Uramate resin composition and laminate

Abstract

This invention provides a carbamate resin composition, characterized by containing: a carbamate resin (A) having a nonionic group, water (B), and a film-forming aid (C) being polyethylene glycol (C1) and / or polyethylene glycol (C2) having an alkoxy group having 11 or fewer carbon atoms. Furthermore, this invention provides a laminate, characterized by having at least a substrate (i) and a foamed layer (ii) formed from the aforementioned carbamate resin composition. This carbamate resin composition can form a film with excellent tear resistance, texture, peel strength, and flexibility at low temperatures.

Description

Technical Field

[0001] This invention relates to water-containing urethane resin compositions. Prior Technology

[0002] Uraffinate resins are widely used in the manufacture of synthetic leather (including artificial leather) due to their good mechanical strength and texture. To date, the mainstream urethane resins used in this application have been solvent-based urethane resins containing N,N-dimethylformamide (DMF). However, due to stricter DMF regulations in Europe, enhanced VOC emission regulations in China and Taiwan, and DMF regulations for large garment manufacturers, there is a growing demand for the removal of DMF from the urethane resin components used in the various layers of synthetic leather.

[0003] In this context, we began to explore the use of urethane dispersions (PUDs) that disperse urethane resins in water as a substitute for the intermediate porous layer formed by the wet coagulation of conventional solvent-based urethane resins. For this substitution, various foams of PUDs were explored to impart a texture equivalent to that of wet-formed products.

[0004] Regarding methods for obtaining the aforementioned PUD foam, for example, the incorporation of microcapsules or mechanical foaming by dispersing gases such as carbon dioxide in the PUD blending liquid has been explored (see, for example, Patent Document 1). However, in the method of incorporating microcapsules, the texture of the resulting foam becomes undesirable, or the smoothness is poor due to the expansion of the microcapsules. Furthermore, in the method of dispersing gases, bubbles in the blending liquid may disappear during the manufacturing process of the foam, making it difficult to control the bubble size, etc., and thus difficult to consistently obtain synthetic leather with good texture.

[0005] Against this backdrop, in recent years, mechanical foaming methods have been explored to easily obtain foamed materials by mechanically stirring PUD. However, in mechanical foaming methods, the urethane film of PUD cracks when the water is dried, resulting in instability in physical properties such as texture, peel strength, and low-temperature bending resistance. [Previous Technical Documents] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2007-191810 Summary of the Invention

[0007] [The problem the invention aims to solve]

[0008] The problem to be solved by the present invention is to provide a water-containing urethane resin composition that, even when mechanically foamed, can form a film with excellent crack resistance, texture, peel strength, and low-temperature flexibility. [Methods used to solve problems]

[0009] This invention provides a carbamate resin composition characterized by containing: a carbamate resin (A) having a nonionic group, water (B), and a film-forming aid (C) that is polyethylene glycol (C1) and / or polyethylene glycol (C2) having an alkoxy group having 11 or fewer carbon atoms. Furthermore, this invention provides a laminate characterized by having at least a substrate (i) and a foamed layer (ii) formed from the aforementioned carbamate resin composition. [Effects of the Invention]

[0010] The urethane resin composition of the present invention contains water and is environmentally friendly. Furthermore, the urethane resin composition of the present invention, even when mechanically foamed, can form a film with excellent tear resistance, texture, peel strength, and low-temperature bending properties. Therefore, the urethane resin composition of the present invention is suitable for use as a material for synthetic leather, and particularly suitable for use as a foaming layer for synthetic leather. Simple Explanation of the Diagram

[0011] none. Implementation

[0012] [The form in which the invention is carried out]

[0013] The urethane resin composition of the present invention contains an urethane resin (A) having a nonionic group, water (B), and a specific film-forming aid (C).

[0014] In this invention, the aforementioned specific film-forming aid (C) must be included. It is speculated that by using the specific film-forming aid (C), the evaporation rate of water in the urethane resin composition during drying can be slowed and uniform, thereby inhibiting film rupture and obtaining a film with excellent texture and peel strength.

[0015] Regarding the aforementioned film-forming aid (C), polyethylene glycol (c1) and / or polyethylene glycol (c2) having alkoxy groups with 11 or fewer carbon atoms must be used.

