Laminate and shoe sole

Abstract

The present invention was made in view of the aforementioned circumstances, and its objective is to provide a laminate that exhibits good adhesion between layers even during continuous molding under high temperature and high humidity conditions. The laminate of the present invention is characterized by having a first urethane foam layer and a second urethane foam layer, wherein the density of the first urethane foam layer is 0.8 g / cm³. 3 Above and 1.2g / cm 3 Hereinafter, the density of the second urethane foam layer is 0.3 g / cm³. 3 Above and 0.7g / cm 3 In the second urethane foam layer, when the average pore diameter of the foaming pores in the range greater than 200 μm from the interface with the first urethane foam layer is set as a (μm), and the average pore diameter of the foaming pores in the range less than 200 μm from the interface with the first urethane foam layer is set as b (μm), b / a is less than 1.2.

Description

Technical Field

[0001] This invention relates to laminated bodies and shoe soles. Background Technology

[0002] In recent years, from the perspective of preventing electrostatic explosions in the workplace, research has been conducted on imparting electrostatic properties to resins and fibers used in shoes, clothes, gloves, etc. worn on the human body, such as in the soles of antistatic shoes.

[0003] One method for imparting antistatic properties to resins is to coat the surface of a resin molded article with an antistatic agent containing conductive or ionic substances, or to add it into the resin. Examples of applying these methods to polyurethane resins include: 1) adding carbon black, conductive fillers, etc.; 2) coating or adding ionic surfactants; 3) adding alkali metal salts such as perchloric acid, thiocyanate, or nitric acid; 4) adding alkyl sulfate quaternary ammonium salts or perchlorate quaternary ammonium salts; and 5) adding non-metallic antistatic compounds such as substituted sulfonate quaternary ammonium salts, metallic antistatic compounds such as sulfonate metal salts, and polar organic solvents (Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2005-060682 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] On the other hand, the materials used in shoes, clothes, gloves, etc., are often made into components of different densities to meet the required performance. For example, in the case of antistatic shoes, the surface that is placed on the ground or floor is made of high-density molded material from the viewpoint of abrasion resistance, scratch resistance, and hydrolysis resistance, while the surface that comes into contact with the human body is made of low-density molded material from the viewpoint of bending resistance and softness, and the components are made by bonding them together.

[0009] Because of their self-adhesive properties, urethane resins can be molded by first molding the high-density portion and then continuously molding the low-density portion to obtain a composite. However, the antistatic agents added to the resin to improve its electrostatic properties can sometimes hinder the adhesion of the composite. With shoe sole production shifting to Southeast Asia where wages are low, the continuous molding process under particularly high temperatures and humidity has exacerbated this adhesion problem.

[0010] The present invention was made in view of the above circumstances, and its objective is to provide a laminate that maintains good adhesion between layers even when continuous molding is performed under high temperature and high humidity conditions.

[0011] Methods for solving problems

[0012] The inventors conducted in-depth research and found that when the density of each layer and the size of the foaming pores contained in each layer are set within a specific range, the adhesion between the layers becomes good, thus completing the present invention.

[0013] That is, the laminate of the present invention is characterized by having a first urethane foam layer and a second urethane foam layer, wherein the density of the first urethane foam layer is 0.8 g / cm³. 3 Above and 1.2g / cm 3 The density of the second urethane foam layer is 0.3 g / cm³. 3 Above and 0.7g / cm 3 In the second urethane foam layer described above, when the average pore diameter of the foaming pores in the range greater than 200 μm from the interface with the first urethane foam layer is set as a (μm), and the average pore diameter of the foaming pores in the range less than 200 μm from the interface with the first urethane foam layer is set as b (μm), b / a is less than 1.2.

[0014] Invention Effects

[0015] Even when the laminate of the present invention is continuously molded under high temperature and high humidity, the adhesion between the layers is good. Detailed Implementation

[0016] The laminate of the present invention has a first urethane foam layer and a second urethane foam layer.

[0017] [First carbamate foam layer]

[0018] The aforementioned first urethane foam layer is formed from a foam of urethane resin. Examples of such urethane resins include polyether-based urethane resins, polyester-based urethane resins, and polycarbonate-based urethane resins. In this invention, for example, "polyester-based urethane resin" refers to a urethane resin having units derived from polyester in its molecular chain.

[0019] The density of the first carbamate foam layer is preferably 0.8 g / cm³. 3 The above, more preferably 0.9 g / cm³ 3 The above, and preferably 1.2 g / cm³ 3 The following is more preferably 1.1 g / cm³ 3 the following.

[0020] When the hardness of the first urethane foam layer is measured according to the Japanese Industrial Standard JIS K 7312-1996 (Hardness Test) using a spring hardness test (Type C), it is preferably 50 or more, more preferably 60 or more, and preferably 100 or less, more preferably 90 or less.

[0021] In the first urethane foam layer described above, the diameter of the foam pores is preferably 101 μm or more, more preferably 20 μm or more, even more preferably 30 μm or more, and preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less.

[0022] In this invention, the term "foaming pore diameter" refers to the major axis of the foaming pores observed in the fracture surface of the urethane foam. The aforementioned foaming pore diameter can be measured using a scanning electron microscope (SEM), and the average foaming pore diameter represents the average value obtained from measuring more than 50 foaming pores.

[0023] The aforementioned first urethane foam layer can be manufactured by foaming, molding, and curing a first polyurethane resin composition containing a main agent (i) and a curing agent (ii).

[0024] The main agent (i) preferably comprises a urethane prepolymer (A) having isocyanate groups.

[0025] The aforementioned urethane prepolymer (A) is preferably a reaction product of a polyol (A1) and a polyisocyanate (A2), and preferably has an isocyanate group. The isocyanate group is preferably located at the end of the urethane prepolymer (A).

[0026] As the aforementioned polyol (A1), one or more types can be used, such as high molecular weight polyols like polyester polyols, polyether polyols, and polycarbonate polyols; and low molecular weight polyols. The aforementioned polyol (A1) can be a polyol with two or more functions.

[0027] As the aforementioned polyester polyol, one or more types can be used, such as polyester polyols obtained by reacting low molecular weight polyols with polycarboxylic acids; polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as ε-caprolactone; and polyester polyols obtained by copolymerizing them.

