34 mgKOH/g. In addition, the hydroxyl value is a value measured based on JIS K0070.

From the viewpoint of the viscosity and liquid properties of the polyol B, the polyol B is preferably selected from polyether polyols with 3 functional groups (hereinafter, simply referred to as "polyether polyols") and polyether polyols based on polyether polyols. One or more kinds of polymer polyols (hereinafter, simply referred to as "polymer polyols").

Examples of polyether polyols include polyethers obtained by addition polymerization of polyhydric alcohols such as glycerin, trimethylolpropane, and 1,2,6-hexanetriol as polymerization initiators, and alkylene oxides. Polyol, polyoxybutylene glycol, etc. Among these, polyether polyols obtained by addition-polymerizing glycerin as a polymerization initiator with alkylene oxide are preferred.

Typical examples of polymer polyols include polymers in which polymer microparticles obtained by polymerizing polymerizable unsaturated group-containing monomers are dispersed in polyether polyols. The polymer can be produced by, for example, a method of mixing and dispersing polymer microparticles obtained by polymerizing a monomer containing a polymerizable unsaturated group with a polyether polyol; Polymerize the above-mentioned polymerizable unsaturated group-containing monomer in alcohol to produce polymer particles obtained from the above-mentioned polymerizable unsaturated group-containing monomer, and disperse them in polyether polyol method etc. Among these methods, the latter method is preferable because it is easy to obtain a polymer polyol in which polymer fine particles are uniformly dispersed in polyether polyol.

Examples of monomers containing a polymerizable unsaturated group include styrene; acrylonitrile; Alkyl methacrylate; glycidyl methacrylate; methyl acrylate, ethyl acrylate, butyl acrylate and other alkyl acrylates with 1 to 4 carbon atoms in the alkyl group; glycidyl acrylate, etc., these These substances may be used alone or in combination of two or more.

From the viewpoint of imparting low resilience to the polyurethane foam and improving the elongation of the polyurethane foam, the polyol component preferably contains a polyether polyol (hereinafter referred to as " Polyol C").

Polyol C can be easily prepared by adding sorbitol to propylene oxide. The average number of moles of polyoxypropylene groups added to sorbitol is preferably 7-15, more preferably 8-12, and still more preferably 9 or 10, from the viewpoint of imparting low resilience.

From the viewpoint of imparting low resilience to polyurethane foam and improving foam elongation and foam strength, the hydroxyl value of polyol C is preferably 380 to 550 mgKOH/g, more preferably 400 to 530 mgKOH/g, and even more preferably 450 to 500 mgKOH /g. In addition, the hydroxyl value is a value measured based on JIS K0070.

From the viewpoint of improving foam strength, the content of polyol A in the polyol component is preferably 50% by weight or more, more preferably 55% by weight or more, and even more preferably 60% by weight or more; from the viewpoint of maintaining hydrolysis resistance, Preferably it is 80 weight% or less, More preferably, it is 70 weight% or less, More preferably, it is 65 weight% or less.

From the viewpoint of imparting dimensional stability, the content of polyol B in the polyol component is preferably 15% by weight or more, more preferably 20% by weight or more, and even more preferably 25% by weight or more; from the viewpoint of improving foam strength, Preferably it is 50 weight% or less, More preferably, it is 40 weight% or less, More preferably, it is 30 weight% or less.

From the viewpoint of foam strength and dimensional stability, polyol A/polyol B (weight ratio) is 1.2-3, preferably 1.2-2, more preferably 1.3-2, still more preferably 1.3-1.7.

From the viewpoint of improving foam strength, the content of polyol C in the polyol component is preferably 1% by weight or more, more preferably 2% by weight or more, and even more preferably 4% by weight or more; from the viewpoint of imparting dimensional stability, Preferably it is 25 weight% or less, More preferably, it is 20 weight% or less, More preferably, it is 10 weight% or less.

In addition, polyols other than polyol A, polyol B, and polyol C may be contained in the polyol component as long as the object of the present invention is not hindered.

