JP2021055030A - Polyurethane resin composition, molded body and shoe sole using the same - Google Patents

Abstract

To provide a urethane resin composition which is less likely to cause peeling of an outsole and a midsole even when a shoe sole is manufactured under high temperature and high humidity, and to provide a molded article and a shoe sole using the composition.SOLUTION: A polyurethane resin molded article of the present invention comprises a polyurethane resin, a quaternary ammonium salt (E1) and an ionic liquid (E2). The quaternary ammonium salt (E1) comprises, as an anionic component, one or more kinds selected from the group consisting of a sulfate ester anion and a sulfonate anion. The ionic liquid (E2) comprises, as a cationic component, one or more kinds selected from the group consisting of an imidazolium cation having an alkyl group having 3 or more carbon atoms, a pyridinium cation having an alkyl group having 3 or more carbon atoms, a pyrrolidinium cation having an alkyl group having 3 or more carbon atoms, a piperidinium cation having an alkyl group having 3 or more carbon atoms, and a quaternary ammonium cation having an alkyl group having 3 or more carbon atoms.SELECTED DRAWING: None

Description

The present invention relates to a polyurethane resin composition, a molded product using the polyurethane resin composition, and a sole.

Antistatic properties (antistatic properties) for footwear and clothing worn on the human body as a preventive measure against electrostatic disasters in places where dangerous materials are handled, such as complexes, chemical factories, work sites, hazardous materials handling areas, and experimental facilities. Also known as) is being actively considered. As footwear and clothing with antistatic properties, for example, soles for antistatic safety shoes, work shoes, clean room shoes, medical shoes, safety gloves, safety work clothes, safety caps, etc. have been proposed. There is.

As a method of imparting antistatic property, a method of applying or spraying an antistatic agent such as a conductive substance or an ionic substance on the surface, a method of internally adding the antistatic substance, and the like are known. For example, Patent Document 1 describes an antistatic agent composition containing an ionic antistatic compound and a polar organic solvent. Patent Document 2 describes a polyurethane containing quaternary ammonium alkylsulfate and trifluoromethanesulfonate. Patent Document 3 describes a polyurethane resin molded product using an antistatic aid containing an antistatic agent and a lactone-based monomer. Patent Document 4 describes a urethane resin composition containing an alkyl-substituted quaternary ammonium salt and an alkyl-substituted imidazolium salt as an antistatic agent.

Japanese Unexamined Patent Publication No. 2001-329253 Japanese Unexamined Patent Publication No. 2000-103958 Japanese Unexamined Patent Publication No. 2005-060682 Japanese Unexamined Patent Publication No. 2013-053265

However, as a result of studies by the present inventors, it has been clarified that the following problems occur when a shoe sole is manufactured using a conventionally known resin composition. That is, the soles of various shoes are divided into an outsole on the sole (the surface that comes into contact with the ground), a midsole and an insole on the inside (the inner surface of the shoe), and are manufactured by molding these. It has been clarified that when a shoe sole is manufactured using a conventionally known resin composition, the outsole and the midsole are likely to peel off under high temperature and high humidity.

The present invention has been made in view of the above circumstances, and is a urethane resin composition capable of making it difficult for the outsole and the midsole to peel off even when the sole is manufactured under high temperature and high humidity. It is an object of the present invention to provide a molded product and a sole of a shoe using the above.

The urethane resin molded product of the present invention contains a polyurethane resin, a quaternary ammonium salt (E1), and an ionic liquid (E2), and the quaternary ammonium salt (E1) contains a sulfate ester anion as an anion component. The ionic liquid (E2) contains an imidazolium cation having an alkyl group having 3 or more carbon atoms as a cation component, and an imidazolium cation having 3 or more carbon atoms. It contains one or more selected from the group consisting of a pyrrolidinium cation having an alkyl group and a quaternary ammonium cation having an alkyl group having 3 or more carbon atoms.

According to the present invention, a urethane resin composition capable of preventing the outsole and the midsole from peeling off even when the sole is manufactured under high temperature and high humidity, and a molded product and the sole using the urethane resin composition are provided. Can be done.

The polyurethane resin molded product of the present invention contains a polyurethane resin, a quaternary ammonium salt (E1), and an ionic liquid (E2). By using the quaternary ammonium salt (E1) in combination with the specific ionic liquid (E2), the adhesiveness between the outsole and the midsole can be enhanced even when manufactured under high temperature and high humidity.

The quaternary ammonium salt (E1) contains at least one selected from the group consisting of a sulfate ester anion and a sulfonic acid anion as an anion component, and preferably contains a sulfate ester anion. Examples of the sulfate ester anion include carbon atoms such as methyl sulfate ester anion, ethyl sulfate ester anion, propyl sulfate ester anion, butyl sulfate ester anion, pentyl sulfate ester anion, hexyl sulfate ester anion, heptyl sulfate ester anion, and octyl sulfate anion. Examples thereof include an alkyl sulfate anion having an alkyl group having a number of 1 to 10 (preferably 1 to 5 carbon atoms). Examples of the sulfonic acid anion include carbon atoms such as methane sulfonic acid anion, ethane sulfonic acid anion, propane sulfonic acid anion, butane sulfonic acid anion, pentan sulfonic acid anion, hexane sulfonic acid anion, heptane sulfonic acid anion, and octane sulfonic acid anion. Examples thereof include an alkane sulfonic acid anion having an alkyl group having a number of 1 to 10 (preferably 1 to 5 carbon atoms).

The quaternary ammonium salt (E1) contains a quaternary ammonium cation as a cation component, and the quaternary ammonium cation is preferably a cation represented by the following formula (1). ..

[In the formula (1), R ^{1 to} R ⁴ independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms. ]

The ^{aliphatic hydrocarbon groups represented by R 1} , R ² , R ³ , and R ⁴ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, and nonyl group. Linear or branched alkyl groups such as decyl group, undecyl group, dodecyl group, tridecyl group, butadecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, icosyl group; ethenyl group, propenyl group , Butenyl group, pentenyl group, hexenyl group, heptenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, butadesenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadesenyl group, icosenyl group, etc. Examples thereof include an alkenyl group (hereinafter, also referred to as “alkenyl group corresponding to the alkyl group”), and an alkyl group is preferable, and a linear alkyl group is more preferable.