[0028] Regarding the low molecular weight polyols used as raw materials for the aforementioned polyester polyols, one or more types can be used. Examples include polyols with a molecular weight of 50 or higher but less than 300, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentanediol, 1,6-hexanediol, diethylene glycol, neopentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, and 2-butyl-2-ethyl-1,3-propanediol. Aliphatic polyols (diols or polyols with three or more functions) such as diols, 2-methyl-1,3-propanediol, glycerol, trimethylolethane, and trimethylolpropane; alicyclic polyols (diols or polyols with three or more functions) such as 1,4-cyclohexanediol, 1,4-cyclohexanediethanol, and hydrogenated bisphenol A; aromatic polyols (diols or polyols with three or more functions) such as bisphenol A, bisphenol S, bisphenol AF, bisphenol Si2, dihydroxynaphthalene, and bisphenol F; epoxide adducts of the above aromatic polyols; sugars such as sorbitol, sucrose, and aconite; and amine compounds. Among these, aliphatic polyols are preferred, and the number of carbon atoms in the above aliphatic polyols is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4. The content of the aforementioned aliphatic polyol in the low molecular weight polyols used as raw materials for the aforementioned polyester polyol is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and the upper limit is 100% by mass.

[0029] Regarding the polycarboxylic acids used as raw materials for the aforementioned polyester polyols, one or more can be used. Examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, maleic acid, and fumaric acid; alicyclic polycarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, biphenyl dicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, trimellitic acid, and pyromellitic acid; and their anhydrides or esters, such as maleic anhydride. Among these, aliphatic polycarboxylic acids are preferred, and adipic acid is particularly preferred.

[0030] As the aforementioned polyether polyols, one or more can be used, such as polyethylene glycol (PEG), polypropylene glycol (PPG), polyoxyethylene polyoxypropylene glycol (PEPG), poly1,4-butanediol (PTMG), polyoxybutylene glycol, polyoxypentanediol, polyoxyhexanediol, and other polyether polyols having olefinic units with 2 to 6 carbon atoms (preferably 2 to 4 carbon atoms). The aforementioned polyether polyols can have any structure, including linear, branched, and cyclic structures.

[0031] The aforementioned polyether polyol can be a difunctional polyol or a polyol with three or more functions, preferably a difunctional polyol.

[0032] The aforementioned polycarbonate polyol is a compound obtained by esterification of carbonic acid and carbonate with a polyol. One or more of these polyols can be used, for example, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polyoxypropylene glycol, and poly-1,4-butanediol.

[0033] Examples of the aforementioned carbonates include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonates, and diphenyl carbonate.

[0034] As the aforementioned high molecular weight polyols, polyols obtained by ring-opening addition polymerization of ε-caprolactone and other lactone compounds from the aforementioned polyether polyols can also be used; polycaprolactone polyols obtained by ring-opening polymerization of caprolactone monomers; polyether ester polyols; aromatic polyester polyols; acrylic polyols; polyolefin polyols; polybutadiene polyols; castor oil-based polyols; and polymer polyols obtained by polymerizing olefinic unsaturated monomers such as acrylonitrile and styrene in the presence of polyether ester polyols.

[0035] In the above-mentioned high molecular weight polyols, the total content of polyester polyols, polyether polyols and polycarbonate polyols (preferably polyester polyols) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and preferably 100% by mass or less.

[0036] The hydroxyl value of the aforementioned high molecular weight polyol is preferably 20 mg KOH / g or more, more preferably 35 mg KOH / g or more, even more preferably 55 mg KOH / g or more, and preferably 225 mg KOH / g or less, more preferably 120 mg KOH / g or less. If the hydroxyl value of the aforementioned polyester polyol is within the above range, the viscosity of the urethane prepolymer (A) described later can be suppressed. In this invention, the hydroxyl value of the high molecular weight polyol can be determined according to JIS K 1557-1.

[0037] In the above-mentioned polyols (A1), the content of high molecular weight polyols is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 75% by mass or more, and preferably 100% by mass or less.

[0038] Examples of low molecular weight polyols include ethylene glycol (EG), 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-pentanediol, 1,5-pentanediol, neopentanediol, 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-cyclohexanediol, hydrogenated bisphenol A, and other alicyclic diols; and compounds containing hydroxyl groups with three or more functions, such as glycerol, trimethylolpropane, and pentaerythritol. Among these, ethylene glycol (EG) is preferred. The aforementioned low molecular weight diols can have any type of structure, including straight-chain, branched-chain, and cyclic structures.

[0039] The molecular weight of the aforementioned low molecular weight polyol is preferably 50 or more, more preferably 300 or less, and even more preferably 200 or less. If the molecular weight of the aforementioned low molecular weight diol is within this range, it is easy to obtain a molded article with the target hardness when used as a polyol component.

[0040] As the aforementioned polyisocyanate (A2), one or more types can be used, and it can be any type of aliphatic polyisocyanate, alicyclic polyisocyanate, or aromatic polyisocyanate. Examples of aliphatic polyisocyanates include hexamethylene diisocyanate (HDI), dimer acid diisocyanate, norbornene diisocyanate, lysine diisocyanate, and tetramethylphenyldimethyl diisocyanate; examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated phenylmethane diisocyanate (hydrogenated XDI), cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate; examples of aromatic polyisocyanates include… Examples of suitable polyisocyanates include diphenylmethane diisocyanate (MDI; its 4,4', 2,4', or 2,2' forms, or mixtures thereof, crude MDI), carbodiimide-modified MDI (modified MDI), polymethylene polyphenyl polyisocyanate, carbodiimide-modified diphenylmethane polyisocyanate, xylene diisocyanate, toluene diisocyanate (TDI; its 2,4', or 2,6' forms, or mixtures thereof), phenylenediethylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), tetramethylxylene diisocyanate, and phenylene diisocyanate. Among these, aromatic polyisocyanates are preferred due to their superior reactivity with polyol components, reactivity with moisture (water), and workability; MDI and TDI are more preferred; and MDI with a low vapor pressure when used after heating and melting is particularly preferred.