A polyol component can be contained in a polyol mixture and used. In addition, the term "polyol mixture" refers to a mixture containing a polyol and, if necessary, a foaming agent, a chain extender, a catalyst, and the like.

The content of the polyol component in the polyol mixture is preferably 60% by weight or more, more preferably 70% by weight or more, from the viewpoint of improving foam strength, imparting flexibility, and improving dimensional stability.

Isocyanate prepolymers etc. are mentioned as a typical example of the polyisocyanate component used for manufacturing a polyurethane foam. Since the isocyanate prepolymer is in a liquid state at 15°C or higher and can flow out even at low pressure, it has the advantage that, for example, it can be supplied to polyurethane foam without any problem even at a molding temperature of 40 to 50°C.

The isocyanate prepolymer can be obtained by stirring and reacting a polyol and excess isocyanate monomer by a conventional method.

Specific examples of isocyanate monomers include m-phenylene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isofor Ketone diisocyanate, polymethylene polyphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-bis Isocyanate components such as phenylmethane diisocyanate, 3,3'-dichloro-4,4'-biphenyl diisocyanate, 1,5-naphthalene diisocyanate, and their modified products, such as carbodiimide modified products wait. These substances may be used alone or in combination of two or more. Among these monomers, 4,4'-diphenylmethane diisocyanate and carbodiimide-modified products of 4,4'-diphenylmethane diisocyanate are preferable from the viewpoint of ensuring sufficient foam strength, and more It is preferable to use 4,4'-diphenylmethane diisocyanate alone, or to use 4,4'-diphenylmethane diisocyanate and a carbodiimide-modified body of 4,4'-diphenylmethane diisocyanate in combination.

Among isocyanate prepolymers, from the viewpoint of securing sufficient foam strength, 4,4'-diphenylmethane diisocyanate and carbodiimide-modified 4,4'-diphenylmethane diisocyanate are preferred Isocyanate prepolymers used as raw materials.

In addition, 4,4'-diphenylmethane diisocyanate may be mixed with an isocyanate prepolymer using a carbodiimide modified product of 4,4'-diphenylmethane diisocyanate as a raw material.

When preparing the isocyanate prepolymer, additives may also be added as needed.

As additives, for example, additives used as needed in the preparation of polyester polyol are typified. In order to prevent self-polymerization of isocyanate prepolymers, acid gases such as hydrogen chloride gas and sulfurous acid gas, acetyl chloride, benzoyl chloride, m- Acid chlorides such as phthaloyl chloride, isocyanate self-polymerization inhibitors such as phosphoric acid, phosphoric acid compounds such as monoethyl phosphate and diethyl phosphate, and the like can be used alone or in combination of two or more.

In order not to increase the viscosity and make it difficult to form through a low-pressure foaming machine, the NCO% of the isocyanate prepolymer is preferably 14% or more, more preferably 16% or more; The decrease in measurement accuracy is preferably 23% or less, more preferably 20% or less, even more preferably 18% or less.

The NCO% of the polyisocyanate component is preferably 10 to 25% from the viewpoint of preventing a rise in liquid viscosity and storage stability of the liquid.

Moreover, it is preferable to use a catalyst in the manufacturing method of the polyurethane foam of this invention from a viewpoint of raising a reaction rate. A catalyst may be included in the polyol mixture.

As a catalyst, for example, TEDA [1,4-diazabicyclo-[2.2.2]-octane], N,N,N',N'-tetramethylhexamethylenediamine, N , N, N', N'-tetramethylpropylenediamine, N, N, N', N'-pentamethyldiethylenetriamine, trimethylaminoethylpiperazine, N, N-two Methylcyclohexylamine, N,N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, triethylamine, tributylamine, bis(dimethylaminoalkyl)piperazine, N,N,N',N'-tetramethylethylenediamine, N,N-diethylbenzylamine, bis(N,N-diethylaminoethyl)adipate, N,N,N ', N'-tetramethyl-1,3-butanediamine, N,N-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole, etc., these substances These can be used alone or in combination of two or more. Among these catalysts, tertiary amines are preferable from the viewpoint of increasing the reaction rate.