The ^{number of carbon atoms of the aliphatic hydrocarbon group represented by R 1} , R ² , R ³ , and R ⁴ is preferably 1 to 15, and more preferably 1 to 12. The total number of carbon atoms of the aliphatic hydrocarbon groups represented by R ¹ , R ² , R ³ , and R ⁴ is preferably 4 to 40, more preferably 6 to 30, and even more preferably 10 to 20. is there. At ^{least one of R 1} , R ² , R ³ and R ⁴ is preferably an aliphatic hydrocarbon group having 3 to 20 carbon atoms (preferably 4 to 15).

The quaternary ammonium salt (E1) is preferably a combination of a sulfate ester anion and a quaternary ammonium cation represented by the formula (1).

The quaternary ammonium salt (E1) and the ionic liquid (E2) described later are both composed of a cationic component and an anionic component, but the quaternary ammonium salt is a molecular solvent. Ionic liquids differ in that they are soluble in water and exhibit ionic conductivity only through a solvent, whereas ionic liquids exhibit ionic conductivity without the addition of a molecular solvent.

The content of the quaternary ammonium salt (E1) is preferably 0.5 parts by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more in the polyurethane resin molded product, and is preferable. Is 15% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass or less.

The ionic liquid (E2) represents a salt having a melting point of 100 ° C. or lower under atmospheric pressure (1013 hPa), and is preferably a liquid at normal temperature (25 ° C.) under atmospheric pressure (1013 hPa). The ionic liquid (E2) has an imidazolium cation having an alkyl group having 3 or more carbon atoms, a pyridinium cation having an alkyl group having 3 or more carbon atoms, and a pyroli having an alkyl group having 3 or more carbon atoms as cation components. It contains one or more selected from the group consisting of a dinium cation, a piperidinium cation having an alkyl group having 3 or more carbon atoms, and a quaternary ammonium cation having an alkyl group having 3 or more carbon atoms. However, the ionic liquid (E2) is different from the quaternary ammonium salt (E1).

Imidazolium cation having an alkyl group with 3 or more carbon atoms, pyridinium cation having an alkyl group with 3 or more carbon atoms, pyroridinium cation having an alkyl group with 3 or more carbon atoms, alkyl group having 3 or more carbon atoms By using at least one of a pyridinium cation having a temperature and a quaternary ammonium cation having an alkyl group having 3 or more carbon atoms, the electrostatic performance is maintained even when the sole is manufactured under high temperature and high humidity. At the same time, the adhesiveness between the outsole and the midsole can be improved.

The imidazolium cation may be any cation having an alkyl group having 3 or more carbon atoms, and for example, a cation represented by the following formula (2) is preferable. The cation represented by the formula (2) also includes a tautomer thereof and a cation represented by a structural formula having a resonance relationship with the formula (2).

[In equation (2),
R ⁵ and R ⁷ each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
R ⁶ , R ^{8 to} R ⁹ independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
However, ^{at least one of R 5 to} R ⁹ represents an alkyl group having 3 or more carbon atoms. ]

The aliphatic hydrocarbon group represented by ^{R 5 to} R ⁹ is a group similar to the group exemplified as the aliphatic hydrocarbon group represented by ^{R 1, that is, a linear or branched alkyl group, described above.} Examples thereof include an alkenyl group corresponding to the alkyl group, and an alkyl group is preferable, and a linear alkyl group is more preferable.

The ^{number of carbon atoms of the aliphatic hydrocarbon group represented by R 5 to} R ⁹ is preferably 1 to 15, and more preferably 1 to 12. The total number of carbon atoms of the aliphatic hydrocarbon groups represented by R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is preferably 2 to 20, more preferably 2 to 15, and even more preferably 4. It is 10. At ^{least one of R 5} , R ⁶ , R ⁷ , R ⁸ and R ⁹ is preferably an aliphatic hydrocarbon group having 3 to 20 carbon atoms (preferably 4 to 15), and R ⁶ and R ⁹ It is preferable that at least one of the above is an aliphatic hydrocarbon group having 3 to 20 carbon atoms (preferably 4 to 15).

R ^{8 to} R ⁹ are preferably hydrogen atoms. Further, R ⁵ and R ⁷ are preferably aliphatic hydrocarbon groups.

At ^{least one of R 5 to} R ⁹ is an alkyl group having 3 or more carbon atoms, preferably ^{at least one of R 5 to} R ⁷ is an alkyl group having 3 or more carbon atoms, and more preferably R ⁵ or more. At ^{least one of R 7} is an alkyl group having 3 or more carbon atoms.

As the imidazolium cation, 1-butyl-3-methylimidazolium is particularly preferable.

The pyridinium cation may have an alkyl group having 3 or more carbon atoms, and is preferably a cation represented by the following formula (3), for example. The cation represented by the formula (3) also includes a tautomer thereof and a cation represented by a structural formula having a resonance relationship with the formula (3).

[In equation (3),
R ¹⁰ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
R ^{11 to} R ¹⁵ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. ]

The aliphatic hydrocarbon group represented by ^{R 10 to} R ¹⁵ is a group similar to the group exemplified as the aliphatic hydrocarbon group represented by ^{R 1, that is, a linear or branched alkyl group, described above.} Examples thereof include an alkenyl group corresponding to the alkyl group, and an alkyl group is preferable, and a linear alkyl group is more preferable.

The ^{number of carbon atoms of the aliphatic hydrocarbon group represented by R 10} is preferably 1 to 12, more preferably 1 to 10. The ^{number of carbon atoms of the aliphatic hydrocarbon group represented by R 11 to} R ¹⁵ is preferably 1 to 5, and more preferably 1 to 3.

The pyridinium cation may have one or two or more substituents, and preferably has at least one or two substituents substituted with a nitrogen atom, and is substituted with a nitrogen atom. It preferably has at least two substituents. Examples of the substituent include an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Examples of the aliphatic hydrocarbon group include an alkyl group and an alkenyl group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 8, and more preferably 1 to 6.

As the pyridinium cation, 1-octyl-4-methylpyridinium cation is particularly preferable.

The pyrrolidinium cation may have an alkyl group having 3 or more carbon atoms, and is preferably a cation represented by the following formula (4), for example. The cation represented by the above formula (4) also includes its tautomer.

[In equation (4),
R ^{16 to} R ¹⁷ each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
R ^{18 to} R ²⁵ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
However, ^{at least one of R 16 to} R ²⁵ represents an alkyl group having 3 or more carbon atoms.

The aliphatic hydrocarbon group represented by ^{R 16 to} R ²⁵ is a group similar to the group exemplified as the aliphatic hydrocarbon group represented by ^{R 1, that is, a linear or branched alkyl group, described above.} Examples thereof include an alkenyl group corresponding to the alkyl group, and an alkyl group is preferable, and a linear alkyl group is more preferable.