[0041] The molar ratio (NCO / OH) of the isocyanate group contained in the above-mentioned polyisocyanate (A2) to the hydroxyl group contained in the above-mentioned polyol (A1) is preferably 2 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less.

[0042] The reaction between the polyol (A1) and the polyisocyanate (A2) can be carried out under solvent-free conditions or in an organic solvent. Examples of suitable organic solvents 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 best to remove these organic solvents during or after the reaction using methods such as reduced pressure heating or thin-film distillation.

[0043] The reaction temperature of the polyol (A1) and the polyisocyanate (A2) is preferably 50–90°C, the reaction time is preferably 2–24 hours, and the reaction pressure can be any of atmospheric pressure, pressurized pressure, or depressurized pressure. The reaction mode can be any of the known reaction modes such as batch, semi-continuous, or continuous.

[0044] The reaction atmosphere of the above polyol (A1) and the above polyisocyanate (A2) can be an inactive gas atmosphere such as nitrogen or argon, a dry air atmosphere, or a closed condition where no moisture is mixed in.

[0045] When reacting the polyol (A1) with the polyisocyanate (A2), a carbamate catalyst may be coexisting as needed. The catalyst can be appropriately added at any stage of the feedstock input process or the reaction process. Furthermore, the catalyst can be added in a single step, in batches, or continuously.

[0046] As the above-mentioned carbamate esterification catalyst, one or more can be used, such as nitrogen-containing compounds such as triethylamine, tributylamine, benzyl dibutylamine, triethylenediamine, and N-methylmorpholine; organometallic compounds such as tetrabutyl titanate, dibutyltin oxide, dibutyltin dilaurate, tin 2-ethylhexanoate, zinc naphthenate, cobalt naphthenate, zinc 2-ethylhexanoate, molybdenum glycolate, potassium acetate, zinc stearate, tin octanoate, and dibutyltin dilaurate; and inorganic compounds such as ferric chloride and zinc chloride.

[0047] The aforementioned urethane prepolymer (A) has isocyanate groups at its ends. The isocyanate group equivalent of the aforementioned urethane prepolymer (A) is preferably 150–350 g / mol, more preferably 200–300 g / mol. By keeping the isocyanate group equivalent of the urethane prepolymer within the above range, the viscosity of the urethane prepolymer can be suppressed. The isocyanate group equivalent of the aforementioned urethane prepolymer can be determined according to JIS K1603-2007 Plastics—Test Methods for Aromatic Isocyanates in Polyurethane Raw Materials, Part 1: Determination of Isocyanate Group Content.

[0048] The curing agent (ii) described above preferably comprises a compound (B) having two or more functional groups capable of reacting with isocyanate groups (hereinafter sometimes referred to as "compound (B)").

[0049] As the aforementioned compound (B), one or more can be used, such as polyols, polyamines, and other compounds containing active hydrogen atoms.

[0050] Regarding the polyol (B1) that is the above-mentioned compound (B), one or more can be used, for example, the same compound as the compound exemplified as the above-mentioned polyol (A1) can be used. Among them, high molecular weight polyols such as polyester polyols, polyether polyols, and polycarbonate polyols are preferred, and polyester polyols are more preferred.

[0051] In the above-mentioned high molecular weight polyols, the content of polyols with 3 or more functions is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and preferably 5% by mass or less, more preferably 10% by mass or less.

[0052] In the above-mentioned polyol (B1), the content of high molecular weight polyol is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and preferably 100% by mass or less.

[0053] In the above-mentioned polyol (B1), the content of the low molecular weight polyol is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, further preferably 3 parts by mass or more, and preferably 10 parts by mass or less, more preferably 7 parts by mass or less, relative to 100 parts by mass of the high molecular weight polyol.

[0054] In the above compound (B), the content of polyol (B1) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and preferably 100% by mass or less.

[0055] Regarding the polyamine (B2) that is the aforementioned compound (B), examples include aliphatic or alicyclic amine compounds such as ethylenediamine, propylenediamine, hexamethylenediamine, and isophoronediamine; and aromatic amine compounds such as phenylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, and polyaminochlorophenylmethane compounds.

[0056] As the above-mentioned compound (B), polyol (B1) is preferred.

[0057] The aforementioned first polyurethane resin composition preferably further comprises an antistatic agent (E). Examples of such antistatic agents include quaternary ammonium salts (E1), organometallic salts (E2), ionic liquids (E3), antistatic agents (E4), and antistatic additives (E5), with quaternary ammonium salts (E1), organometallic salts (E2), and ionic liquids (E3) being preferred, and quaternary ammonium salts (E1) and organometallic salts (E2) being more preferred. Regarding the content of the aforementioned antistatic agent (E) in the aforementioned first urethane foam layer, from the perspective of obtaining superior peel strength and antistatic properties, and from the perspective of easily adjusting the aforementioned b / a value to the range specified in this invention, the aforementioned content is preferably 0.1% by mass or more and less than 4.0% by mass, more preferably 3.15% by mass or more and 3.95% by mass or less.

[0058] The aforementioned quaternary ammonium salt (E1) contains both cationic and anionic components, with the quaternary ammonium salt being the cationic component.

[0059] As the aforementioned anionic component, it is preferable to include one or more selected from sulfate anions and sulfonic acid anions, and more preferably, sulfate anions. Examples of the aforementioned sulfate anions include alkyl sulfate anions having an alkyl group with 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as methyl sulfate anion, ethyl sulfate anion, propyl sulfate anion, butyl sulfate anion, pentyl sulfate anion, hexyl sulfate anion, heptayl sulfate anion, and octyl sulfate anion. Examples of the aforementioned sulfonic acid anions include alkyl sulfonic acid anions having an alkyl group with 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as methanesulfonic acid anion, ethanesulfonic acid anion, propanesulfonic acid anion, butanesulfonic acid anion, pentasulfonic acid anion, hexanesulfonic acid anion, heptasulfonic acid anion, and octylsulfonic acid anion.

[0060] The quaternary ammonium cation is preferably the cation represented by the following formula (1).

[0061] [Chemistry 1]

[0062]

[0063] In equation (1), R 1 ~R 4Each group independently represents an aliphatic hydrocarbon group with 1 to 20 carbon atoms.