Moreover, as a catalyst, organometallic compounds, such as dibutyltin dilaurate, stannous oleate, cobalt naphthenate, lead naphthenate, etc. other than an amine catalyst can also be used.

When making polyurethane foam, blowing agents can be used. Blowing agents may be included in the polyol mixture. As the blowing agent, water may be used alone, or water, hydrocarbons, chlorofluorocarbons, or hydrofluorocarbons may be used in combination. In addition, from the viewpoint of avoiding the problem of the destruction of the earth's ozone layer, it is preferable to use water alone as the blowing agent.

When water is used as a blowing agent, generally the water reacts with the polyisocyanate component to form strong hard segments. However, due to the influence of carbon dioxide generated by the reaction of the polyisocyanate component and water, the polyurethane foam is reduced in density. Therefore, the amount of water as a blowing agent is preferably 0.3 to 2 parts by weight, more preferably 0.5 to 1.8 parts by weight, and even more preferably 0.6 to 1.5 parts by weight relative to 100 parts by weight of the total amount of the polyol component.

In the present invention, chain extenders, silicone-based antifoaming agents, pigments, antioxidants, yellowing inhibitors, and the like can be used as additives. These additives may be included in the polyol mixture.

As the chain extender, a compound having a number average molecular weight of 1000 or less and having two or more active hydrogens in the molecule can be used.

Typical examples of chain extenders include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, methylpentanediol, and 1,6-hexanediol. , trimethylolpropane, glycerin, pentaerythritol, diglycerin, glucose, sorbitol and other polyols; ethylenediamine, hexamethylenediamine and other aliphatic polyamines; aromatic polyamines, diethanolamine, triethanolamine, di Alkanolamines such as isopropanolamine, their modified products, and the like can be used alone or in combination of two or more.

Examples of suitable chain extenders include ethylene glycol, diethylene glycol, 1,4-butanediol, pentaerythritol, and modified products thereof having a number average molecular weight of 1,000 or less.

From the viewpoint of improving formability, the mixing ratio of the polyol component and the polyisocyanate component is desirably adjusted so that the isocyanate index is preferably 60-100, more preferably 65-95, and still more preferably 70-90.

As a method for producing polyurethane foam, for example, mixing and stirring a polyol component, a catalyst, a blowing agent, an additive, etc. in advance, and then mixing and stirring the obtained polyol mixture and a polyisocyanate component with a molding machine, and A method of injecting into a molding die to make it foam, etc. More specifically, for example, mixing and stirring a polyol component, a catalyst, a foaming agent, an additive, etc. in a container etc., and adjusting the temperature of the obtained polyol mixture to about 40° C. A foaming machine such as a foaming machine and an automatic mixing type injection foaming machine mixes a polyol mixture and a polyisocyanate component to react and foam them.

From the viewpoint of ensuring sufficient foam strength and dimensional stability, the density of the polyurethane foam thus obtained is 0.1 g/cm ³ or more, preferably 0.1 to 0.70 g/cm ³ , more preferably 0.2 to 0.65 g/cm ³ , More preferably, it is 0.3 to 0.60 g/cm ³ .

In addition, the hardness of the polyurethane foam (measured at 25° C. with an Asker C durometer specified in JIS K7312) is preferably 40 to 80, more preferably 45 to 75, from the viewpoint of foam strength and imparting flexibility.

If the tensile strength (based on the measurement method described in JIS K6301, using a dumbbell No. 2 test piece punched out of a polyurethane foam with a thickness of 10mm and measured at a temperature of 25°C) as an index, sufficient From the viewpoint of mechanical strength and durability, the strength of the polyurethane foam is preferably 2 MPa or more, more preferably 2.2 MPa or more, and still more preferably 2.5 to 10 MPa.