[0016] Regarding the number of carbon atoms of the aforementioned alkoxy groups in the aforementioned polyethylene glycol (C2), from the perspective of obtaining superior crack resistance, the range is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, and most preferably 1 (methoxy). Furthermore, the number of the aforementioned alkoxy groups in one molecule of the aforementioned polyethylene glycol (C2) is in the range of 1 to 2, preferably 1.

[0017] Regarding the weight-average molecular weights of the aforementioned polyethylene glycol (c1) and polyethylene glycol (c2), from the perspective of obtaining superior rupture resistance, a range of 100 to 4,000 is preferred, more preferably 100 to 3,000, and even more preferably 400 to 2,000. Furthermore, the weight-average molecular weights of the aforementioned polyethylene glycol (c1) and polyethylene glycol (c2) represent values ​​determined by gel permeation column chromatography (GPC).

[0018] Regarding the amount of the aforementioned film-forming aid (C), it is preferably in the range of 0.05 to 50 parts by weight, and more preferably in the range of 0.1 to 20 parts by weight, relative to 100 parts by weight of the urethane resin (A) (= solid content).

[0019] The aforementioned urethane resin (A) has nonionic groups and is dispersible in water. Furthermore, since it does not require a crosslinking agent, it can achieve excellent low-temperature bending properties.

[0020] Regarding the method for obtaining the aforementioned urethane resin with nonionic groups, examples include: using a compound with an oxyethylene structure as a raw material.

[0021] Regarding the aforementioned compounds with an oxyethylene structure, polyether polyols with an oxyethylene structure, such as polyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, and polyethylene glycol dimethyl ether, can be used. These compounds can be used alone or in combination of two or more. Among these, polyethylene glycol and / or polyethylene glycol dimethyl ether are preferred from the perspective of easier control over hydrophilicity.

[0022] Regarding the number average molecular weight of the aforementioned compounds with the ethylene oxide structure, from the perspective of obtaining superior emulsifying properties and water dispersion stability, a range of 200 to 10,000 is preferred, more preferably 300 to 3,000, even more preferably 300 to 2,000, and particularly preferably 300 to 1,000. Furthermore, the aforementioned number average molecular weight of the compounds with the ethylene oxide structure represents the value determined by gel permeation column chromatography (GPC).

[0023] Specifically, regarding the aforementioned urethane resin (A), it is possible to use, for example, chain extenders (a1), polyols (a2), polyisocyanates (a3), and reactants of the aforementioned compounds having an oxyethylene structure.

[0024] Regarding the aforementioned chain extender (a1), those with a molecular weight less than 500 (preferably in the range of 50 to 450) can be used. Specifically, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerol, sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl... Chain extenders containing hydroxyl groups include diphenyl ether and trimethylolpropane; chain extenders containing amine groups include ethylenediamine, 1,2-propanediamine, 1,6-hexanediamine, piperazine, 2,5-dimethylpiperazine, isoflavone diamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethyldiamine, 3,3'-dimethyl-4,4'-dicyclohexylmethyldiamine, 1,4-cyclohexanediamine, and hydrazine. These chain extenders can be used alone or in combination of two or more. Furthermore, the molecular weight of the aforementioned chain extender (a1) is expressed as a value calculated from the chemical formula.

[0025] Regarding the aforementioned chain extender (a1), considering the advantages of easy chain extension at lower temperatures below 30°C, suppressing energy consumption during the reaction, and the superior mechanical strength, film-forming properties, bubble retention, texture, low-temperature flexibility, and peel strength resulting from the introduction of urea groups, as well as the ease with which the high solids content of the urethane resin (A) can be achieved, a chain extender with amine groups (hereinafter referred to as "amine chain extender") is preferred. Furthermore, considering the superior bubble retention, emulsifying properties, low-temperature flexibility, texture, and water dispersion stability, an amine chain extender with a molecular weight in the range of 30 to 250 is even more preferred. Moreover, when two or more of the aforementioned chain extenders are used, the aforementioned molecular weight refers to their average value, which only needs to be within the aforementioned preferred molecular weight range.

[0026] Regarding the aforementioned chain extender (a1), considering the advantages of obtaining superior mechanical strength, film-forming properties, texture, peel strength, bubble retention, emulsifying properties, low-temperature bending properties, and water dispersion stability, and the ease with which the high solids content of the urethane resin (A) can be achieved, it is further preferred to be in the range of 0.1 to 30% by mass of the total mass of the raw materials constituting the urethane resin (X), and particularly preferred to be in the range of 0.5 to 10% by mass.