[0064] As R 1 R 2 R 3 R 4 Examples of aliphatic hydrocarbon groups include straight-chain or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; and alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecanyl, octadecenyl, nonadecanyl, and eicosyl (hereinafter also referred to as "alkenyl groups corresponding to the above alkyl groups"). Alkyl groups are preferred, and straight-chain alkyl groups are more preferred.

[0065] R 1 R 2 R 3 R 4 The aliphatic hydrocarbon group shown preferably has 1 to 15 carbon atoms, more preferably 1 to 12. Additionally, R... 1 R 2 R 3 R 4 The total number of carbon atoms in the aliphatic hydrocarbon groups shown is preferably 4 to 40, more preferably 6 to 30, and even more preferably 10 to 20. 1 R 2 R 3 R 4 At least one of the aliphatic hydrocarbon groups preferably has 3 to 20 carbon atoms (preferably 4 to 15).

[0066] The above-mentioned quaternary ammonium salt (E1) is preferably a combination of sulfate ester anion and quaternary ammonium cation shown in formula (1).

[0067] It should be noted that both the aforementioned quaternary ammonium salt (E1) and the ionic liquid (E3) described later are formed from cationic and anionic components. However, quaternary ammonium salts dissolve in molecular solvents and only exhibit ionic conductivity with the aid of solvents. In contrast, ionic liquids exhibit ionic conductivity even without the addition of molecular solvents. This is the difference between them.

[0068] The content of the aforementioned quaternary ammonium salt (E1) in the aforementioned polyurethane resin molded article is preferably 0.5 parts by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less.

[0069] Examples of organometallic salts (E2) include trifluoromethanesulfonic acid, bis(trifluoromethanesulfonyl)imine metal salt, tri(trifluoromethanesulfonyl)methane metal salt, alkyl sulfonate metal salt, benzene sulfonate metal salt, alkylbenzene sulfonate metal salt, and sulfate ester metal salt.

[0070] The metal component of the organometallic salt (E2) is preferably, from the viewpoint of solubility in organic solvents, an alkali metal such as lithium, sodium, or potassium, or an alkaline earth metal such as magnesium, with lithium being particularly preferred.

[0071] The content of the organometallic salt (E2) in the polyurethane resin molded article is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

[0072] The mass ratio (E1 / E2) of the quaternary ammonium salt (E1) to the organometallic salt (E2) is preferably in the range of 1 / 1 or more and 10 / 1 or less, and more preferably in the range of 3 / 1 or more and 8 / 1 or less, from the perspective of obtaining better peel strength and antistatic properties, and from the perspective of making it easier to adjust the value of b / a to the range specified in the present invention.

[0073] The aforementioned ionic liquid (E3) refers to a salt with a melting point below 100°C at atmospheric pressure (1013 hPa), preferably being liquid at atmospheric pressure (1013 hPa) and room temperature (25°C). The cation component of the aforementioned ionic liquid (E3) includes one or more selected from imidazolium cations, pyridinium cations, pyrrolidineium cations, piperidinium cations, and quaternary ammonium cations. However, the aforementioned ionic liquid (E3) differs from the aforementioned quaternary ammonium salt (E1).

[0074] Examples of the aforementioned ionic liquids (E3) include 1-ethyl-3-methyl-imidazolium methanesulfonate, 1-ethyl-3-methyl-imidazolium ethyl sulfate, 1-ethyl-3-methyl-imidazolium thiocyanate, 1-ethyl-3-methyl-imidazolium acetate, 1-butyl-3-methyl-imidazolium methanesulfonate, 1-butyl-3-methyl-imidazolium ethyl sulfate, 1-butyl-3-methyl-imidazolium thiocyanate, and 1-butyl-3-methyl-imidazolium acetate. Among these, 1-ethyl-3-methyl-imidazolium ethyl sulfate and 1-ethyl-3-methyl-imidazolium thiocyanate are preferred for their superior antistatic properties. They can be used alone or in combination of two or more.

[0075] The content of the aforementioned ionic liquid (E3) in the polyurethane resin molded article is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0076] Examples of antistatic agents (E4) include cationic antistatic compounds such as methanesulfonate derivatives and p-toluenesulfonate derivatives.

[0077] Examples of antistatic additives (E5) include cyclic ketones, sorbitan fatty acid esters, and lactone monomers. Examples of cyclic ketones include cyclopentanone, cyclohexanone, cycloheptanone, and their derivatives. Examples of sorbitan fatty acid esters include sorbitan sesquioleate, sorbitan monooleate, sorbitan monostearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan monooleate. Examples of lactone monomers include β-propiolactone, γ-butyrolactone, δ-pentanolactone, ε-caprolactone, and γ-crotonyllactone.

[0078] All or part of the above-mentioned antistatic agent may be included in the main agent (i), but from the viewpoint of uniform mixing and control of curing reaction, it is preferable to include all of it in the curing agent (ii).

[0079] The aforementioned first polyurethane resin composition preferably includes a foaming agent. By including a foaming agent, the polyurethane resin composition can be foamed. Water is preferred as the foaming agent. The content of the foaming agent relative to 100 parts by weight of the aforementioned compound (B) is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, and preferably 0.8 parts by weight or less, more preferably 0.4 parts by weight or less. If the content of the foaming agent is within the above range, a stable foaming state is easily achieved.

[0080] The above-mentioned urethane resin composition may further include a foaming agent. As the foaming agent, one or more compounds (hydrocarbon compounds or halogenated hydrocarbon compounds, preferably halogenated hydrocarbon compounds) with low boiling points (e.g., below 50°C, preferably below 40°C) can be used, such as 1,1-dichloro-1-fluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, dichloromethane, pentane, etc.

[0081] The aforementioned foaming agent and foaming aid may be partially or wholly included in at least one of the main agent (i) and the curing agent (ii), preferably all of them are included in the curing agent (ii).