The ^{number of carbon atoms of the aliphatic hydrocarbon group represented by R 16 to} R ²⁵ is preferably 1 to 12, more preferably 1 to 10. R ^{16 to} R ¹⁷ are preferably aliphatic hydrocarbon groups. Further, R ^{18 to} R ²⁵ are preferably hydrogen atoms.

At ^{least one of R 16 to} R ²⁵ is an alkyl group having 3 or more carbon atoms, and preferably ^{at least one of R 16 to} R ¹⁷ is an alkyl group having 3 or more carbon atoms.

As the pyrrolidinium cation, 1-butyl-1-methylpyrrolidinium cation is particularly preferable.

The piperidinium cation may be any one having an alkyl group having 3 or more carbon atoms, and for example, a cation represented by the following formula (5) is preferable. The cation represented by the above formula (5) also includes its tautomer.

[In equation (5),
R ^{26 to} R ²⁷ each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
R ^{28 to} R ³⁷ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
However, ^{at least one of R 26 to} R ³⁷ represents an alkyl group having 3 or more carbon atoms. ]

The aliphatic hydrocarbon group represented by ^{R 26 to} R ³⁷ is a group similar to the group exemplified as the aliphatic hydrocarbon group represented by ^{R 1, that is, a linear or branched alkyl group, described above.} Examples thereof include an alkenyl group corresponding to the alkyl group, and an alkyl group is preferable, and a linear alkyl group is more preferable.

The ^{number of carbon atoms of the aliphatic hydrocarbon group represented by R 26 to} R ³⁷ is preferably 1 to 15, and more preferably 1 to 12. R ^{26 to} R ²⁷ are preferably aliphatic hydrocarbon groups. Further, R ^{28 to} R ³⁷ are preferably hydrogen atoms.

At ^{least one of R 26 to} R ³⁷ is an alkyl group having 3 or more carbon atoms, and preferably ^{at least one of R 26 to} R ²⁷ is an alkyl group having 3 or more carbon atoms.

As the piperidinium cation, 1-butyl-1-methylpiperidinium cation is preferable.

The quaternary ammonium cation may have an alkyl group having 3 or more carbon atoms, and for example, a cation represented by the following formula (6) is preferable. The cation represented by the above formula (6) also includes its tautomer.

[In formula (6), R ^{38 to} R ⁴¹ each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
However, ^{at least one of R 38 to} R ⁴¹ represents an alkyl group having 3 or more carbon atoms. ]

The aliphatic hydrocarbon group represented by ^{R 38 to} R ⁴¹ is a group similar to the group exemplified as the aliphatic hydrocarbon group represented by ^{R 1, that is, a linear or branched alkyl group, described above.} Examples thereof include an alkenyl group corresponding to the alkyl group, and an alkyl group is preferable, and a linear alkyl group is more preferable.

The ^{number of carbon atoms of the aliphatic hydrocarbon group represented by R 38 to} R ⁴¹ is preferably 1 to 15, and more preferably 1 to 12. The total number of carbon atoms of the aliphatic hydrocarbon groups represented by R ^{38 to} R ⁴¹ is preferably 4 to 50, more preferably 4 to 40, and even more preferably 4 to 40. At least one of R ³⁸ to R ⁴¹ (preferably two, more preferably three) is an alkyl group having 3 or more carbon atoms, preferably at least two 3 carbon atoms R ³⁸ to R ⁴¹ The above alkyl groups, more preferably ^{at least three of R 38 to} R ⁴¹ are alkyl groups having 3 or more carbon atoms.

As the quaternary ammonium cation, butyltrimethylammonium cation and trioctylmethylammonium cation are particularly preferable.

The imidazolium cation having an alkyl group having 3 or more carbon atoms, a pyridinium cation having an alkyl group having 3 or more carbon atoms, a pyroridinium cation having an alkyl group having 3 or more carbon atoms, and an alkyl having 3 or more carbon atoms. The total content of the piperidinium cation having a group and the quaternary ammonium cation having an alkyl group having 3 or more carbon atoms is preferably 70% by mass or more, more preferably 80% by mass or more, among the cation components. More preferably, it is 90% by mass or more, and preferably 100% by mass or less.

The ionic liquid (E2) is composed of a bis (trifluoromethanesulfonyl) imide anion, a bis (pentafluoroethanesulfonyl) imide anion, a tris (trifluoromethanesulfonyl) methide anion, a trifluoromethanesulfonate anion and a tetrafluorobolate anion as anion components. It preferably contains one or more selected from the group, and preferably contains one or more selected from the group consisting of bis (trifluoromethanesulfonyl) imide anion, trifluoromethanesulfonate anion and tetrafluoroborate anion. By combining the cation component and the anion component, it is possible to prevent the outsole and the midsole from peeling off even when the sole is manufactured under high temperature and high humidity while maintaining the electrostatic performance.

The total content of the bis (trifluoromethanesulfonyl) imide anion, the tris (trifluoromethanesulfonyl) methide anion, the trifluoromethanesulfonate anion and the tetrafluoroborate anion in the anion component is preferably 70% by mass or more, more preferably 80% by mass. % Or more, more preferably 90% by mass or more, and preferably 100% by mass or less.

The ionic liquid (E2) may be an arbitrary combination of the cation component and the anion component, for example, an imidazolium cation, a pyrrolidinium cation or a quaternary ammonium cation, and a bis (trifluoromethanesulfonyl). ) Combination with an imide anion; a combination of an imidazolium cation with a bis (trifluoromethanesulfonyl) imide anion, a tris (trifluoromethanesulfonyl) methide anion, a trifluoromethanesulfonate anion or a tetrafluorobolate anion is preferred.

The content of the ionic liquid (E2) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 10% by mass in the polyurethane resin molded product. % Or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.

The ratio (E1 / E2) of the content of the quaternary ammonium salt (E1) to the ionic liquid (E2) is preferably 2 or more, more preferably 4 or more, and preferably 30 or less on a mass basis. , More preferably 20 or less, still more preferably 15 or less.

The polyurethane resin molded product may further contain an antistatic agent (E3). Examples of the antistatic agent (E3) include cationic antistatic compounds such as methanesulfonic acid ester derivative and p-toluenesulfonic acid ester derivative; bis (trifluoromethanesulfonyl) imide metal salt, and tris (trifluoromethanesulfonyl) methane metal. Organic metal salts such as salts, sulfonic acid metal salts, alkane sulfonic acid metal salts, perfluoroalkane sulfonic acid metal salts (trifluoromethane sulfonic acid metal salts, etc.), benzene sulfonic acid metal salts, or alkylbenzene sulfonic acid metal salts. Examples include electric compounds.