[0027] Regarding the aforementioned polyol (a2), examples such as polyether polyols, polyester polyols, polyacrylic acid polyols, polycarbonate polyols, and polybutadiene polyols can be used. These polyols can be used alone or in combination of two or more. Furthermore, regarding the aforementioned polyol (a2), compounds other than those with an oxyethylene structure that impart the aforementioned nonionic group can be used.

[0028] Regarding the number-average molecular weight of the aforementioned polyol (a2), from the perspective of the mechanical strength of the resulting membrane, it is preferably in the range of 500 to 100,000, and more preferably in the range of 800 to 10,000. Furthermore, the aforementioned number-average molecular weight of the polyol (a2) represents the value determined by gel permeation column chromatography (GPC).

[0029] Regarding the aforementioned proportion of polyol (a2), from the point of view that superior mechanical strength can be obtained, it is further preferred to be in the range of 40 to 90% by mass of the total mass of the raw materials constituting the urethane resin (A), and more preferably in the range of 50 to 80% by mass.

[0030] Regarding the aforementioned polyisocyanate (a3), aromatic polyisocyanates such as phenyl diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, styrene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimide diphenylmethane polyisocyanate can be used; aliphatic polyisocyanates or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isoflavone diisocyanate, dicyclohexylmethane diisocyanate, styrene diisocyanate, tetramethylstyrene diisocyanate, dimeric acid diisocyanate, and norcamphene diisocyanate can be used. These polyisocyanates can be used alone or in combination of two or more.

[0031] Regarding the aforementioned proportion of polyisocyanate (a3), from the point of obtaining superior mechanical strength, it is further preferred to be in the range of 5 to 40% by mass of the total mass of the raw materials constituting the urethane resin (A), and more preferably in the range of 10 to 35% by mass.

[0032] Regarding the proportion of the aforementioned compound with an oxyethylene structure used, from the perspective of obtaining better bubble retention, emulsification, water dispersion stability, low-temperature bending and film-forming properties, it is preferable that the total mass of the raw materials constituting the urethane resin (A) is 5% or less by mass, more preferably 3% or less by mass, and even more preferably in the range of 0.25 to 3% by mass.

[0033] Regarding the average particle size of the aforementioned urethane resin (A), from the perspective of obtaining superior bubble retention, surface smoothness, texture, low-temperature bending properties, and film-forming properties, a range of 0.01 to 1 μm is preferred, and a range of 0.05 to 0.9 μm is more preferred. Furthermore, the method for determining the average particle size of the aforementioned urethane resin (A) is described in the examples described later.

[0034] Regarding the content of the aforementioned urethane resin (A) in the urethane resin composition of the present invention, it is preferably 50-80% by mass, more preferably 50-70% by mass. Because the so-called urethane resin (A) solid content is high in the aqueous dispersion, its foam retention is even better even by mechanical foaming, and the drying properties of the urethane resin composition are improved. Therefore, its crack resistance during and / or after drying is also better, and excellent texture and low-temperature bending properties can be obtained.

[0035] Regarding the water (B) used in this invention, deionized water, distilled water, etc., can be used. These types of water can be used alone or in combination of two or more.

[0036] Next, the manufacturing method of the urethane resin (A) used in this invention will be described.

[0037] The method for manufacturing the urethane resin (A) used in this invention comprises the following steps: reacting the aforementioned polyol (a2), the aforementioned polyisocyanate (a3), and the aforementioned compound having an oxyethylene structure in the absence of a solvent to obtain an urethane prepolymer (i) having isocyanate groups (hereinafter referred to as the "prepolymer step"); then dispersing the urethane prepolymer (i) in the aforementioned water (hereinafter referred to as the "emulsification step"); and then reacting the aforementioned chain extender (a1) to obtain the urethane resin (A) (hereinafter referred to as the "chain extension step").