[0082] The aforementioned first polyurethane resin composition preferably further comprises a catalyst (D). One or more catalysts (D) may be used, such as triethylamine, triethylenediamine, palmityl dimethylamine, pentamethyldiethylenetriamine, N,N-dimethylaminoethyl ether, dimethylethanolamine, triethanolamine, N,N,N',N'-tetramethylhexamethylenediamine, N-methylimidazolium, N-ethylmorpholine, toluenediamine, 4,4'-diaminodiphenylmethane, and other amine compounds, or organometallic compounds such as dioctyltin dilaurate, stannous octoate, and dibutyltin dilaurate. From the viewpoint of controlling foaming properties, triethylenediamine and N,N-dimethylaminoethyl ether are more preferred as the catalyst (D).

[0083] The content of the catalyst (D) is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and more preferably 1.5 parts by mass or less, more preferably 1 part by mass or less, relative to 100 parts by mass of the compound (B). By keeping the content of the catalyst (D) within the above range, stabilization of the foaming state becomes easier.

[0084] The catalyst (D) may be partially or wholly contained in at least one of the main agent (i) and the curing agent (ii), and more preferably, it may be wholly contained in the curing agent (ii).

[0085] The aforementioned first polyurethane resin composition may contain other additives. Examples of such other additives include flame retardants, foam stabilizers, chain extenders, plasticizers, fillers, colorants, weather stabilizers, light stabilizers, and antioxidants. As a foam stabilizer, one or more can be used, such as silicone compounds like polydimethylsiloxane and polysiloxane-polyalkylene oxide block copolymers, metal soaps, alkylphenols, and surfactants such as ethylene oxide and / or propylene oxide adducts of fatty acids. As a plasticizer, one or more can be used, such as adipate-based polyester plasticizers and benzoic acid-based polyester plasticizers. These other additives may be included in the main agent (i) or in the curing agent (ii).

[0086] The first polyurethane resin composition described above can be manufactured by mixing the main agent (i) and the curing agent (ii). Of all the components contained in the main agent (i) and the curing agent (ii), the molar ratio (NCO / groups containing active hydrogen atoms, such as isocyanate groups, hydroxyl groups, and -NH- groups) is preferably 0.7 or more, more preferably 0.85 or more, and preferably 1.2 or less, more preferably 1.1 or less. By keeping the above molar ratio (NCO / groups containing active hydrogen atoms) within the above range, the strength, flexibility, and wear resistance of the resulting polyurethane resin molded article can be improved.

[0087] When foaming the first polyurethane resin composition described above, the foaming agent described above can be used, hollow beads can be added, and mechanical or chemical foaming can be performed. Alternatively, a low-pressure foaming molding machine, an injection molding machine, or other foaming molding machine can be used.

[0088] The aforementioned first urethane foam layer can be formed using methods such as mold forming (injecting the mixed foaming liquid discharged from the molding machine into the mold) or injection molding (directly injecting the mixed foaming liquid into a closed mold that is directly connected to the outlet of the molding machine).

[0089] As the forming mold (die) mentioned above, an open mold including an upper mold and a lower mold; a planar mold; a cylindrical mold; a concave closed mold, etc. can be used. As the material for the forming mold mentioned above, metals such as iron and aluminum; resins such as epoxy resin can be used.

[0090] [Second carbamate foam layer]

[0091] The aforementioned second urethane foam layer is formed from a foam of urethane resin. Examples of such urethane resins include polyether-based urethane resins, polyester-based urethane resins, and polycarbonate-based urethane resins. In this invention, for example, "polyester-based urethane resin" refers to a urethane resin having units derived from polyester in its molecular chain.

[0092] The density of the second carbamate foam layer is preferably 0.3 g / cm³. 3 The above, more preferably 0.4 g / cm 3 The above, and preferably 0.7 g / cm³ 3 The following is more preferably 0.6 g / cm³ 3 the following.

[0093] The hardness of the second urethane foam layer, when measured according to the Japanese Industrial Standard JIS K 7312-1996 (Hardness Test) using a spring hardness test (Type C), is preferably 40 or more, more preferably 50 or more, and preferably 90 or less, more preferably 80 or less.

[0094] In the second urethane foam layer described above, the diameter of the foam pores is preferably 20 μm or more, more preferably 40 μm or more, even more preferably 60 μm or more, and preferably 400 μm or less, more preferably 300 μm or less, and even more preferably 200 μm or less.

[0095] In the second urethane foam layer described above, when the average pore diameter of the foamed pores in the range greater than 200 μm from the interface with the first urethane foam layer is set as a (μm), and the average pore diameter of the foamed pores in the range less than 200 μm from the interface with the first urethane foam layer is set as b (μm), b / a is less than 1.2, preferably less than 1.15, more preferably less than 1.1, and for example, can be more than 0.7, more than 0.8, or more than 0.9. As a method for adjusting the value of b / a, for example, a method for adjusting the antistatic agent (E) can be cited.

[0096] The aforementioned second urethane foam layer can be manufactured by foaming, molding, and curing a second polyurethane resin composition containing a main agent (i') and a curing agent (ii').

[0097] The main agent (i') preferably comprises a urethane prepolymer (A') having isocyanate groups.

[0098] The aforementioned urethane prepolymer (A') is preferably a reaction product of a polyol (A1') and a polyisocyanate (A2'), and preferably has an isocyanate group. The isocyanate group is preferably located at the end of the urethane prepolymer (A').

[0099] As the aforementioned polyol (A1'), a compound identical to the compound exemplified as the aforementioned polyol (A1) can be given; and as the aforementioned polyisocyanate (A2'), a compound identical to the compound exemplified as the aforementioned polyisocyanate (A2) can be given.

[0100] The molar ratio (NCO / OH) of the isocyanate group contained in the above-mentioned polyisocyanate (A2') to the hydroxyl group contained in the above-mentioned polyol (A1') is preferably 2 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less.

[0101] The reaction between the polyol (A1') and the polyisocyanate (A2') can be carried out under solvent-free conditions or in an organic solvent. Examples of suitable organic solvents 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 best to remove these organic solvents during or after the reaction using methods such as reduced pressure heating or thin-film distillation.

[0102] The reaction temperature of the polyol (A1') and the polyisocyanate (A2') is preferably 50-90°C, the reaction time is preferably 2-24 hours, and the reaction pressure can be any of atmospheric pressure, pressurized pressure, or depressurized pressure. The reaction mode can be any of the known reaction modes such as batch, semi-continuous, or continuous.

