Two-component urethane resin composition for synthetic leather and synthetic leather

Abstract

To provide a two-liquid type urethane resin composition for synthetic leather, which is quickly hardened when a liquid main agent and a liquid hardener are mixed at room temperature and enables an urethane resin coat applied on a surface of a synthetic leather to be formed so as to have a state of excellent peeling-resisting strength and flexibility, and also to create a synthetic leather having excellent peeling-resisting strength and flexibility using the same.SOLUTION: A two-liquid type urethane resin composition consists of a main agent containing a polyol compound and a chain extender, and a hardener containing an isocyanate compound. The polyol compound is a liquid polyol compound including 1 to 15 mass% of autocatalytic amine-based polyol containing two or more tertiary amine groups and three or more hydroxyl groups in 100 mass% of the polyol compound in the two-liquid type urethane resin composition for synthetic leather.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a two-component urethane resin composition for synthetic leather and synthetic leather using the same. [Background technology]

[0002] Generally, synthetic leathers used in automobile seats, sports shoes, etc. are manufactured by overlaying and integrating a resin layer onto a knitted or woven fabric base. Artificial leather, which has a similar structure to synthetic leather, uses a nonwoven fabric impregnated with a resin liquid as a base fabric, but the structure in which a resin layer is layered and integrated onto the surface of the base fabric is the same as that of synthetic leather, so in this invention, artificial leather is also referred to as synthetic leather.

[0003] Two-component urethane resins used in the resin layer of such synthetic leathers are known to be environmentally friendly, using bio-polyols and bio-chain extenders. One known example is a urethane resin-based prepolymer for synthetic leather that can be instantaneously heated and mixed in a mixer without using organic solvents, and then immediately applied to the base fabric (Patent Document 1).

[0004] Furthermore, a catalyst is used to promote the reaction between the polyol, which is the main component of the two-component urethane resin, and the isocyanate, which is the curing agent component. Known catalysts include tertiary amine compounds, amines having an isocyanate-reactive group, and autocatalytic polyols based on amine initiators containing a tertiary amine group (paragraph 0068 of Patent Document 2).

[0005] The above-mentioned autocatalytic amine polyol is a polyol compound in which a catalytic function has been added to a main component polyol, for example, a functionality of 2 to 8, a hydroxyl value of 15 to 200, and at least one tertiary amine group, which imparts an autocatalytic function, and is known to be used in the production of flexible polyurethane foams (Patent Document 3). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 7295539 [Patent Document 2] Special Publication No. 2003-533565 [Patent Document 3] Special Publication No. 2007-535606 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the two-component urethane resin for synthetic leather described in Patent Document 1 requires a large amount of heat energy during prepolymer preparation, as the polyol (OH) component and isocyanate (NCO) component are heated individually or in a mixed state to lower the viscosity and allow the reaction to occur. Furthermore, after the urethane resin is applied, a large amount of heat energy and time is required for drying and curing, and the amount of filler that can be added is also limited, making it difficult to reduce costs.

[0008] To produce synthetic leather using the above-mentioned urethane resin-based prepolymer, a catalyst must be used just before the polyurethane resin is applied to the base fabric, and the prepolymer and polyol must be mixed instantaneously in an instantaneous mixer to quickly react the OH and NCO components.However, depending on the type and amount of catalyst required, the synthetic leather may be prone to bleed (discoloration) and its physical properties may be reduced.

[0009] The autocatalytic amine polyols disclosed in Patent Documents 2 and 3 contain 2 to 100% by weight of polyols having a hydroxyl value of 15 to 200 in 100% by weight of a foamable polyol composition. The compound contains an unspecified amount of the above-mentioned synthetic leather, and it cannot be said to be applicable to synthetic leather in terms of foaming, peel strength, and sense of unity. In other words, it has not been previously anticipated that such autocatalytic amine polyols would be used to formulate two-component urethane resins for synthetic leather. Even if such polyols were accidentally used, it would be difficult to adjust the heating temperature without impairing the quality in order to adjust the pot life for application to a base fabric or release paper, and it would be difficult to consistently obtain synthetic leather of environmentally friendly quality that has the required flexibility and peel strength resistance.