The polyurethane resin molded product may further contain an antistatic aid (E4). Examples of the antistatic aid (E4) include cyclic ketones, sorbitan fatty acid esters, and lactone-based monomers. Examples of the cyclic ketones include cyclopentanone, cyclohexanone, cycloheptanone and derivatives thereof, and examples of sorbitan fatty acid esters include sorbitan sesquioleate, sorbitan monooleate, sorbitan monostearate, and sorbitan monolaurate. Rate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, etc., or as lactone-based monomers, for example, β-propiolactone, γ-butyrolactone, δ- Examples thereof include lactone monomers such as valerolactone, ε-caprolactone and γ-crotonolactone.

As the urethane resin, one kind or two or more kinds can be used, and examples thereof include a polyether urethane resin, a polyester urethane resin, and a polycarbonate urethane resin. In the present invention, for example, the polyester-based urethane resin represents a urethane resin having a unit derived from polyester in the molecular chain.

The polyurethane resin molded product is preferably a polyurethane resin foam molded product.

The density of the polyurethane resin molded product is preferably 0.2 g / cm ³ or more, more preferably 0.3 g / cm ³ or more, preferably 1.8 g / cm ³ or less, and more preferably 1.5 g / cm. ^{It is 3} or less, more preferably 1.3 g / cm ³ or less. The density of the polyurethane resin molded product may differ depending on the application. For example, when the polyurethane resin molded product is used for an outsole, the density is preferably 0.4 g / cm ³ or more, more preferably 0. 6 g / cm ³ or more, more preferably 0.7 g / cm ³ or more, preferably 1.8 g / cm ³ or less, more preferably 1.5 g / cm ³ or less, still more preferably 1.3 g / cm ³ or less. Is. When the polyurethane resin molded product is used for the midsole, its density is preferably 0.2 g / cm ³ or more, more preferably 0.3 g / cm ³ or more, and preferably 1.2 g / cm ³ or less. , More preferably 1 g / cm ³ or less, still more preferably 0.8 g / cm ³ or less.

The hardness of the polyurethane resin molded product is preferably 50 or more, more preferably 60 or more when measured by a spring hardness test (type C) in accordance with Japanese Industrial Standards JIS K 7312-1996 (hardness test). It is preferably 100 or less, more preferably 80 or less.

The polyurethane resin molded body includes automobile interior materials, shoe soles (safety shoes, work shoes, clean room shoes, especially antistatic shoe soles), safety gloves, safety work clothes, safety caps, rollers for copying machines, and cushioning materials. , Sealing material, packing (particularly packing for electronic materials), hose, sheet, cushioning agent, packaging member, etc., and particularly preferably used for shoe soles.

The polyurethane resin molded body is a polyurethane resin composition containing a main agent (i) and a curing agent (ii), and the main agent (i) contains a urethane prepolymer (A) having an isocyanate group. A polyurethane resin composition in which the curing agent (ii) contains a compound (B) having two or more functional groups capable of reacting with an isocyanate group, the quaternary ammonium salt (E1), and the ionic liquid (E2). The polyurethane resin composition is also included in the technical scope of the present invention.

The urethane prepolymer (A) is preferably a reaction product of a polyol (A1) and a polyisocyanate (A2), and has an isocyanate group. The isocyanate group is preferably located at the end of the urethane prepolymer (A).

As the polyol (A1), one kind or two or more kinds can be used, and examples thereof include high molecular weight polyols such as polyester polyols, polyether polyols, and polycarbonate polyols; and low molecular weight polyols. The polyol (A1) may be a bifunctional or trifunctional or higher functional polyol.

As the polyester polyol, one kind or two or more kinds can be used. For example, a polyester polyol obtained by reacting a low molecular weight polyol with a polycarboxylic acid; a ring-opening polymerization of a cyclic ester compound such as ε-caprolactone. Polyester polyols obtained by reaction; polyester polyols obtained by copolymerizing these compounds and the like can be mentioned.

As the low molecular weight polyol which is a raw material of the polyester polyol, one kind or two or more kinds can be used, and examples thereof include polyols having a molecular weight of 50 or more and less than 300, for example, ethylene glycol, 1,2-propanediol, and the like. 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol , Tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, Aliper polyols (diols or trifunctional or higher functional polyols) such as glycerin, trimethylolethane, trimethylolpropane; alicyclic polyols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A (diols or trifunctional or higher functional polyols) Diol or trifunctional or higher functional polyol); aromatic polyols such as bisphenol A, bisphenol S, bisphenol AF, bisphenol Si ₂ , dihydroxynaphthalene and bisphenol F (diol or trifunctional or higher functional polyol); alkylene oxide addition of the aromatic polyol. Goods; sugars such as sorbitol, sucrose, aconit sugar; amine compounds and the like. Of these, an aliphatic polyol is preferable, and the number of carbon atoms of the aliphatic polyol is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4. The content of the aliphatic polyol is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and the upper limit is 100% by mass, among the low molecular weight polyols which are the raw materials of the polyester polyol. Is.

As the polycarboxylic acid as a raw material of the polyester polyol, one kind or two or more kinds can be used, and for example, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid, maleic acid, fumaric acid and the like can be used. Aliphatic polycarboxylic acid; alicyclic polycarboxylic acid such as 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1, Aromatic polycarboxylic acids such as 2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, trimellitic acid, pyromellitic acid; maleine anhydride Examples thereof include anhydrides or esterified products thereof such as acids. Of these, aliphatic polycarboxylic acids are preferable, and adipic acid is particularly preferable.

As the polyether polyol, one kind or two or more kinds can be used, for example, polyethylene glycol (PEG), polypropylene glycol (PPG), polyoxyethylene polyoxypropylene glycol (PEPG), polytetramethylene glycol (PTMG). ), Polyoxybutylene glycol, polyoxypentylene glycol, polyoxyhexylene glycol and the like, and examples thereof include polyether polyols having an oxyalkylene unit having 2 to 6 carbon atoms (preferably 2 to 4 carbon atoms). The polyether polyol may have any linear, branched or cyclic structure.

The polyether polyol may be a bifunctional polyol or a trifunctional or higher functional polyol, and is preferably a bifunctional polyol.

The polycarbonate polyol is obtained by esterifying a carbonic acid and a carbonic acid ester with a polyhydric alcohol. As the polyhydric alcohol, one kind or two or more kinds can be used, for example, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polyoxypropylene. Glycol, polytetramethylene glycol and the like can be mentioned.

Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like.

The high molecular weight polyol is a polyol obtained by ring-opening addition polymerization of a lactone compound such as ε-caprolactone to the polyether polyol; a polycaprolactone polyol obtained by ring-opening polymerization of a caprolactone monomer; a polyether ester polyol; an aromatic polyester polyol; Acrylic polyol; polyolefin polyol; polybutadiene polyol; ring-opening oil-based polyol; polymer polyol obtained by polymerizing an ethylenically unsaturated monomer such as acrylonitrile or styrene in the presence of polyether ester polyol can also be used.

The total content of the polyester polyol, the polyether polyol and the polycarbonate polyol (preferably polyester polyol) in the high molecular weight polyol is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more. It is preferably 100% by mass or less.

The hydroxyl value of the high molecular weight polyol is preferably 20 mgKOH / g or more, more preferably 35 mgKOH / g or more, still more preferably 55 mgKOH / g or more, preferably 225 mgKOH / g or less, and more preferably 120 mgKOH / g or less. .. When the hydroxyl value of the polyester polyol is in the above range, the viscosity of the urethane prepolymer (A) described later can be suppressed. In the present invention, the hydroxyl value of the high molecular weight polyol can be measured according to JIS K 1557-1.

The content of the high molecular weight polyol in the polyol (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 75% by mass or more, and preferably 100% by mass or less.

Examples of the low molecular weight polyol include ethylene glycol (EG), 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 2-methyl-1,3. -Pentanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol , 3-Methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol and other aliphatic diols; 1,4-cyclohexanediol , 1,4-Cyclohexanedimethanol, alicyclic diols such as hydrogenated bisphenol A; trifunctional or higher hydroxyl group-containing compounds such as glycerin, trimethylolpropane, pentaerythritol, etc. Among these, diethylene glycol (DEG) ) Is preferable. The low molecular weight glycol may have a linear, branched or cyclic structure.

The molecular weight of the low molecular weight polyol is preferably 50 or more, preferably 300 or less, and more preferably 200 or less. If the molecular weight of the low molecular weight glycol is within such a range, a molded product having a target hardness can be easily obtained when used in combination as a polyol component.

As the polyisocyanate (A2), one type or two or more types can be used, and any of an aliphatic polyisocyanate, an alicyclic polyisocyanate, and an aromatic polyisocyanate may be used. Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate (HDI), diisocyanate dimerate, norbornene diisocyanate, lysine diisocyanate, tetramethylxylylene diisocyanate and the like; as the alicyclic polyisocyanate, or isophorone diisocyanate (IPDI). , Hydrogenated diphenylmethane diisocyanate (hydrous MDI), hydrogenated xylylene diisocyanate (hydrous XDI), cyclohexanediisocyanis, dicyclohexylmethane diisocyanate, isophoron diisocyanate and the like; Examples of the aromatic polyisocyanate include diphenylmethane diisosocyanate. (MDI; its 4,4'body, 2,4'body or 2,2'body, or a mixture thereof, crude MDI), carbodiimide-modified MDI (modified MDI), polymethylene polyphenyl polyisocyanate, carbodiimided diphenylmethane poly Diisocyanate, xylene diisocyanate, tolylene diisocyanate (TDI; 2, 4 or 2, 6 bodies thereof, or a mixture thereof), xylylene diisocyanate (XDI), 1,5-naphthalenediocyanate (NDI), tetra Examples thereof include methyl xylene diisocyanate and phenylenedi isocyanate. Among them, aromatic polyisocyanate is preferable, MDI and TDI are more preferable, and vapor when used by heating and melting is preferable because it is excellent in reactivity with a polyol component, reactivity with moisture (water), workability and the like. MDI with low pressure is particularly preferred.

The molar ratio (NCO / OH) of the isocyanate group contained in the polyisocyanate (A2) to the hydroxyl group contained in the polyol (A1) is preferably 2 or more, more preferably 3 or more, preferably 20 or less. More preferably, it is 15 or less.

The reaction between the polyol (A1) and the polyisocyanate (A2) may be carried out in a solvent-free environment or in an organic solvent. Examples of the organic solvent include ester solvents such as ethyl acetate and n-butyl acetate; ketone solvents such as acetone and methyl ethyl ketone; and aromatic hydrocarbon solvents such as toluene. It is desirable to remove the organic solvent during the reaction or after the reaction is completed by heating under reduced pressure, distilling off a thin film, or the like.

The reaction temperature of the polyol (A1) and the polyisocyanate (A2) is preferably, for example, 50 to 90 ° C., the reaction time is preferably, for example, 2 to 24 hours, and the reaction pressure is normal pressure, pressurization, and so on. Either decompression may be used. As the reaction method, a known reaction method such as batch, semi-continuous, continuous, etc. can be selected.

The reaction atmosphere of the polyol (A1) and the polyisocyanate (A2) may be an inert gas atmosphere such as nitrogen or argon, or may be a dry air atmosphere, and the moisture content under closed conditions or the like may be present. It may be a condition that does not mix.

When the polyol (A1) and the polyisocyanate (A2) are reacted, a urethanization catalyst may coexist if necessary. The catalyst can be appropriately added at any stage of the raw material charging step and the reaction step. Further, the method of adding the catalyst may be batch, division, continuous or the like.

As the urethanization catalyst, one kind or two or more kinds can be used, for example, nitrogen-containing compounds such as triethylamine, tributylamine, benzyldibutylamine, triethylenediamine, N-methylmorpholin; titanium tetrabutoxide, dibutyltin oxide, etc. Organic metal compounds such as dibutyltin dilaurate, tin 2-ethylcaproate, zinc naphthenate, cobalt naphthenate, zinc 2-ethylcaproate, molybdenum glycolate, potassium acetate, zinc stearate, tin octylate, dibutyltin dilaurate; Examples thereof include inorganic compounds such as iron chloride and zinc chloride.

The urethane prepolymer (A) has an isocyanate group at the end. The isocyanate group equivalent of the urethane prepolymer (A) is preferably 150 to 350 g / mol, more preferably 200 to 300 g / mol. When the isocyanate group equivalent of the urethane prepolymer is within the above range, the viscosity of the urethane prepolymer can be suppressed. The isocyanate group equivalent of the urethane prepolymer can be measured in accordance with JIS K1603-2007 Plastic-Polyurethane Raw Material Aromatic Isocyanate Test Method Part 1: How to Obtain Isocyanate Group Content.