[0103] The reaction atmosphere of the above polyol (A1') and the above polyisocyanate (A2') can be an inactive gas atmosphere such as nitrogen or argon, a dry air atmosphere, or a closed environment where no moisture is introduced.

[0104] When reacting the polyol (A1') with the polyisocyanate (A2'), the carbamate catalyst can be coexisted as needed. The catalyst can be appropriately added at any stage of the feedstock input process or the reaction process. Furthermore, the catalyst can be added in a single step, in batches, or continuously.

[0105] The isocyanate group equivalent of the above-mentioned urethane prepolymer (A') is preferably 150-350 g / mol, more preferably 200-300 g / mol. By keeping the isocyanate group equivalent of the urethane prepolymer within the above range, the viscosity of the urethane prepolymer can be suppressed. The isocyanate group equivalent of the above-mentioned urethane prepolymer can be determined according to JIS K1603-2007 Plastics—Test Methods for Aromatic Isocyanates in Polyurethane Raw Materials, Part 1: Determination of Isocyanate Group Content.

[0106] The curing agent (ii') described above preferably comprises a compound (B') having two or more functional groups capable of reacting with isocyanate groups (hereinafter sometimes referred to as "compound (B')").

[0107] As the aforementioned compound (B'), one or more can be used, such as polyols, polyamines, and other compounds containing active hydrogen atoms.

[0108] Regarding the polyol (B1') that is the above-mentioned compound (B'), the same compounds as those exemplified as the above-mentioned polyol (B1) can be cited. Among them, high molecular weight polyols such as polyester polyols, polyether polyols, and polycarbonate polyols are preferred, and polyester polyols are more preferred.

[0109] In the above-mentioned high molecular weight polyols, the content of polyols with 3 or more functions is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and preferably 10% by mass or less, more preferably 7% by mass or less.

[0110] In the above-mentioned polyols (B1'), the content of high molecular weight polyols is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and preferably 100% by mass or less.

[0111] In the above-mentioned polyol (B1'), the content of the low molecular weight polyol is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, further preferably 3 parts by mass or more, and preferably 10 parts by mass or less, more preferably 7 parts by mass or less, relative to 100 parts by mass of the high molecular weight polyol.

[0112] In the above compound (B'), the content of polyol (B1') is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and preferably 100% by mass or less.

[0113] Regarding the polyamine (B2') that is the above-mentioned compound (B'), the same compound as the compound exemplified as polyamine (B2) can be cited.

[0114] As the above-mentioned compound (B'), a polyol (B1') is preferred.

[0115] The second polyurethane resin composition described above preferably further comprises an antistatic agent (E'). Examples of such antistatic agents include quaternary ammonium salts (E1'), organometallic salts (E2'), ionic liquids (E3'), antistatic agents (E4'), and antistatic additives (E5'), with quaternary ammonium salts (E1'), organometallic salts (E2'), and ionic liquids (E3') being more preferred, and quaternary ammonium salts (E1') and organometallic salts (E2') being even more preferred.

[0116] The mass ratio (E1' / E2') of the quaternary ammonium salt (E1') to the organometallic salt (E2') is preferably in the range of 1 / 1 or more and 10 / 1 or less, and more preferably in the range of 3 / 1 or more and 8 / 1 or less, from the perspective of obtaining better peel strength and antistatic properties, and from the perspective of making it easier to adjust the value of b / a to the range specified in the present invention.

[0117] As the above-mentioned quaternary ammonium salt (E1'), organometallic salt (E2'), ionic liquid (E3'), antistatic agent (E4'), and antistatic additive (E5'), the same compounds as those exemplified as the above-mentioned quaternary ammonium salt (E1), organometallic salt (E2), ionic liquid (E3), antistatic agent (E4), and antistatic additive (E5) can be cited.

[0118] The content of the antistatic agent (E') in the second urethane foam layer is preferably 0.1% by mass or more and 3.0% by mass or less, from the perspective of obtaining better peel strength and antistatic properties, and from the perspective of easily adjusting the b / a value to the range specified in the present invention.

[0119] All or part of the aforementioned antistatic agent may be included in the main agent (i'), but from the viewpoint of uniform mixing and control of the curing reaction, it is preferable to include all of it in the curing agent (ii').

[0120] The above-described second urethane resin composition preferably includes the above-described foaming agent, and may also include the above-described foaming aid. The above-described foaming agent and the above-described foaming aid may be partially or wholly included in at least one of the main agent (i') and the curing agent (ii), preferably all included in the curing agent (ii').

[0121] The first polyurethane resin composition described above preferably further comprises a catalyst (D'). Examples of the catalyst (D') are compounds identical to those exemplified as catalyst (D).

[0122] 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, more preferably 1.5 parts by mass or less, relative to 100 parts by mass of the compound (B'). By keeping the content of the catalyst (D') within the above range, stabilization of the foaming state becomes easier.

[0123] The catalyst (D') may be partially or wholly contained in at least one of the main agent (i') and the curing agent (ii'), and more preferably, it may be wholly contained in the curing agent (ii').

[0124] The second polyurethane resin composition described above may contain the other additives mentioned above. These other additives may be contained in the main agent (i') or in the curing agent (ii').

[0125] The aforementioned second polyurethane resin composition can be manufactured by mixing the aforementioned main agent (i') with the aforementioned curing agent (ii'). Among all the components contained in the main agent (i') and curing agent (ii'), the molar ratio (NCO / groups containing active hydrogen atoms, such as isocyanate groups, hydroxyl groups, and -NH- groups) is preferably 0.7 or more, more preferably 0.85 or more, and preferably 1.2 or less, more preferably 1.1 or less. By keeping the above molar ratio (NCO / groups containing active hydrogen atoms) within the above range, the strength, flexibility, and wear resistance of the resulting polyurethane resin molded article can be improved.

[0126] When foaming the second polyurethane resin composition described above, the aforementioned foaming agent can be used, hollow beads can be added, and mechanical or chemical foaming can be performed. Alternatively, a low-pressure foaming molding machine, an injection molding machine, or other foaming molding machine can be used.