[0038] The aforementioned prepolymerization step is preferably carried out in a solvent-free environment. In the prior art, the prepolymerization step is generally carried out in organic solvents such as methyl ethyl ketone and acetone. However, after the emulsification step, a solvent removal step is required to distill off the aforementioned organic solvents, which in actual production requires several production days. Furthermore, it is difficult to completely remove the organic solvents in the aforementioned solvent removal step, and small amounts of organic solvents often remain, making it difficult to be completely environmentally friendly. On the other hand, by manufacturing the prepolymer in a solvent-free environment, it is possible to obtain a completely solvent-free urethane resin, and it is also possible to simplify the production step.

[0039] Regarding the molar ratio [isocyanate group / (hydroxyl and amino group)] of the total number of hydroxyl groups in the aforementioned polyol (a2) and the hydroxyl and amino groups in the aforementioned compound with the oxyethylene structure to the isocyanate groups in the aforementioned polyisocyanate (a3), from the perspective of obtaining better bubble retention, low-temperature bending, crack resistance, surface smoothness, film-forming properties, texture, peel strength, and mechanical strength, it is preferably in the range of 1.1 to 3, and more preferably in the range of 1.2 to 2.

[0040] The reaction of the aforementioned prepolymer step can be exemplified by carrying out the reaction at 50-120°C for 1-10 hours.

[0041] The aforementioned emulsification step can be performed using, for example, a reaction vessel equipped with stirring blades; a kneader, continuous kneader, conical roller, single-shaft extruder, twin-shaft extruder, triaxial extruder, universal mixer, plastic mill, BODEEDA type mixer, etc.; a homogenizer, static mixer, rotary dispersion mixer such as FILMIX, EBARAMILDER, CLEARMIX, Ultra Turrax, Cavitron, Biomixer, etc.; an ultrasonic dispersion device; or a device that does not have moving parts such as an in-tube mixer and can mix by the flow of the fluid itself.

[0042] The emulsification step is preferably carried out at a temperature at which water will not evaporate, for example, in the range of 10 to 90°C. The emulsification step can be carried out using the same equipment as the prepolymer step.

[0043] The aforementioned chain extension step involves reacting the isocyanate groups of the aforementioned urethane prepolymer (i) with the aforementioned chain extender (a1) to increase the molecular weight of the urethane prepolymer (i) and obtain the urethane resin (A). From a production standpoint, the chain extension step is preferably carried out at a temperature below 50°C.

[0044] Regarding the molar ratio [(hydroxyl and amino groups) / isocyanate groups] of the total isocyanate groups of the aforementioned carbamate prepolymer (i) and the hydroxyl and amino groups of the aforementioned chain extender (a1) in the aforementioned chain extension step, it is preferably in the range of 0.8 to 1.1, and more preferably in the range of 0.9 to 1, from the point of obtaining better low-temperature bending properties, crack resistance, film-forming properties and mechanical strength.

[0045] The aforementioned chain extension step can be performed using the same equipment as the aforementioned prepolymer step.

[0046] The urethane resin composition of the present invention contains the aforementioned urethane resin (A), water (B), and film-forming aid (C) as essential components, but may also contain other additives as needed.

[0047] Regarding the aforementioned other additives, examples include: surfactants, crosslinking agents, emulsifiers, neutralizers, tackifiers, carbamate catalysts, fillers, pigments, dyes, flame retardants, leveling agents, and antiblocking agents. These additives can be used alone or in combination of two or more. Furthermore, when manufacturing the aforementioned carbamate resin (A), it is preferable that it is practically free of organic solvents, but the addition of organic solvents as additives is also acceptable.

[0048] Regarding the aforementioned surfactants, from the perspective of preventing the disappearance of bubbles generated by mechanical foaming and obtaining better crack resistance and texture, it is preferable to use surfactants with a hydrophobic part having 10 or more carbon atoms (D).

[0049] Regarding the aforementioned surfactant (D), surfactants such as those shown in formula (2) below can be used; fatty acid salts, succinates, sulfonic acid succinates, octadecyl sulfonic acid succinates, sulfonic acid succinates, etc. These surfactants can be used alone or in combination of two or more.

[0050] (In formula (2), R represents a straight-chain or branched alkyl group with 10 to 20 carbon atoms, and X represents Na, K, NH4, α-porphyrin, ethanolamine, or triethanolamine.)

[0051] Regarding the aforementioned surfactant (D), from the point of view that it can obtain better bubble retention, it is preferable to use the surfactant shown in the aforementioned formula (2), more preferably a straight-chain alkyl group with 13 to 19 carbon atoms, and especially preferably a stearate.