The curing agent (ii) includes a compound (B) having two or more functional groups capable of reacting with an isocyanate group (hereinafter, may be referred to as “compound (B)”) and a quaternary ammonium salt (E1). And an ionic liquid (E2).

As the compound (B), one kind or two or more kinds can be used, and examples thereof include active hydrogen atom-containing compounds such as polyols and polyamines.

As the polyol (B1) as the compound (B), one kind or two or more kinds can be used, and examples thereof include compounds similar to the compound exemplified as the polyol (A1). Of these, polyester polyols, polyether polyols, and polycarbonate polyols are preferable, and polyester polyols are more preferable.

The content of the trifunctional or higher functional polyol in the high molecular weight polyol is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and preferably 10% by mass or less. More preferably, it is 7% by mass or less.

The content of the high molecular weight polyol in the polyol (B1) is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more, and preferably 100% by mass or less.

The content of the low molecular weight polyol in the polyol (B1) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass or more with respect to 100 parts by mass of the high molecular weight polyol. It is preferably 10 parts by mass or less, and more preferably 7 parts by mass or less.

The content of the polyol (B1) in the compound (B) is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass or less.

Examples of the polyamine (B2) as the compound (B) include aliphatic or alicyclic amine compounds such as ethylenediamine, propanediamine, hexanediamine, and isophoronediamine; phenylenediamine, 3,3'-dichloro-4,4'-. Examples thereof include aromatic amine compounds such as diaminodiphenylmethane and polyaminochlorophenylmethane compounds.

As the compound (B), a polyol (B1) is preferable.

The content of the quaternary ammonium salt (E1) is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and preferably 12 in the polyurethane resin composition. It is mass% or less, more preferably 10 mass% or less, still more preferably 7 mass% or less, still more preferably 5 mass% or less.

The ratio (E1 / E2) of the content of the quaternary ammonium salt (E1) to the ionic liquid (E2) is preferably 2 or more, more preferably 4 or more, and preferably 30 or less on a mass basis. , More preferably 20 or less, still more preferably 15 or less.

The curing agent (ii) may contain the antistatic agent (E3) and the antistatic aid (E4).

The quaternary ammonium salt (E1), the ionic liquid (E2), and all or part of the antistatic agent (E3) and the antistatic aid (E4) used as needed are contained in the main agent (i). However, from the viewpoint of uniform mixing and control of curing reaction, it is preferable that all of them are contained in the curing agent (ii).

The polyurethane resin composition preferably contains a foaming agent. By including a foaming agent, the polyurethane resin composition can be foamed. Water is preferable as the foaming agent. The content of the foaming agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 0.8 parts by mass or less with respect to 100 parts by mass of the compound (B). More preferably, it is 0.4 parts by mass or less. When the content of the foaming agent is within the above range, it is easy to realize a stable foaming state.

The polyurethane resin composition may further contain a foaming aid. As the foaming aid, one kind or two or more kinds can be used, for example, 1,1-dichloro-1-fluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1, Low boiling point (for example, 50 ° C. or lower, preferably 40 ° C. or lower) compounds (hydrocarbon compounds or halogenated hydrocarbon compounds, preferably halogenated hydrocarbon compounds) such as 1,3,3-pentafluorobutane, methylene chloride, pentane and the like. ).

The foaming agent and the foaming aid need only be partially or wholly contained in at least one of the main agent (i) and the curing agent (ii), and all of them are contained in the curing agent (ii). Is preferable.

The polyurethane resin composition preferably further contains a catalyst (D). As the catalyst (D), one kind or two or more kinds can be used, for example, triethylamine, triethylenediamine, palmityldimethylamine, pentamethyldiethylenetriamine, N, N-dimethylaminoethyl ether, dimethylethanolamine, tri. Amine compounds such as ethanolamine, N, N, N', N'-tetramethylhexamethylenediamine, N-methylimidazole, N-ethylmorpholine, toluenediamine, 4,4'-diaminodiphenylmethane, or dioctyltin dilaurate, Examples thereof include organic metal compounds such as stanas octoate and dibutyltin dilaurate. As the catalyst (D), triethylenediamine and N, N-dimethylaminoethyl ether are more preferable from the viewpoint of controlling foamability.

The content of the catalyst (D) is preferably 0.15 parts by mass or more, more preferably 0.3 parts by mass or more, and preferably 2 parts by mass or less, based on 100 parts by mass of the compound (B). More preferably, it is 1.5 parts by mass or less. When the content of the catalyst (D) is within the above range, the foaming state can be easily stabilized.

The catalyst (D) may be partially or wholly contained in at least one of the main agent (i) and the curing agent (ii), and the catalyst (D) may be entirely contained in the curing agent (ii). preferable.

The polyurethane resin composition may contain other additives. Examples of the other additives include flame retardants, defoamers, chain extenders, plasticizers, fillers, colorants, weather stabilizers, light stabilizers, antioxidants and the like. As the defoaming agent, one kind or two or more kinds can be used, for example, silicon compounds such as polydimethylsiloxane and polysiloxane-polyalkylene oxide block copolymers, metal soaps, ethylene oxides of alkylphenols and fatty acids, and / Or a surfactant such as a propylene oxide adduct can be mentioned. As the plasticizer, one type or two or more types can be used, and examples thereof include adipate-based polyester plasticizers and benzoic acid-based polyester plasticizers. The other additive may be contained in the main agent (i) or in the curing agent (ii).

The polyurethane resin composition can be produced by mixing the main agent (i) and the curing agent (ii). Among all the components contained in the main agent (i) and the curing agent (ii), the molar ratio (NCO / active hydrogen atom-containing group) of the isocyanate group to the active hydrogen atom-containing group such as a hydroxyl group and -NH- group is preferable. Is 0.7 or more, more preferably 0.85 or more, preferably 1.2 or less, and more preferably 1.1 or less. When the molar ratio (NCO / active hydrogen atom-containing group) is in the above range, the strength, flexibility and abrasion resistance of the obtained polyurethane resin molded product can be enhanced.

When the polyurethane resin composition is foamed, the foaming agent may be used, hollow beads may be added, or mechanical foaming or chemical foaming may be performed. Further, a foam molding machine such as a low pressure foam molding machine or an injection foam molding machine can be used.

The polyurethane resin composition can be used by a molding method (open injection of a mixed foam liquid discharged from a molding machine into a mold) or an injection molding method (direct injection of a mixed foam liquid into a closed mold directly connected to a discharge port of a molding machine). It can be molded by such as.