[0127] The aforementioned second urethane foam layer can be formed using methods such as mold forming (injecting the mixed foaming liquid discharged from the molding machine into the mold) or injection molding (directly injecting the mixed foaming liquid into a closed mold that is directly connected to the outlet of the molding machine).

[0128] As the forming mold (die) mentioned above, an open mold including an upper mold and a lower mold; a planar mold; a cylindrical mold; a concave closed mold, etc. can be used. As the material for the forming mold mentioned above, metals such as iron and aluminum; resins such as epoxy resin can be used.

[0129] The laminate of the present invention can be manufactured by forming a second urethane foam layer on the first urethane foam layer after forming a first urethane foam layer.

[0130] The laminate of the present invention exhibits good adhesion between layers even when formed under high temperature and high humidity conditions, making it useful as a shoe sole.

[0131] Example

[0132] The present invention will be further described in detail below with examples. However, the present invention is not limited to the following examples. Of course, it can also be implemented with appropriate modifications within the scope of the above and below principles, and all such modifications are included in the technical scope of the present invention.

[0133] [Preparation Example 1: Preparation of the Main Agent (X)]

[0134] 543 parts of 4,4'-diphenylmethane diisocyanate (hereinafter referred to as "4,4'MDI", trademark: MILLIONATE MT, manufactured by Nippon Polyurethane Kogyo Co., Ltd.) and 28.6 parts of carbodiimide-modified MDI (trademark: COSMONATE LL, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) as isocyanate components were added to the reaction vessel, and stirring was started.

[0135] Then, 443.5 parts of polyol a (a polyester polyol with a hydroxyl value of 56.1 mgKOH / g synthesized from ethylene glycol (EG) / 1,4-butanediol (1,4BG) and adipic acid (AA). The polyester polyol has a 5 / 5 molar ratio of EG / 1,4BG) was added in batches and mixed. The reaction was carried out at 60°C for 8 hours under a nitrogen atmosphere to obtain the main agent (X) of isocyanate-terminated urethane prepolymer (A) containing 250 NCO equivalent.

[0136] [Preparation Example 2: Preparation of the first layer curing agent (Y11)]

[0137] A curing agent (Y11) was prepared by thoroughly mixing and stirring polyol b (a polyester polyol with a hydroxyl value of 74.8 synthesized from 2M1,3PD / 1,4BG and AA, where 2M1,3PD / 1,4BG = 6 / 4 molar ratio of polyester polyol) as the isocyanate-based reactive compound (B1), 7.6 parts of EG, 0.17 parts of water (C) as a foaming agent, 1.00 parts of triethylenediamine (TEDA) as a catalyst (D), 7.2 parts of N-ethyl-N,N-dimethyl-N-dodecylammonium ethyl sulfate, and 1.2 parts of lithium trifluoromethanesulfonate.

[0138] [Preparation Examples 3-6: Preparation of the first layer curing agent (Y12)-(Y15)]

[0139] Except for changing the composition of the polyol and antistatic agent as shown in Table 1, curing agents (Y12) to (Y15) were obtained in the same manner as in Preparation Example 2.

[0140] [Table 1]

[0141]

[0142] [Preparation Example 7: Preparation of the second layer curing agent (Y21)]

[0143] A curing agent (Y21) was prepared by thoroughly mixing and stirring the following ingredients: 96.00 parts of polyol c (a polyester polyol with a hydroxyl value of 56 synthesized from EG / 1,4BG and AA, where EG / 1,4BG is in a 5 / 5 molar ratio) as the isocyanate-based reactive compound (B2); 8.10 parts of EG; 0.35 parts of water (C) as a foaming agent; 0.80 parts of triethylenediamine (TEDA) as a catalyst (D); 4.8 parts of N-ethyl-N,N-dimethyl-N-dodecylammonium ethyl sulfate; and 0.80 parts of lithium trifluoromethanesulfonate.

[0144] [Preparation Examples 8-11: Preparation of the second layer curing agent (Y22)-(Y25)]

[0145] Except for changing the composition of the polyol and antistatic agent as shown in Table 2, curing agents (Y22) to (Y25) were prepared in the same manner as in Preparation Example 7.

[0146] [Table 2]

[0147]

[0148] [Example 1]

[0149] Manufacturing of Two-Component Curable Polyurethane Foam Components

[0150] The room temperature for constructing the structure was adjusted to 30°C and the relative humidity to 80%. Then, the main agent (X) and the curing agent (Y11) were mixed in a mixing container at a mass ratio of (X) / (Y11) = 100 / 111, and stirred to prepare the two-component curable foamed polyurethane resin composition (A-1) of the present invention. 160g of this composition was poured into a mold (100mm × 200mm × 8mm) preheated to 40°C. The mold was immediately covered and left at 40°C for 2.5 minutes to form the first layer. The first layer was then removed from the mold and subsequently placed into a mold (100mm x 200mm × 20mm).

[0151] The above-mentioned main agent (X) and the above-mentioned polyol mixture (Y21) were mixed in a mixing container at a mass ratio of (X) / (Y21) = 100 / 107 and stirred to prepare the two-component curable foamed polyurethane resin composition (B-1) of the present invention. 120g was injected into a mold (100mm×200mm×20mm) in which the first layer was placed, and the mold was immediately covered and placed at 40°C for 3.5 minutes. After that, the foamed product was taken out.

[0152] [Example 2]

[0153] Except for changing the composition of the resin compositions of the first and second layers as shown in Table 3, a laminate was obtained in the same manner as in Example 1.

[0154] [Comparative Example 1]

[0155] Manufacturing of Two-Component Curable Polyurethane Foam Components

[0156] The room temperature for constructing the structure was adjusted to 30°C and the relative humidity to 80%. The main agent (X) and the curing agent (Y13) were mixed in a mixing container at a mass ratio of (X) / (Y13) = 100 / 150, and stirred to prepare the two-component curable foamed polyurethane resin composition (A-3) of the present invention. 160g of this composition was poured into a mold (100mm × 200mm × 8mm) preheated to 40°C. The mold was immediately covered and left at 40°C for 2.5 minutes to form the first layer. The first layer was then removed from the mold and subsequently placed into a mold (100mm × 200mm × 20mm).