[0010] Therefore, the object of the present invention is to solve the above-mentioned problems and to provide a two-component urethane resin composition that can reduce the component ratio of prepolymer, which requires a lot of thermal energy to produce, in the resin composition to 50% or less, and that allows the curing reaction to proceed quickly by simply mixing the liquid base agent and curing agent at room temperature without the need for a large amount of catalyst, and that provides a urethane resin coating on synthetic leather that has excellent peel strength resistance and flexibility, or to provide synthetic leather using the two-component urethane resin composition. [Means for solving the problem]

[0011] In order to solve the above problems, the present invention provides a two-component urethane resin composition for synthetic leather, which is composed of a base agent consisting of a mixture of a polyol compound and a chain extender, and a curing agent containing an isocyanate compound, and wherein the polyol compound is a liquid polyol compound containing 1 to 15 mass% of an autocatalytic amine polyol containing two or more tertiary amine groups and three or more hydroxyl groups, relative to 100 mass% of the polyol compound; and synthetic leather using the same.

[0012] The above-mentioned autocatalytic amine polyol is preferably an amine polyether polyol having a hydroxyl value of 300 to 1000 KOHmg / g, which is obtained by addition polymerization of propylene oxide (PO) or ethylene oxide (EO) together with propylene oxide (PO) to one or more amines selected from ethylenediamine, diethylenetriamine, toluenediamine, and tetraethylenepentamine.

[0013] In the two-component urethane resin composition for synthetic leather of the present invention constructed as described above, the liquid polyol compound contained in the base contains a predetermined amount of a specific autocatalytic amine-based polyol. Therefore, simply by mixing the composition with the curing agent at room temperature, the liquid polyol and chain extender react quickly. Therefore, there is less need to react polyol and isocyanate in advance to form a prepolymer, and the prepolymer component ratio in the resin composition can be reduced to 50% or less, resulting in a two-component urethane resin composition that contributes to energy savings and process reductions.

[0014] Furthermore, the reaction rate of the amine polyol containing two or more tertiary amine groups and three or more hydroxyl groups is appropriate, so that the composition has an appropriate usable time for producing synthetic leather. Furthermore, since no organic solvent is required for viscosity adjustment, the drying and curing time of the two-component urethane resin composition is shortened, and the thermal energy consumed in the manufacturing process is also significantly reduced.

[0015] The two-component urethane resin composition of the present invention, in which the base resin and curing agent are in a low-viscosity liquid state, allows for the use of relatively inexpensive fillers in large quantities in the production of synthetic leather. Furthermore, the minimum amount of catalyst required is small, which prevents bleeding and deterioration of the physical properties of the synthetic leather.

[0016] When the base agent contains a biopolyol, a biochain extender, or both, the resulting two-component urethane resin composition is more resource-efficient and environmentally friendly. Furthermore, it is preferable to incorporate a filler such as a biofiller into the base agent in order to achieve the above-mentioned environmentally friendly two-component urethane resin composition.

[0017] Furthermore, when the R value, which is the equivalent ratio (isocyanate group / hydroxyl group) of the two-component urethane resin composition, is 1.0 to 1.4, the physical properties such as the required usable time for application to base fabric or release paper as synthetic leather are stabilized. Furthermore, synthetic leather whose base fabric surface is coated with the above-mentioned two-component urethane resin composition will more stably have the required quality characteristics such as flexibility and peel strength resistance. [Effects of the Invention]

[0018] In this invention, the liquid polyol compound contains a predetermined amount of a specified autocatalytic amine polyol, eliminating the need to prepare large amounts of prepolymer in advance, which requires a lot of thermal energy for production. For example, even when the prepolymer component ratio is 50 mass% or less, the reactivity is excellent, and the liquid base agent and curing agent can be mixed at room temperature without heating, using a small amount of catalyst as needed, and the curing reaction occurs quickly. When applied to the surface of synthetic leather, the two-component urethane resin composition for synthetic leather provides a urethane resin coating with excellent peel strength and flexibility, and this composition has the further advantage of allowing synthetic leather with excellent peel strength and flexibility to be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0019] The two-component urethane resin composition for synthetic leather, which is an embodiment of the present invention, and the raw materials, their blending ratios, and manufacturing conditions for synthetic leather using the same are described in detail below. Where necessary, the abbreviations for chemical components are listed in parentheses after their general names.