[0052] Regarding the amount of the aforementioned surfactant (D) used, from the perspective of obtaining better bubble retention, the preferred range is 0.01 to 30 parts by weight relative to 100 parts by weight of the aforementioned urethane resin (A) (= solid content), and more preferably 0.1 to 20 parts by weight.

[0053] Next, the laminate of the present invention will be described.

[0054] The aforementioned laminated system has at least a substrate (i) and a foamed layer (ii) formed from the aforementioned urethane resin composition.

[0055] Regarding the aforementioned substrate (i), fiber substrates such as nonwoven fabrics, woven fabrics, and braided fabrics formed from polyester fibers, polyethylene fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, polylactic acid fibers, cotton, linen, silk, wool, glass fibers, carbon fibers, and such blended fibers can be used; nonwoven fabrics formed by impregnating the aforementioned nonwoven fabrics with resins such as polyurethane resins; nonwoven fabrics formed by further providing a porous layer on the aforementioned nonwoven fabrics; and resin substrates such as thermoplastic polyurethane (TPU).

[0056] Next, the method for manufacturing the laminate of the present invention will be described.

[0057] Regarding the aforementioned method for manufacturing laminates, examples can be cited as follows: (X) A method of foaming the aforementioned urethane resin composition to obtain a foaming liquid, coating the foaming liquid onto release paper, drying it, and bonding it to the aforementioned substrate (i); (Y) A method of foaming the aforementioned urethane resin composition to obtain a foaming liquid, applying the foaming liquid to a skin layer made on release paper, drying it, and bonding it to the aforementioned substrate (i); (Z) A method for foaming the aforementioned urethane resin composition to obtain a foaming liquid, applying the foaming liquid to the aforementioned substrate (i), drying it, and, as needed, attaching a skin layer (iii) made on release paper onto it.

[0058] Regarding methods for foaming the aforementioned carbamate resin composition to obtain a foaming liquid, examples include: hand stirring, mechanical foaming using a mixer such as a mechanical mixer. Among these, the method of using a mixer is preferred from the perspective of easily obtaining a foaming liquid. When using a mixer, for example, stirring at 500 to 3,000 rpm for 10 seconds to 10 minutes can be used. In this case, from the perspective of obtaining a foam layer (ii) with good texture, it is preferable that the volume is 1.3 to 7 times before and after foaming, and more preferably 1.2 to 2 times the volume.

[0059] Regarding methods for applying the obtained foaming liquid to a substrate (i), examples include using roller coaters, knife coaters, corner roller coaters, and coaters.

[0060] Regarding the aforementioned drying method for the coated material, one example is drying it at a temperature of 60 to 130°C for 30 seconds to 10 minutes.

[0061] The thickness of the foamed layer (ii) obtained by the above method is, for example, 5 to 300 μm.

[0062] Regarding the density of the aforementioned foam layer (ii), from the perspective of obtaining a superior texture, it is preferably in the range of 200 to 1,000 kg / m³, and more preferably in the range of 400 to 800 kg / m³. Furthermore, the density of the aforementioned foam layer (ii) is expressed as the value obtained by subtracting the weight of the substrate (i) per 10 cm square from the weight of the laminated body per 10 cm square, and dividing the result by the thickness of the foam layer (ii).

[0063] Regarding the aforementioned skin layer (iii), it can be formed using well-known materials and methods, such as solvent-based urethane resins, water-based urethane resins, silicone resins, polypropylene resins, and polyester resins. When a soft texture, heat resistance, and hydrolysis resistance are important, polycarbonate-based urethane resins are preferred. Furthermore, to reduce DMF in an environmentally friendly manner, water-based polycarbonate-based urethane resins are preferred.

[0064] On the aforementioned skin layer (iii), a surface treatment layer (iv) may be further provided as needed for purposes such as improving scratch resistance and imparting gloss. As for the aforementioned surface treatment layer (iv), it can be formed using known materials and known methods.

[0065] The urethane resin composition of the present invention contains water and is environmentally friendly. Furthermore, the urethane resin composition of the present invention, even when mechanically foamed, can form a film with excellent tear resistance, texture, peel strength, and low-temperature bending properties. Therefore, the urethane resin composition of the present invention is suitable for use as a material for synthetic leather, and particularly suitable for use as a foaming layer for synthetic leather. [Example]

[0066] The present invention will be described in more detail below using examples.