From the viewpoint of absorbing impact energy imparted from the outside, the rebound rate of the polyurethane foam (based on the rebound resilience test specified in JIS K6301, measured at a temperature of 25° C. using a polyurethane foam having a diameter of 32 mm and a thickness of 10 mm) is preferable. It is 35% or less, more preferably 32% or less, still more preferably 30% or less. In addition, when deformed by external force, the spring rate of the polyurethane foam is preferably 10% or more, more preferably 12% or more, and still more preferably 14% or more, from the viewpoint of easy return to the original shape. From these viewpoints, the resiliency of the polyurethane foam is preferably 10 to 35%, more preferably 12 to 32%, and still more preferably 14 to 30%.

The polyurethane foam of the present invention is suitable for shoe soles, as well as cushioning materials used in automobiles and other means of transportation, furniture, bedding, and the like. Moreover, when it is used as a shoe sole, shoe soles of men's shoes, casual shoes, etc. are mentioned as the suitable use. Generally, a shoe sole is composed of parts for soles classified into an outsole for sandals, men's shoes, etc., a midsole for sports shoes, etc., and an insole (sole) mounted inside a shoe. The polyurethane foam of the present invention can be suitably used for these parts for shoe soles, but among them, it is preferably used for outsoles of shoes in terms of excellent foam strength and low resiliency.

The shoe of the present invention includes the sole having the above-mentioned polyurethane foam, and can generally be manufactured by integrating the shoe body (upper leather, etc.) and the sole. The shoe body is the part that wraps the instep, and is not particularly limited by material or shape.

Example

Hereinafter, the mode of the present invention will be further described and disclosed through examples. This embodiment is only an example of the present invention and does not have any limiting meaning.

Examples 1-15 and Comparative Examples 1-5

According to the composition shown in Table 1, a polyol component, a chain extender (ethylene glycol or diethylene glycol), a catalyst (triethylenediamine), a silicone defoamer (manufactured by Dow Coming Toray Co., Ltd., A product name: SH193 or SRX253), a foaming agent (water), and a pigment (manufactured by Nippon Pigment Co., Ltd., product name: NV-7-478) were mixed to prepare a polyol mixture.

As the polyisocyanate component, Kao Corporation's trade name EDDYFOAM B-6106M (NCO%: 16%) was used, and the mixing ratio of the polyol mixture and the polyisocyanate component was adjusted so that the isocyanate index obtained based on the following formula was Values shown in "Index" in Table 1.

[Isocyanate index] = (Amount of isocyanate actually used) ÷ (Amount of isocyanate equivalent to stoichiometric polyol) × 100

Put the polyol mixture and polyisocyanate components into an automatic mixing injection foaming machine (manufactured by Polyurethane Engineering, model: MU-203S, model: 6-018), and mix at a temperature of 35 to 45°C to obtain The mixture is put into a forming mold with a mold temperature of 45-55°C (the inner surface is coated with a silicone release agent), and it is foamed under the following forming conditions to make a polyurethane foam of 10mm×100mm×300mm Formed test piece.

[Molding conditions]

Reactivity: emulsification time 5-15 seconds

Demoulding time: 5.5～6.5 minutes

In addition, the abbreviation of each component means the following meaning.

(1) Polyol component

[Polyol A]

A1: 3-methyl-1,5-pentanediol/adipic acid polycondensate, (number of functional groups: 2, hydroxyl value: 86mgKOH/g)

A2: 2,4-dimethyl-1,5-pentanediol/adipic acid polycondensate (manufactured by Kyowa Hakko Kogyo Co., Ltd., trade name: 2000PA, number of functional groups: 2, hydroxyl value: 56 mgKOH/g)

A3: 2-butyl-2-ethyl-1,3-propanediol/adipic acid polycondensate (manufactured by Kyowa Hakko Kogyo Co., Ltd., trade name: 2000BA, number of functional groups: 2, hydroxyl value: 56 mgKOH/g)

A4: 3-methyl-1,5-pentanediol/adipic acid/terephthalic acid polycondensate (number of functional groups: 2, hydroxyl value: 86mgKOH/g, terephthalic acid/adipic acid (molar ratio) :0.2)