[0020] <Autocatalytic amine polyol> The autocatalytic amine polyol used in the present invention has two or more tertiary amine groups (sometimes also referred to as N groups) and three or more hydroxyl groups, preferably has a hydroxyl value of 300 to 1000 KOHmg / g, and is preferably an amine polyether polyol.

[0021] Specific examples of amine-based polyols include those obtained by addition polymerization of propylene oxide (PO) and / or ethylene oxide (EO) with one or more amines selected from ethylenediamine, diethyltriamine, toluenediamine, and tetraethylenepentamine, and examples thereof include Sannix NP-300, NL-300, NL-270, NE-240, and AP-470 manufactured by Sanyo Chemical Industries, Ltd., which are commercially available products obtained by addition polymerization of PO or PO together with EO.

[0022] These amine-based polyols are multifunctional polyols containing tertiary amine groups, have excellent reactivity with isocyanates, cure in an extremely short time, and serve as the main component for producing high-strength urethane resins. In order to obtain such properties, the amine polyol preferably has two or more tertiary amine groups and 3 to 7 hydroxyl groups.

[0023] The amount of autocatalytic amine polyol added is preferably 1 to 15 mass % of the OH component, more preferably 1 to 5 mass %, because if it is less than 1 mass %, the desired effect is insufficient, and if it exceeds 15 mass %, the composition becomes hard, cannot obtain sufficient flexibility, and the usable time is shortened.

[0024] If the hydroxyl value is less than 300 KOHmg / g, the reactivity will be insufficient and quick release from the release paper will be difficult, while if it exceeds 1000 KOHmg / g, the resin will become hard and its flexibility will be poor.

[0025] <Liquid polyol> The liquid polyol used in the present invention is preferably one or more polyols selected from polyester polyols, polyether polyols, polycarbonate polyols, lactone polyols, and castor oil polyols, which are liquid at room temperature. Incidentally, the room temperature in this invention refers to the room temperature defined by the Japanese Industrial Standards (JIS Z 8703), which is in the range of 20°C ± 15°C (5 to 35°C).

[0026] <Chain lengthener (also known as chain extender)> The chain extender used in this invention is preferably one or more selected from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol (1,3PDO), 3-methyl-1,5-pentanediol (MPD), 2-methyl-1,3-propanediol (MPO), etc., which are liquid at room temperature. However, such chain extenders are used selectively depending on the use and purpose of the synthetic leather.

[0027] <Isocyanate> Specific examples of isocyanates used in the present invention include 4,4'-diphenylmethane diisocyanate (MDI), carbodiimide-modified MDI (liquid MDI), 2,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hydrogenated MDI. These dimers and trimers may also be used, and two or more of these may also be used in combination.

[0028] <Additive-1> Specific examples of additives that may be used as needed in the present invention include antioxidants, ultraviolet absorbers, weather resistance agents, viscosity reducers, thickeners, thixotropy-imparting agents, flame retardants, silicone foam stabilizers, foaming agents, antistatic agents, hydrolysis inhibitors, plasticizers, retarders, moisture absorbers, and coupling agents.

[0029] <Additive-2> Other additives include calcium carbonate, aluminum hydroxide, and talc, which have an average particle size of 100 μm or less and are highly dispersible; biofillers such as eggshell powder, seashell powder, apple powder, and wood flour (cellulose); glass balloons (hollow foams); microsphere powder foams; and diatomaceous earth. Two or more of these additives can also be used in combination. Biofillers are particularly preferred as environmentally friendly additives, and examples of such additives (fillers) include biofillers derived from eggshell powder and recycled biofillers, whose main component is calcium carbonate (CaCO3). An example of commercially available eggshell powder is eggshell powder (membrane-removed, average particle size 15 μm) manufactured by Green Techno 21 Co., Ltd.