[0157] The above-mentioned main agent (X) and the above-mentioned polyol mixture (Y23) were mixed in a mixing container at a mass ratio of (X) / (Y23) = 100 / 127 and stirred to prepare the two-component curable foamed polyurethane resin composition (B-1) of the present invention. 120g was injected into a mold (100mm×200mm×20mm) in which the first layer was placed, and the mold was immediately covered and placed at 40°C for 3.5 minutes. After that, the foamed product was taken out.

[0158] [Comparative Examples 2-3]

[0159] Except for changing the composition of the resin compositions of the first and second layers as shown in Table 3, a laminate was obtained in the same manner as in Comparative Example 1.

[0160] [Table 3]

[0161] Table 3 Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Level 1 A-1 A-2 A-3 A-4 A-5 2nd floor B-1 B-2 B-3 B-4 B-5 <![CDATA[Density of the first layer (g / cm 3 )]]> 1.04 1.03 0.96 0.98 0.99 <![CDATA[Density of the second layer (g / cm 3 )]]> 0.5 0.5 0.49 0.49 0.53 Average cell diameter b 88 85 115 150 130 Average bubble diameter a 81 78 80 80 90 b / a 1.1 1.1 1.4 1.9 1.4 Peel strength between layer 1 and layer 2 (N / inc) 120.5 110.5 45.0 35.0 70.0 Resistance value (MΩ) at 23℃ × 65% RH 15 12 10 110 15 Resistance value (MΩ) at 10℃ × 40% RH 80 75 71 530 88

[0162] Examples 1 and 2 of the present invention exhibit high peel strength. They also possess excellent antistatic properties.

[0163] On the other hand, Comparative Examples 1 to 3 all had b / a values ​​greater than the range specified in this invention, resulting in poor peel strength.

Claims

1. A laminated body, characterized in that, It has a first urethane foam layer and a second urethane foam layer. The density of the first urethane foam layer is 0.8 g / cm³. 3 Above and 1.2g / cm 3 the following, The density of the second urethane foam layer is 0.3 g / cm³. 3 Above and 0.7g / cm 3 the following, In the second urethane foam layer, when the average pore diameter of the foamed pores in the range greater than 200 μm from the interface with the first urethane foam layer is defined as 'a', and the average pore diameter of the foamed pores in the range less than 200 μm from the interface with the first urethane foam layer is defined as 'b', b / a is greater than 0.7 and less than 1.2, where the units of a and b are μm. The first urethane foam layer is formed by a first polyurethane resin composition comprising a main agent i and a curing agent ii. The main agent i comprises an isocyanate prepolymer A, which is a product of the reaction between polyol A1 and polyisocyanate A2. The polyol A1 comprises one or more high molecular weight polyols selected from polyester polyols, polyether polyols, and polycarbonate polyols. The curing agent ii comprises compound B having two or more functional groups capable of reacting with isocyanate groups. The compound B contains polyol B1. The polyol B1 comprises one or more high molecular weight polyols selected from polyester polyols, polyether polyols, and polycarbonate polyols, as well as low molecular weight polyols. The low molecular weight polyols comprise at least one or more aliphatic diols selected from ethylene glycol (EG), 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-pentanediol, 1,5-pentanediol, neopentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 2-butyl-2-ethyl-1,3-propanediol, and 2-methyl-1,3-propanediol. The first urethane foam layer further contains an antistatic agent E. The antistatic agent E contains at least a quaternary ammonium salt E1. The content of the antistatic agent E in the first urethane foam layer is less than 4.0% by mass. The second urethane foam layer is formed by a second polyurethane resin composition comprising a main agent i' and a curing agent ii'. The main agent i' comprises a urethane prepolymer A' with isocyanate groups, which is the reaction product of polyol A1' and polyisocyanate A2'. The polyol A1' comprises one or more high molecular weight polyols selected from polyester polyols, polyether polyols, and polycarbonate polyols. The curing agent ii' comprises a compound B' having two or more functional groups capable of reacting with isocyanate groups. The compound B' contains polyol B1'. The polyol B1' comprises one or more high molecular weight polyols selected from polyester polyols, polyether polyols, and polycarbonate polyols, as well as low molecular weight polyols. The low molecular weight polyols comprise at least one or more aliphatic diols selected from ethylene glycol (EG), 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-pentanediol, 1,5-pentanediol, neopentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 2-butyl-2-ethyl-1,3-propanediol, and 2-methyl-1,3-propanediol. The second urethane foam layer further contains an antistatic agent E'. The antistatic agent E' contains at least a quaternary ammonium salt E1'. The content of the antistatic agent E' in the second urethane foam layer is less than 3.0% by mass.

2. The laminated body according to claim 1, wherein, The polyol B1 comprises at least one of the low molecular weight polyols selected from ethylene glycol, 1,3-butanediol, and 1,4-butanediol.

3. The laminated body according to claim 1, wherein, The polyol B1' comprises at least one of the low molecular weight polyols selected from ethylene glycol, 1,3-butanediol, and 1,4-butanediol.

4. The laminated body according to claim 1, wherein, The antistatic agent E further comprises an ionic liquid E3.

5. The laminated body according to claim 1, wherein, The antistatic agent E' further comprises an ionic liquid E3'.

6. The laminate according to claim 1, wherein, The first urethane foam layer further comprises catalyst D.

7. The laminated body according to claim 1, wherein, The second urethane foam layer further comprises catalyst D'.

8. The laminated body according to claim 1, wherein, The first urethane foam layer further comprises an organometallic salt E2 as the antistatic agent E, wherein the mass ratio of the quaternary ammonium salt E1 to the organometallic salt E2, i.e., E1 / E2, is more than 1 / 1 and less than 10 / 1.

9. The laminate according to claim 1, wherein, The second urethane foam layer further comprises an organometallic salt E2' as the antistatic agent E', wherein the mass ratio of the quaternary ammonium salt E1' to the organometallic salt E2', i.e., E1' / E2', is more than 1 / 1 and less than 10 / 1.

10. A shoe sole, characterized in that, A laminate having any one of claims 1 to 9.

Images