A5: 3-methyl-1,5-pentanediol/adipic acid/terephthalic acid polycondensate (number of functional groups: 2, hydroxyl value: 86mgKOH/g, terephthalic acid/adipic acid (molar ratio) : 0.5)

A6: 3-methyl-1,5-pentanediol/adipic acid/terephthalic acid polycondensate (number of functional groups: 2, hydroxyl value: 86mgKOH/g, terephthalic acid/adipic acid (molar ratio) : 1.0)

A7: 3-methyl-1,5-pentanediol/adipic acid/terephthalic acid polycondensate (manufactured by Kuraray Co., Ltd., trade name: P-2011, number of functional groups: 2, hydroxyl value: 56 mgKOH/g, Terephthalic acid/adipic acid (molar ratio): 1.0)

[Polyol B]

B1: Polyglycerol (manufactured by Asahi Glass Urethane Co., Ltd., trade name: EXCENOL 820, number of functional groups: 3, hydroxyl value: 34 mgKOH/g)

B2: Polyglycerol (manufactured by Asahi Glass Urethane Co., Ltd., trade name: EXCENOL 845, number of functional groups: 3, hydroxyl value: 28 mgKOH/g)

B3: Polyglycerol (manufactured by Asahi Glass Urethane Co., Ltd., trade name: EXCENOL 850, number of functional groups: 3, hydroxyl value: 24 mgKOH/g)

[Polyol C]

C1: Polyoxypropylene sorbitol ether (Sorbitol propylene oxide adduct, manufactured by Sanyo Chemical Industry Co., Ltd., trade name: SUNNIX SP-750, number of functional groups: 6, hydroxyl value: 480 mgKOH/g)

[other polyols]

D1: Pentaerythritol PO adduct (manufactured by Sanyo Chemical Industry Co., Ltd., brand name: SUNNIX HD-402, number of functional groups: 4, hydroxyl value: 405 mgKOH/g)

D2: Polypropylene glycol (manufactured by Asahi Glass Urethane Co., Ltd., trade name: PREMINOL 5005, number of functional groups: 2, hydroxyl value: 28 mgKOH/g)

(2) Defoamer

Antifoaming agent 1: Dow Corning Toray Co., Ltd., brand name: SH-193

Antifoaming agent 2: Dow Corning Toray Co., Ltd., brand name: SRX-253

In addition, as the polyisocyanate component, Kao Corporation trade name EDDYFOAM B-6106M (NCO%: 16.0%, the isocyanate used for the isocyanate prepolymer is 4,4'-diphenylmethane diisocyanate) was used.

[Table 1]

Example 1 Comparative example 1 Example comparative example Example Comparative Example 5 2 3 4 5 6 2 3 4 7 8 9 10 11 12 13 14 15 Composition/weight part of polyol mixture polyol component A1 62.5 50 50 50 20 40 60 60 A2 50 A3 50 A4 60 A5 60 A6 60 A7 60 60 60 60 B1 37.5 37.5 30 30 30 30 48 36 40 twenty four twenty four twenty four twenty four twenty four 40 32 twenty four 30 B2 30 B3 30 C1 16 16 16 16 16 8 16 D1 20 20 20 20 20 20 32 twenty four 20 D2 62.5 50 50 ethylene glycol 7.2 7.2 72 7.2 7.2 7.2 7.2 7.2 7.2 7.2 11.9 11.9 11.9 12 11.9 11.9 6.5 6.5 6.5 8.4 Diethylene glycol 1.2 1.2 1.2 catalyst 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.5 0.5 0.5 0.6 Defoamer 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Defoamer 2 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 water 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.9 0.9 0.9 0.9 0.9 0.9 0.8 0.8 0.8 0.9 pigment 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 A/B 1.7 0 1.7 1.7 1.7 1.7 1.7 0 0.4 1.1 1.5 2.5 2.5 2.5 2.5 2.5 1.5 1.9 2.5 0 index 95 92 80 80 80 82 81 78 73 74 93 81 83 83 83 83 89 80 74 77

Note: A/B means the weight ratio of polyol A/polyol B

Next, the physical properties of the prepared test pieces were studied in accordance with the methods of Test Examples 1 to 4 below. The results are shown in Table 2.