[0030] The amount of additive-2 such as calcium carbonate can be 10 to 200 parts by mass per 100 parts by mass of the OH component, and preferably 30 to 80 parts by mass. This amount can be adjusted within the allowable range of the instantaneous mixer, but adding an excessive amount is not preferable because it hardens the synthetic leather and impairs its flexibility or softness.

[0031] <Catalyst> The catalyst used in this invention is preferably an amine catalyst including an acid-blocked type and a temperature-sensitive thermal dissociation type, and it is preferable to select and use one or more of these. Commercially available products of such catalysts include U-CAT (registered trademark, manufactured by San-Apro Co., Ltd.) SA102, which is a DBU-octylate salt and has a long usable time, and U-CAT (registered trademark, manufactured by San-Apro Co., Ltd.) 1102, which is a DBN-octylate salt.

[0032] <Composition and manufacturing conditions> (a) Polyol component Liquid polycarbonate has good hydrolysis resistance, and liquid polyether polyol has good low-temperature flexibility, and these can be selected and combined depending on the application. Since the manufacturing process involves only mixing, including the liquid chain extender, a combination with good compatibility is preferred.

[0033] (b) Isocyanate component The isocyanate compound is preferably liquid 4,4'-diphenylmethane diisocyanate (MDI) or a prepolymer with an NCO% of 7 to 30%. For prepolymers with an NCO group content of 7 to 30%, if the NCO% is less than 7%, the viscosity increases and reactivity decreases. If the NCO% is 30% or more, the resin becomes hard and its flexibility decreases. The prepolymer component ratio in the resin component is preferably 0 to 50%. If liquid MDI is used instead of the prepolymer, the viscosity decreases and curing improves, but the resin becomes slightly hard and its flexibility decreases slightly.

[0034] (c) R value [(isocyanate group / hydroxyl group) equivalent ratio] The R value is preferably in the range of 1.0 to 1.4, because if it is less than 1.0, the reactivity will be slow and the physical properties will be insufficient, and if it exceeds 1.4, the resin will be hard and its flexibility will be poor.

[0035] (d) Liquid temperature It is used at room temperature (for example, 25°C), but can be heated up to 50°C if necessary. However, as the temperature increases, the viscosity decreases, but the usable time also becomes shorter, and the amount of catalyst required must be reduced.

[0036] (e) Curing time The curing time used in this invention is the total time including pre-drying and post-drying. Pre-drying is carried out under conditions that result in a semi-cured state with adequate tackiness and that does not penetrate the base fabric. Typically, a curing time of 2 minutes at 120°C is used as a guideline, and the amount of catalyst is adjusted so that the curing time is 2 to 3 minutes at 120 to 130°C. The post-drying is carried out so that the pattern does not collapse and sufficient physical properties can be obtained even when the release paper is peeled off after the base fabric is bonded. [Example]

[0037] The polyol (OH) components (Production Examples 1-4) and isocyanate (NCO) components (Production Examples 5-6) used as the base resin were produced in the blending ratios shown in Tables 1 to 3 below, and comparative prepolymers (OH-R1, OH-R2) were also produced. The raw materials used in the above production are listed below, with the abbreviations shown in Table 1-3 written in brackets. Note that OHV shown below is the hydroxyl value, expressed in KOHmg / g, and f indicates the number of functional groups.

[0038] (1) Bio-liquid polyether polyol (SK Chemicals Co., Ltd.; ECOTRION H-2000, bifunctional (2f), hydroxyl value (OHV) = 56) [H-2000] (2) Liquid polyether polyol (Sanyo Chemical Industries, Ltd.; Sannix PP-1000, 2f, OHV=112) [PPG-1000] (3) Bioliquid chain extender (DuPont; 1,3PDO, 2f, OHV=112) [1,3PDO] (4) 4,4'-Diphenylmethane diisocyanate [MDI] (5) Autocatalytic amine polyol (ethylenediamine PO adduct polyol, manufactured by Sanyo Chemical Industries, Ltd.; Sannix NP-300, 4f, OHV=750) [NP-300] (6) Autocatalytic amine polyol (diethylenetriamine PO adduct polyol, manufactured by Sanyo Chemical Industries, Ltd.; Sannix NP-400, 5f, OHV=700) [NP-400] (7) Liquid polycarbonate dipolyol (Kuraray Co., Ltd.; C-2090, 2f, OHV=56) [C-2090] (8) Liquid polyester dipolyol (Kuraray Co., Ltd.; P-2010, 2f, OHV=56) [P-2010] (9) Liquid castor oil-based polyol (Toyokuni Oil Mills; HS CM-025P, 3f, OHV=200) [HS CM-025P] (10) Carbodiimide-modified liquid MDI (Mitsui Chemicals; Cosmonate LL) [liquid MDI]