[0067] [Synthetic Example 1] Preparation of the urethane resin (A-1) composition In the presence of 0.1 parts by mass of stannous octoate, 1,000 parts by mass of polyether polyol (PTMG2000 manufactured by Mitsubishi Chemical Corporation, quantity average molecular weight: 2,000), 38 parts by mass of polyethylene glycol (PEG600 manufactured by Nippon Oil Corporation, quantity average molecular weight: 600), and 262 parts by mass of dicyclohexylmethane diisocyanate (HMDI) were reacted at 100°C until the NCO% reached 2.8% to obtain a carbamate prepolymer. Using a homogenizer, 65 parts by weight of the aforementioned urethane prepolymer heated to 70°C, 20% aqueous solution of sodium dodecylbenzenesulfonate (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Neogen S-20F"), and 948 parts by weight of water were stirred and mixed to obtain an emulsion. Immediately afterwards, an aqueous dilution of isophorone diamine (IPDA) with an amine group content equivalent to the molar amount of NCO groups was added to extend the chain, ultimately yielding an urethane resin (A-1) composition containing 58% by weight of urethane resin (A-1).

[0068] [Synthetic Example 2] Preparation of the urethane resin (A-2) composition In the presence of 0.1 parts by mass of stannous octoate, 1,000 parts by mass of polycarbonate polyol (based on 1,6-hexanediol, with a number average molecular weight of 2,000), 18 parts by mass of PEG600, and 262 parts by mass of HMDI were reacted at 100°C until the NCO% reached 3.1% by mass, to obtain a urethane prepolymer. Using a homogenizer, 64 parts by weight of the aforementioned urethane prepolymer heated to 70°C, 20% aqueous solution of sodium dodecylbenzenesulfonate emulsifier (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., "Neogen S-20F"), and 811 parts by weight of water were stirred and mixed to obtain an emulsion. Immediately afterwards, an aqueous dilution of IPDA with an amine content equivalent to 95% of the NCO groups was added to extend the chain, ultimately yielding an urethane resin (A-2) composition containing 60% by weight of urethane resin (A-2).

[0069] [Example 1] Using a mechanical mixer at 2,000 rpm, 100 g of the urethane resin (A-1) composition obtained in Synthesis Example 1, 2.0 g of the thickener "Borch Gel ALA" (manufactured by Borchers), 2.0 g of ammonium stearate, and 5.0 g of methoxy polyethylene glycol (manufactured by Nippon Oil Co., Ltd. "Uniox M-550", hereinafter referred to as "MPEG") were stirred to incorporate air, thereby adjusting the mixture to a volume of 150% relative to the initial volume. It is coated onto release paper and dried at 80°C for 3 minutes to obtain a 300μm thick urethane foam layer, which is then laminated with nonwoven fabric to obtain synthetic leather.

[0070] [Example 2] Using a mechanical mixer at 2,000 rpm, 100 g of the urethane resin (A-1) composition obtained in Synthesis Example 1, 2.0 g of the thickener "Borch Gel ALA" (manufactured by Borchers), 2.0 g of ammonium stearate, and 5.0 g of polyethylene glycol (manufactured by Nippon Oil Co., Ltd. "PEG#400", quantity average molecular weight: 400, hereinafter referred to as "PEG") were stirred to incorporate air, thereby adjusting the mixture to a volume of 150% relative to the initial volume. It is coated onto release paper and dried at 80°C for 3 minutes to obtain a 300μm thick urethane foam layer, which is then laminated with nonwoven fabric to obtain synthetic leather.

[0071] [Example 3] Using a mechanical mixer at 2,000 rpm, 100 g of the urethane resin (A-2) composition obtained in Synthesis Example 2, 2.0 g of the thickener "Borch Gel ALA" (manufactured by Borchers), 2.0 g of ammonium stearate, and 5.0 g of MPEG were stirred to incorporate air, thereby adjusting the mixture to a volume of 150% relative to the initial volume. It is coated onto release paper and dried at 80°C for 3 minutes to obtain a 300μm thick urethane foam layer, which is then laminated with nonwoven fabric to obtain synthetic leather.