[Test Example 1] (Hardness)

The hardness of the surface of the test piece was measured at 25°C with an Asker C hardness tester.

[Test example 2] (density)

The weight of the test piece (100 mm x 300 mm x 10 mm) was measured and divided by the volume of 300 cm ³ for measurement.

[Test Example 3] (tensile strength and elongation)

The measurement was carried out in accordance with JIS K6251 using a No. 2 dumbbell-shaped test piece punched out from the test piece.

[Test Example 4] (resilience rate)

The measurement was performed in accordance with JIS K6255 using a test piece punched out from the test piece with a diameter of 32 mm (thickness: 10 mm).

[Table 2]

Example 1 Comparative example 1 Example comparative example Example Comparative Example 5 2 3 4 5 6 2 3 4 7 8 9 10 11 12 13 14 15 physical properties Hardness (Asker C) 62 64 60 59 58 61 61 55 55 55 68 68 68 68 70 70 50 53 56 55 Density (g/cm ³ ) 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 Tensile strength (MPa) 3.60 2.99 3.44 3.25 3.35 2.86 3.09 2.72 2.36 2.50 2.99 2.66 2.75 3.09 3.25 3.46 2.48 2.71 2.79 2.09 Elongation(%) 500 550 440 470 490 300 340 450 410 470 330 350 330 320 250 350 320 360 410 380 Resilience (%) 35 45 19 17 18 11 14 25 18 twenty two twenty two 15 14 12 10 16 15 11 7 twenty one

[Test Example 5] (Compatibility)

80 g of a composition having the ratios of terephthalic acid/adipic acid (molar ratio) and hydroxyl value shown in Table 3 was added to a screw jar and mixed with a pen mixer for 1 minute (OHV) 3-methyl-1,5-pentanediol/adipic acid/terephthalic acid condensation polymer 60 parts by weight, polyglycerol (manufactured by Asahi Glass Urethane Co., Ltd., trade name EXCENOL845, number of functional groups: 3 , hydroxyl value: 28mgKOH/g) 36 parts by weight, polyoxypropylene sorbitol ether (sorbitol propylene oxide adduct, manufactured by Sanyo Chemical Industry Co., Ltd., trade name: SUNNIX SP-750, number of functional groups: 6, hydroxyl value : 480mgKOH/g) 4 parts by weight and 8 parts by weight of ethylene glycol.

The compatibility of the mixture was observed with the naked eye (25°C, after standing for 3 days). If it was transparent, it was rated as ◎; if it was cloudy, it was rated as ○; if it was layered, it was rated as △. The results are shown in Table 3.

[table 3]

3-Methyl-1,5-pentanediol/adipic acid/terephthalic acid polycondensate Compatibility (mixed state caused by standing at 25°C for 3 days) Terephthalic acid/adipic acid (molar ratio) OHV(mgKOH/g) 2-1 0.14 75 ◎ 2-2 0.20 86 ◎ 2-3 0.17 75 ◎ 2-4 0.14 67 ○ 2-5 0.25 71 ◎ 2-6 0.00 86 ◎ 2-7 0.00 71 ◎ 2-8 0.21 65 ○ 2-9 0.34 84 ○ 2-10 0.41 77 ○ 2-11 0.19 65 ○ 2-12 0.33 70 ○ 2-13 1.00 56 △ 2-14 1.00 86 △ 2-15 0.00 56 △ 2-16 0.50 86 ○ 2-17 0.60 60 ○

Examples 16-17

According to the composition shown in Table 4, a polyol component, a chain extender (ethylene glycol), a catalyst (triethylenediamine), an antifoaming agent, a foaming agent (water), and a pigment (manufactured by Nippon Pigment Co., Ltd. , Trade name: NV-7-478) is mixed, is prepared into polyol mixture. In addition, the polyol mixture in Example 16 was the same as 2-1 shown in Table 3 used in Test Example 5. In addition, although the polyol mixture shown in Table 4 contains a catalyst, an antifoaming agent, a foaming agent, and a pigment in addition to the polyol component, these components are generally small in amount, and it is considered that the compatibility with the polyol component is almost No effect. Therefore, it is presumed that the polyol mixture in Example 17 has good miscibility when prepared in the same manner as in Example 16, and that it has good compatibility when left to stand at 25° C. for 3 days.