[0039] (Production example 1; OH-1a) The above (1) bio-based liquid polyether polyol [H-2000], (2) liquid polyether polyol [PPG-1000], (3) bio-based liquid chain extender [1,3PDO], and (5) amine-based polyol [NP-300] were mixed uniformly at room temperature for 15 minutes in the proportions shown in Table 1 to produce an OH component mixture "OH-1a" with an OHV of 115.72.

[0040] (Production example 2; OH-1b) In the blending ratio shown in Table 1, (1) bio-based liquid polyether polyol [H-2000], (2) liquid polyether polyol [PPG-1000], (3) bio-based liquid chain extender [1,3PDO], and (6) amine-based polyol [NP-400] were mixed uniformly at room temperature for 15 minutes to produce an OH component mixture "OH-1b" with an OHV of 119.88.

[0041] (Production example 3; OH-2a) In the blending ratio shown in Table 1, (7) liquid polycarbonate dipolyol [C-2090], (8) liquid polyester dipolyol [P-2010], (9) liquid castor oil-based polyol [HS CM-025P], (3) bio-based liquid chain extender [1,3PDO], and (5) amine-based polyol [NP-300] were mixed uniformly at room temperature for 15 minutes to produce an OH component mixture "OH-2a" with an OHV of 139.72.

[0042] (Production example 4; OH-2b) In the blending ratio shown in Table 1, (7) liquid polycarbonate dipolyol [C-2090], (8) liquid polyester dipolyol [P-2010], (9) liquid castor oil-based polyol [HS CM-025P], (3) bio-based liquid chain extender [1,3PDO], and (6) amine-based polyol [NP-400] were mixed uniformly at room temperature for 15 minutes to produce an OH component mixture "OH-2b" with an OHV of 131.00.

[0043] (Manufacturing example 5; NCO-1) In the blending ratio shown in Table 1, (8) liquid polyester dipolyol [P-2010] kept at 60°C was added to (4) 4,4'-diphenylmethane diisocyanate [MDI] kept at 60°C, and after stirring at 80°C for 2 hours, (10) carbodiimide-modified liquid MDI [liquid MDI] was added and stirred at 80°C for 1 hour to produce an isocyanate component "NCO-1" with an NCO% of 22.35%.

[0044] (Production example 6; NCO-2) In the proportions shown in Table 1, (1) bio-based liquid polyether polyol [H-2000] and (2) liquid polyether polyol [PPG-1000] were mixed and stirred uniformly at 60°C, and (4) 4,4'-diphenylmethane diisocyanate [MDI], which had been kept at 60°C, was added. The mixture was then stirred at 80°C for 3 hours to produce an isocyanate component "NCO-2" with an NCO% of 10.08%.

[0045] (Prepolymer: OH-R1) In the proportions shown in Table 1, (1) bio-based liquid polyether polyol [H-2000] and (2) liquid polyether polyol [PPG-1000] were mixed and stirred uniformly at 60°C, and (4) 4,4'-diphenylmethane diisocyanate [MDI], which had been kept at 60°C, was added and stirred at 80°C for 2 hours. Then, (3) bio-based liquid chain extender [1,3PDO] was added and reacted at 80°C for 1 hour to produce an OH-type prepolymer "OH-R1" with an OHV of 71.60.