As the molding mold (mold), an open mold composed of an upper mold and a lower mold; a flat mold; a tubular mold; a concave closed mold and the like can be used. As the material of the molding mold, a metal such as iron or aluminum; a resin such as an epoxy resin can be adopted.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can be adapted to the gist of the above and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention.

[Preparation of main agent (X)]
In the reaction vessel, 560 parts of 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as "4,4'MDI". Trademark: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) was charged as isocyanate (A2), and stirring was started. did.
Next, as the polyol (A1), a polyester polyol having a hydroxyl value of 56.1 mgKOH / g synthesized from polyol a (ethylene glycol (EG) / 1,4-butylene glycol (1,4BG) and adipic acid (AA)). / 1,4BG = 5/5 molar ratio.) 443.5 parts by mass was prepared and mixed in divided portions, and the reaction was carried out at 60 ° C. under a nitrogen stream for 8 hours to obtain an isocyanate group-terminated urethane prepolymer having an NCO equivalent of 250 (A). ) Was obtained as a main agent (X).

[Preparation of curing agent (Y1) for outsole]
Polyester b (polyester polyol having a hydroxyl value of 112 mgKOH / g synthesized from EG / 1,4BG and AA as a compound (B1) having two or more functional groups capable of reacting with an isocyanate group. EG / 1,4BG = 5/5 (Mole ratio.) 65.0 parts by mass and a polyester polyol having a hydroxyl value of 60 mgKOH / g synthesized from polyol c (diethylene glycol (DEG) / trimethylolpropane (TMP) and AA. DEG / TMP = 15/1 mol. Ratio.) 5.0 parts by mass, 30.0 parts by mass of polyol d (polyester polyol having a hydroxyl value of 56 mgKOH / g synthesized from 2-methyl-1,3-propanediol and AA), and EG7. 0 parts by mass of water (C) as a foaming agent, 0.18 parts by mass of water (C) as a foaming agent, and 1.0 part by mass of triethylenediamine (TEDA) as a catalyst (D) were blended, and the mixture was sufficiently stirred and mixed to prepare a curing agent (Y1). Prepared.

[Preparation of curing agent (Y2) for midsole]
Polyester e (polyester polyol having a hydroxyl value of 66 mgKOH / g synthesized from EG / 1,4BG and AA, having an EG / 1,4BG = 5/5 molar ratio) as an isocyanate group-reactive compound (B2) 91.5 Part by mass and polyol c (polyester polyol with hydroxyl value 60 mgKOH / g synthesized from diethylene glycol (DEG) / trimethylolpropane (TMP) and AA. Deg / TMP = 15/1 molar ratio.) 4.8 mass 10.7 parts by mass of EG, 0.40 parts by mass of water (C) as a foaming agent, and 1.0 part by mass of triethylenediamine (TEDA) as a catalyst (D) are mixed, and the mixture is sufficiently stirred, mixed, and cured. Agent (Y2) was prepared.

[Example 1]
<< Production of two-component curable polyurethane foam resin composition (P1) >>
In a mixing container, 107.0 parts by mass of the curing agent (Y1), 8.2 parts by mass of N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate (E1) and (E2K1) 1 as antistatic agents. 1.26 parts by mass of an ionic liquid (E2) composed of −butyl-3-methyl-imidazolium and (E2A1) bis (trifluoromethylsulfonyl) imide was mixed, and the mixture was thoroughly stirred and mixed with a curing agent (Y1). An outsole polyol compound (PCA1) containing an antistatic agent was obtained.

107.0 parts by mass of the curing agent (Y2), 6.5 parts by mass of N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate (E1) and (E2K1) 1 as antistatic agents in a mixing container. 1.0 part by mass of an ionic liquid (E2) composed of −butyl-3-methyl-imidazolium and (E2A1) bis (trifluoromethylsulfonyl) imide was mixed, and the mixture was thoroughly stirred and mixed with a curing agent (Y2). An outsole polyol compound (PCM1) containing an antistatic agent was obtained.

The main agent (X) and the polyol compound (PCA1) are mixed in a mixing container at a mass ratio of (X) / (PCA1) = 89/100, stirred and mixed to form a two-component curable polyurethane foam resin of the present invention. A product (PA1) was prepared, 100 g was injected into a mold (100 mm × 200 mm × 5 mm) preheated to 40 ° C., the mold was immediately covered, and then left at 40 ° C. for 2.5 minutes. After that, the completed outsole foam molded product was taken out. The molded product was allowed to stand in an atmosphere of 30 ° C. and 80% RH for 3 minutes, and then the outsole was placed in a mold (100 mm × 200 mm × 15 mm).

Under the conditions of a temperature of 30 ° C. and a relative humidity of 80% RH, the main agent (X) and the polyol compound (PCM1) are mixed in a mixing container at a mass ratio of (X) / (PCM1) = 109/100, stirred and mixed. The two-component curable polyurethane foam resin composition (PM1) of the present invention was prepared, 100 g was injected into the outsole (100 mm × 200 mm × 15 mm), and the mold was immediately covered. It was left at 40 ° C. for 3.5 minutes, after which the finished foam molded product was taken out. After 3 minutes, the outsole foam molded product was placed in a mold (100 mm × 200 mm × 15 mm).

[Examples 2 to 8]
Foam molded article in the same manner as in Example 1 except that the combination and amount of the cation component and the anion component of the ionic liquid (E2) and the mass ratio of the main agent and the polyol compound were changed as shown in Table 1. Got

[Comparative Example 1]
<< Production of two-component curable polyurethane foam resin composition (P8) >>
As an ionic liquid (E2K5) 1-ethyl-3-methyl-
An effervescent molded product was obtained in the same manner as in Example 1 except that an ionic liquid (E2) composed of imidazolium and (E2A4) ethyl sulfate was used.

[Comparative Examples 2 to 7]
Foam molded article in the same manner as in Example 1 except that the combination and amount of the cation component and the anion component of the ionic liquid (E2) and the mass ratio of the main agent and the polyol compound were changed as shown in Table 1. Got

[Measuring method of density of urethane molded product]
^{The density (g / cm 3} ) was calculated by dividing the mass of the obtained urethane molded product by the volume.

[Measuring method of hardness of urethane molded product]
The hardness of the obtained urethane molded product was evaluated by a spring hardness test (type C) in accordance with Japanese Industrial Standards JIS K 7312-1996 (hardness test).