[0072] [Comparative Example 1] Using a mechanical mixer at 2,000 rpm, 100 g of anionic aqueous carbamate resin (HYDRAN WLS-120AR manufactured by DIC Corporation), 2.0 g of tackifier Borch Gel ALA (manufactured by Borchers Corporation), 2.0 g of ammonium stearate, 5.0 g of MPEG, and 4.0 g of crosslinking agent Carbodilite SV-02 manufactured by Nisshinbo Chemical Co., Ltd. were stirred to incorporate air, thereby adjusting the mixture to 150% of its initial volume. It is coated onto release paper and dried at 80°C for 3 minutes to obtain a 300μm thick urethane foam layer, which is then laminated with nonwoven fabric to obtain synthetic leather.

[0073] [Comparative Example 2] Using a mechanical mixer at 2,000 rpm, 100 g of anionic aqueous carbamate resin (HYDRAN WLS-120AR manufactured by DIC Corporation), 2.0 g of tackifier Borch Gel ALA (manufactured by Borchers Corporation), 2.0 g of ammonium stearate, 5.0 g of PEG, and 4.0 g of crosslinking agent Carbodilite SV-02 manufactured by Nisshinbo Chemical Co., Ltd. were stirred to incorporate air, thereby adjusting the mixture to 150% of its initial volume. It is coated onto release paper and dried at 80°C for 3 minutes to obtain a 300μm thick urethane foam layer, which is then laminated with nonwoven fabric to obtain synthetic leather.

[0074] [Comparative Example 3] Using a mechanical mixer at 2,000 rpm, 100 g of the urethane resin (A-1) composition obtained in Synthesis Example 1, 2.0 g of the thickener "Borch Gel ALA" (manufactured by Borchers) and 3.0 g of ammonium stearate were stirred to incorporate air, thereby adjusting the mixture to a volume of 150% relative to the initial volume. It is coated onto release paper and dried at 80°C for 3 minutes to obtain a 300μm thick urethane foam layer, which is then laminated with nonwoven fabric to obtain synthetic leather.

[0075] [Methods for determining number-average molecular weight, etc.] The quantity-average molecular weight of the polyols, film-forming aids, etc. used in the synthetic examples and comparative synthetic examples is expressed as the value obtained by gel permeation column chromatography (GPC) under the following conditions.

[0076] Measurement apparatus: High-speed GPC device (Tosoh Corporation "HLC-8220GPC") Tube Column: The following tube columns manufactured by Tosoh Corporation are connected in series for use. "TSKgel G5000" (7.8mm I. D. × 30cm) × 1 stick "TSKgel G4000" (7.8mm I. D. × 30cm) × 1 stick "TSKgel G3000" (7.8mm I. D. × 30cm) × 1 stick "TSKgel G2000" (7.8mm I. D. × 30cm) × 1 stick Detector: RI (Differential Refractometer) Column temperature: 40℃ Solution: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (0.4% by mass tetrahydrofuran solution containing the sample) Standard sample: The calibration curve was prepared using the following standard polystyrene.

[0077] (Standard polystyrene) TSKgel Standard Polystyrene A-500 manufactured by Tosoh Corporation TSKgel Standard Polystyrene A-1000 manufactured by Tosoh Corporation TSKgel Standard Polystyrene A-2500 manufactured by Tosoh Corporation TSKgel Standard Polystyrene A-5000 manufactured by Tosoh Corporation TSKgel Standard Polystyrene F-1 manufactured by Tosoh Corporation TSKgel Standard Polystyrene F-2 manufactured by Tosoh Corporation TSKgel Standard Polystyrene F-4 manufactured by Tosoh Corporation TSKgel Standard Polystyrene F-10 manufactured by Tosoh Corporation TSKgel Standard Polystyrene F-20 manufactured by Tosoh Corporation TSKgel Standard Polystyrene F-40 manufactured by Tosoh Corporation TSKgel Standard Polystyrene F-80 manufactured by Tosoh Corporation TSKgel Standard Polystyrene F-128 manufactured by Tosoh Corporation TSKgel Standard Polystyrene F-288 manufactured by Tosoh Corporation TSKgel Standard Polystyrene F-550 manufactured by Tosoh Corporation

[0078] [Method for determining the average particle size of urethane resin (A)] The urethane resin compositions obtained in the examples and comparative examples were measured using a laser diffraction / scattering particle size distribution measuring device (Horiba Manufacturing Co., Ltd. "LA-910") with water as the dispersion, and the average particle size was measured with a relative refractive index of 1.10 and the particle size reference being area.