As the polyisocyanate component, Kao Corporation trade name EDDYFOAM B-6106M (NCO%: 16%) was used, and the mixing ratio of the polyol mixture and the polyisocyanate component was adjusted so that the isocyanate index obtained based on the above formula was Values shown in "Index" in Table 4.

The polyol mixture and the polyisocyanate component were mixed and molded under the same conditions as above to prepare a 10 mm×100 mm×300 mm polyurethane foam test piece.

In addition, the abbreviation of each component means the following meaning.

(1) Polyol component

Polyol A: 3-methyl-1,5-pentanediol/adipic acid/terephthalic acid polycondensate (number of functional groups: 2, hydroxyl value: 75mgKOH/g, terephthalic acid/adipic acid (mol Ratio): 0.14)

Polyol B: Polyglycerol (manufactured by Asahi Glass Urethane Co., Ltd., trade name EXCENOL 845, number of functional groups: 3, hydroxyl value: 28 mgKOH/g)

Polyol C: polyoxypropylene sorbitol ether (sorbitol propylene oxide adduct, manufactured by Sanyo Chemical Industry Co., Ltd., trade name: SUNNIX SP-750, number of functional groups: 6, hydroxyl value: 480 mgKOH/g)

(2) Defoamer

Antifoaming agent: Dow Corning Toray Co., Ltd., trade name: SH-193

In addition, as the polyisocyanate component, Kao Corporation trade name EDDYFOAMB-6106M (NCO%: 16.0%, the isocyanate used for the isocyanate prepolymer is 4,4'-diphenylmethane diisocyanate) was used.

Next, the physical properties of the produced test pieces were studied in accordance with the methods of Test Examples 1 to 4 described above. The results are shown in Table 4.

[Table 4]

Example 16 17 Mixing composition (parts by weight) of polyol mixture Polyol A 60 55 B 36 41 C 4 4 ethylene glycol 8 8 catalyst 0.7 0.7 Defoamer 0.1 0.1 water 0.6 0.6 pigment 4.0 4.0 index 88 88 physical properties hardness Asker C 56 55 density g/ ^cm3 0.40 0.40 Tensile Strength MPa 3.38 3.4 Elongation % 390 420 rebound rate % 14 15 A/B 1.67 1.34

Note: A/B means the weight ratio of polyol A/polyol B.

As can be seen from the results shown in Table 2, comparing Example 1 and Comparative Example 1, in Example 1, since polyol A and polyol B are used in combination, it is possible to improve the tensile strength of polyurethane foam. At the same time reduce the rebound rate. In addition, the polyurethane foams obtained from Examples 2 to 6 having the same density were compared with Comparative Examples 2 to 4, and the polyurethane foams obtained from Examples 7 to 15 were compared with Comparative Example 5. From the above comparison results, it can be seen that , the polyurethane foams obtained from the respective examples were all excellent in tensile strength, and all had low rebound rates. Moreover, from the result of Table 3, it turns out that the compatibility of the polyol component whose aromatic carboxylic acid/aliphatic carboxylic acid is 0-0.25 and a hydroxyl value is 70-90 mgKOH/g is good. From the results in Table 4, it can be seen that the polyurethane foam using the polyol component with good compatibility has the same degree of tensile strength and low rebound rate as the polyurethane foams of Examples 7 to 15 having the same density. Invention, polyurethane foam with high foam strength and low resilience can be obtained.

Example 18

The raw materials of Example 16 were used to manufacture shoe soles.