[Peeling strength measurement]
Under the conditions of a temperature of 30 ° C. and a relative humidity of 80% RH, the outsole resin was injected into a 100 mm × 200 mm × 5 mm mold, demolded for 2.5 minutes, and then taken out from the mold. The molded product was allowed to stand in an atmosphere of 30 ° C. and 80% relative humidity for 3 minutes, and then an outsole was placed in a 100 mm × 200 mm × 15 mm mold, and a midsole resin was injection-molded into the space. After 3.5 minutes, the mold was removed and the mixture was allowed to stand at room temperature for 24 hours. The molded product was punched to a size of 25 mm × 150 mm, and the peel strength of the outsole and the midsole was measured by Shimadzu Autograph AG-1 Co., Ltd. at a peel test speed of 100 mm / min.

[Evaluation method of antistatic property]
Using a battery-powered insulation resistance tester (Yokogawa Electric Co., Ltd., 2604 01 type), an iron plate (300 mm x 200 mm x 1 mm) is placed on the lower surface of the measurement sample (75 mm x 75 mm x 10 mm) prepared above, and an iron plate (300 mm x 200 mm x 1 mm) is placed on the upper surface. (75 mm × 75 mm × 3 mm) were brought into contact with each other, and the electric resistance value at 7 cost after molding was measured to evaluate the antistatic property. The molded sample is stored in an indoor environment with a temperature of 23 ° C and a relative humidity of 50%, and then electricity is applied under two conditions: normal temperature conditions (23 ° C, relative humidity 65%) and low temperature and low humidity conditions (0 ° C). The resistance value (unit: MΩ) was measured.

Tables 1 and 2 show the cationic component of the ionic liquid (E2), the anionic component of the ionic liquid (E2), and the content ratio (mass basis) of the ammonium salt (E1) and the ionic liquid (E2) in the resin composition. , "(E1) / (E2)"), the sum of the contents of the ammonium salt (E1) and the ionic liquid (E2) in the resin composition (mass standard. In the table, "(E1) + (E2)" ) ”, Mass ratio of the main agent to the polyol compound (abbreviated as“ main agent (i) / hardener (ii) ”in the table.) Density (g / cm ³ ) and hardness of outsole and midsole. , Outsole and midsole peel strength (abbreviated as "peeling strength" in the table), electrical resistance value at 23 ° C and relative humidity 65% (abbreviated as "normal temperature and normal pressure electrical resistance value" in the table) The electric resistance value at 0 ° C. and 40% relative humidity (abbreviated as “low temperature and low humidity electric resistance value” in the table) is shown.

The abbreviations and names described in Examples and Comparative Examples are as follows.
4,4'MDI: 4,4'-diphenylmethanediisocyanate EG: Ethyl glycol 1,4BG: 1,4-butylene glycol AA: Adipate DEG: Diethylene glycol TMP: Trimethylol propane TEDA: Triethylenediamine (E1): Alkyl substitution Quadruple ammonium salt (AM1): N-ethyl-N, N-dimethyl-N-dodecyl ammonium ethyl sulfate (E2): (E2K1) 1-butyl-3-methylimidazolium (E2K2) 1 as an ionic liquid cation component -Butyl-1-methylpyrrolidinium (E2K3) Butyltrimethylammonium (E2K4) Trioctylmethylammonium (E2K5) 1-ethyl-3-methylimidazolium As an anion component, (E2A1) bis (trifluoromethylsulfonyl) imide (E2A2) ) Trifluoromethylsulfonate (E2A3) Tetrafluoroborate (E2A4) Ethyl sulphate

Examples 1 to 9 are examples of the present invention, and it was possible to improve the adhesiveness between the outsole and the midsole while maintaining the electrostatic performance even when manufactured under high temperature and high humidity. Comparative Examples 1 and 2 were examples in which an ionic liquid not corresponding to the ionic liquid (E2) was used, and the adhesiveness between the outsole and the midsole was not sufficiently satisfactory. Comparative Example 3 was an example in which the ionic liquid was not contained, and the electrostatic performance was not sufficiently satisfactory. Comparative Example 4 was an example in which the ammonium salt was not contained, and the electrostatic performance was not sufficiently satisfactory.

Claims (6)

It contains a polyurethane resin, a quaternary ammonium salt (E1), and an ionic liquid (E2).
The quaternary ammonium salt (E1) contains at least one selected from the group consisting of sulfate ester anions and sulfonic acid anions as an anion component.
The ionic liquid (E2) has an imidazolium cation having an alkyl group having 3 or more carbon atoms, a pyridinium cation having an alkyl group having 3 or more carbon atoms, and a pyroli having an alkyl group having 3 or more carbon atoms as cation components. A polyurethane resin molded product containing at least one selected from the group consisting of a dinium cation, a piperidinium cation having an alkyl group having 3 or more carbon atoms, and a quaternary ammonium cation having an alkyl group having 3 or more carbon atoms. .. The ionic liquid is selected as an anion component from the group consisting of bis (trifluoromethanesulfonyl) imide anion, bis (pentafluoroethanesulfonyl) anion, tris (trifluoromethanesulfonyl) methide anion, trifluoromethanesulfonate anion and tetrafluoroborate anion. The polyurethane resin molded product according to claim 1, which comprises one or more types. Claim 1 or 2 in which the content ratio ((E1) / (E2)) of the quaternary ammonium salt (E1) to the ionic liquid (E2) is 1/1 or more and 20/1 or less on a mass basis. The polyurethane resin molded article described. The polyurethane resin according to any one of claims 1 to 3, wherein the total content of the quaternary ammonium salt (E1) and the ionic liquid (E2) is 0.5% by mass or more and 10% by mass or less. Molded body. The polyurethane resin molded product according to any one of claims 1 to 4, which is a shoe sole. Contains the main agent (i) and the curing agent (ii),
The main agent (i) contains a urethane prepolymer having an isocyanate group, and the main agent (i) contains a urethane prepolymer.
The curing agent (ii) contains a compound having two or more functional groups capable of reacting with an isocyanate group, a quaternary ammonium salt (E1), and an ionic liquid (E2).
The quaternary ammonium salt (E1) contains at least one selected from the group consisting of sulfate ester anions and sulfonic acid anions as an anion component.
The ionic liquid (E2) has an imidazolium cation having an alkyl group having 3 or more carbon atoms, a pyridinium cation having an alkyl group having 3 or more carbon atoms, and a pyrrolidinium cation having an alkyl group having 3 or more carbon atoms. A polyurethane resin composition containing at least one selected from the group consisting of a piperidinium cation having an alkyl group having 3 or more carbon atoms and a quaternary ammonium cation having an alkyl group having 3 or more carbon atoms.