[0079] [Evaluation methods for fracture resistance] Observe the appearance of the synthetic leather obtained in the examples and comparative examples to confirm whether there are any cracks. Those without cracks are rated as "○", and those with cracks are rated as "×".

[0080] [Methods for evaluating texture] The synthetic leathers obtained in the Examples and Comparative Examples were evaluated by touching them with the hands as follows. "○": It has softness and elasticity. "×": Poor flexibility, hard.

[0081] [Evaluation methods for peel strength] A 2.5 cm wide hot melt adhesive tape (manufactured by Sun Kasei Co., Ltd., "BW-2") was placed on the urethane foam layer side of the synthetic leather obtained in the examples and comparative examples, and heated at 150°C for 30 seconds, followed by the hot melt adhesive tape. The sample was cut along the width of the hot melt adhesive tape. A portion of the sample was peeled off, and the substrate and hot melt adhesive tape were clamped together using a clamp. The peel strength was measured using an Autograph (manufactured by Shimadzu Corporation), and evaluated as follows. The average value of the obtained data was calculated and converted to a width of 1 cm. "○": 3 kgf / cm or more. "×": Less than 3 kgf / cm.

[0082] [Method for determining low-temperature bending properties] The synthetic leather obtained in the examples and comparative examples was subjected to a bending test (-35°C, 100 times / minute) using a deflectometer (manufactured by Yasuda Seiki Co., Ltd., "FLEXOMETER with low temperature chamber"), and the number of times until cracks appeared on the surface of the synthetic leather was measured was evaluated as follows. "○": More than 10,000 times. "×": less than 10,000 times.

[0083] [Table 1] Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Urafrancate resin (A) (A-1) (A-1) (A-2) Ammonium ester resins with anionic groups Ammonium ester resins with anionic groups (A-1) Film-forming aid (C) MPEG PEG MPEG MPEG PEG Surfactant (D) Ammonium stearate Ammonium stearate Ammonium stearate Ammonium stearate Ammonium stearate Ammonium stearate Evaluation of fracture resistance ○ ○ ○ ○ ○ × Texture evaluation ○ ○ ○ ○ ○ × Evaluation of peel strength ○ ○ ○ ○ ○ × Evaluation of low temperature bending performance ○ ○ ○ × × ×

[0084] It is understood that the urethane resin composition of the present invention in Examples 1 to 3 can produce synthetic leather with excellent crack resistance, texture, peel strength and low-temperature bending properties.

[0085] On the other hand, Comparative Examples 1 and 2 are samples in which anionic urethane resins are used instead of nonionic urethane resins (A), and the low-temperature bending performance is poor.

[0086] Comparative Example 3 was the sample without film-forming aid (C), and its tear resistance, texture, peel strength, and low-temperature bending properties were all poor.

[0087] none

Claims

1. A carbamate resin composition comprising: a carbamate resin (A) having a nonionic group, water (B), and a film-forming aid (C) being polyethylene glycol (C1) and / or polyethylene glycol (C2) having an alkoxy group having 11 or fewer carbon atoms, wherein the carbamate resin (A) is made from chain extender (A1), polyol (A2), polyisocyanate (A3), and a compound having an oxyethylene structure as essential raw materials, wherein the polyol (A2) comprises a polycarbonate polyol made from 1,6-hexanediol as an essential raw material, and the content of the compound having an oxyethylene structure is in the range of 0.25% to 3% by mass of the total mass of the raw materials of the carbamate resin (A).

2. The urethane resin composition of claim 1, wherein the weight average molecular weight of the polyethylene glycol (c1) and the polyethylene glycol (c2) is in the range of 100 to 4,000.

3. The urethane resin composition of claim 1 or 2 further contains a surfactant (D) having a hydrophobic portion having 10 or more carbon atoms.

4. The urethane resin composition of claim 3, wherein the surfactant (D) is a stearate.

5. A laminate, characterized in that it has at least a substrate (i) and a foamed layer (ii) formed of an aminocarbamate resin composition as claimed in any one of claims 1 to 4.

6. The laminate as claimed in claim 5, wherein the foamed layer (ii) is formed by mechanically foaming the urethane resin composition.