Coating 0.002g/ ^cm release agent (manufactured by Kao Corporation, trade name: PURAPOWER-2060) on the inner surface of the sole forming mold with the inner surface shape of the sole of men's shoes, and adjusting the temperature to 50 ± 1 ℃. Next, the polyol mixture having the same composition as in Example 16 was mixed with the polyisocyanate component so that the isocyanate index was 88, and the obtained mixture was injected into a molding machine for polyurethane shoe soles (manufactured by Polyurethane Engineering Co., Ltd., model: MU-203S) , the first time was discarded, and then injected into the above-mentioned forming mold for the second time, and the film was released after 6 minutes, so as to obtain the sole formed by polyurethane foam. The obtained shoe sole had no problem as a shoe sole in terms of appearance, strength and resiliency.

The polyurethane foam obtained by the production method of the present invention is suitably used, for example, as shoe soles, and can also be used as cushioning materials used in automobiles and other vehicles, furniture, bedding, and the like.

In the present invention as described above, it is obvious that there are a plurality of inventions having a single scope. As long as such diversity does not deviate from the spirit and scope of the present invention, all changes that are obvious to those skilled in the art are included in the technical scope of the appended claims.

Claims (17)

1. the manufacture method of a polyurethane foam, the density of this polyurethane foam is 0.1g/cm ³More than, described manufacture method comprises the step that polyhydroxy reactant and polymeric polyisocyanate composition are reacted; Described polyhydroxy reactant comprises:

Polyvalent alcohol A: it is by the polyhydroxy-alcohol composition that contains the polyhydroxy-alcohol with side chain and the polycondensation of polyprotonic acid composition and the hydroxyl value that forms is the polyester polyol of 45～115mgKOH/g; With

Polyvalent alcohol B, its be functional group's number be 3 and hydroxyl value be the polyether glycol of 15～40mgKOH/g;

Wherein the weight ratio of polyvalent alcohol A and polyvalent alcohol B is 1.2～3.

2. manufacture method according to claim 1, wherein, the polyhydroxy-alcohol with side chain that uses among the polyvalent alcohol A is to have the polyhydroxy-alcohol that carbonatoms is 1～4 side chain.

3. manufacture method according to claim 1, wherein, the polyprotonic acid composition that uses among the polyvalent alcohol A is the polyprotonic acid composition that contains aromatic carboxylic acid.

4. manufacture method according to claim 1, wherein, the polyprotonic acid composition that uses among the polyvalent alcohol A contains aromatic carboxylic acid and/or aliphatic carboxylic acid, and the mol ratio of aromatic carboxylic acid and aliphatic carboxylic acid is 0～0.25, and the hydroxyl value of polyvalent alcohol A is 70～90mgKOH/g.

5. manufacture method according to claim 1, wherein, polyvalent alcohol B is to use glycerine to carry out addition polymerization as polymerization starter and oxyalkylene and the polyether glycol that forms.

6. manufacture method according to claim 1, wherein, polyhydroxy reactant also contain functional group's number be 6 and hydroxyl value be the polyether glycol of 380～550mgKOH/g.

7. manufacture method according to claim 1, wherein, the polymeric polyisocyanate composition is the isocyanic ester performed polymer.

8. manufacture method according to claim 1, wherein, the polymeric polyisocyanate composition is with 4,4 '-diphenylmethanediisocyanate or 4, the carbodiimide modification body and function of 4 '-diphenylmethanediisocyanate is made raw material and the isocyanic ester performed polymer that makes.

9. polyurethane foam that is obtained by the described manufacture method of claim 1, its density is 0.1～0.70g/cm ³, tensile strength is more than the 2MPa.

10. polyurethane foam according to claim 9, its rebound degree are 10～35%.

11. polyurethane foam according to claim 9, its hardness are 40～80.

12. sole with the described polyurethane foam of claim 9.

13. sole with the described polyurethane foam of claim 10.

14. sole with the described polyurethane foam of claim 11.

15. footwear with the described sole of claim 12.

16. footwear with the described sole of claim 13.

17. footwear with the described sole of claim 14.