[0046] (Prepolymer: OH-R2) In the proportions shown in Table 1, (7) liquid polycarbonate dipolyol [C-2090], (8) liquid polyester dipolyol [P-2010], and (9) liquid castor oil-based polyol [HS CM-025P] were mixed and stirred at 60°C, and (4) 4,4'-diphenylmethane diisocyanate [MDI], which had been kept at 60°C, was added and stirred at 80°C for 2 hours. Then, (3) bio-based liquid chain extender [1,3PDO] was added and reacted at 80°C for 1 hour to produce an OH-type prepolymer "OH-R2" with an OHV of 96.99.

[0047] [Table 1]

[0048] Next, Examples 1-5 and Comparative Example 1 of the two-component urethane resin composition for synthetic leather of the present invention were produced using the raw materials (main component and NCO component containing OH component, catalyst, and filler) and blending ratios (parts by mass) shown in Table 2 below, and synthetic leather for sports shoes was produced using Examples 1-5. The filler (CaCO3) used was a biofiller derived from eggshell powder.

[0049] The instantaneous mixer used in the examples and comparative examples has a well-known structure as described in Patent Document 1, and is a device that instantly uniformly mixes each liquid supplied to a multi-stage impeller rotating at high speed inside a cylinder, and can discharge the resulting mixture from a mixing head.

[0050] The manufacturing conditions (composition of ingredients, temperature conditions, etc.) and the evaluation of the physical properties of the synthetic leather are listed in Table 2. The evaluation of the physical properties of the synthetic leather, "peel strength (kg / cm) and flexural durability at room temperature," was measured using a flexometer in accordance with the test method of JIS K6545.

[0051] [Example 1] The OH component was a mixture of the polyol compound (OH-1a, liquid temperature 25°C) from Production Example 1 and a tertiary amine catalyst (SA1102, temperature-sensitive catalyst, manufactured by San-Apro Co., Ltd.), which was used as the main component. To this mixture was added NCO-2 (25°C) from Production Example 6 as the curing agent (NCO component), which was mixed and stirred using an instantaneous mixer. The mixture was then applied to a release paper with a skin for sports shoes at a rate of 400 g / m using a roll coater (Comma Coater: registered trademark). 2 was applied.

[0052] This was pre-dried for 2 minutes at 120°C to semi-harden it, and then a nonwoven fabric impregnated with a water-based polyurethane resin, which had been prepared separately, was placed on top of it and post-dried at 120°C for 10 minutes. The release paper was then peeled off to produce a synthetic leather for sports shoes.

[0053] [Example 2] The polyol compound (OH-1a, liquid temperature 25°C) from Production Example 1 was used as the OH component, calcium carbonate (CaCO3) was used as the filler, and a tertiary amine catalyst (SA1102, temperature-sensitive catalyst, manufactured by San-Apro Co., Ltd.) was mixed and stirred to form the main component. NCO-2 (25°C) from Production Example 6 was added as the curing agent (NCO component), and the mixture was mixed and stirred using an instantaneous mixer. The mixture was then applied to a release paper with a skin for sports shoes at a rate of 400 g / m using a roll coater (Comma Coater: registered trademark). 2 was applied.

[0054] This was pre-dried for 2 minutes at 120°C to semi-harden it, and then a nonwoven fabric impregnated with a water-based polyurethane resin, which had been prepared separately, was placed on top of it and post-dried for 9 minutes at 120°C. The release paper was then peeled off to produce synthetic leather for sports shoes.

[0055] [Example 3] The OH component was a mixture of the polyol compound (OH-1b, liquid temperature 25°C) from Production Example 2 and a tertiary amine catalyst (SA1102, temperature-sensitive catalyst, manufactured by San-Apro Co., Ltd.), which was used as the main component. To this mixture, NCO-2 (25°C) from Production Example 6 was added as the curing agent (NCO component), and the mixture was mixed and stirred using an instantaneous mixer. The mixture was then applied to a release paper with a skin for sports shoes at a rate of 400 g / m using a roll coater (Comma Coater: registered trademark). 2 was applied.

[0056] This was pre-dried for 2 minutes at 120°C to semi-harden it, and then a nonwoven fabric impregnated with a water-based polyurethane resin, which had been prepared separately, was placed on top of it and post-dried for 7 minutes at 120°C. The release paper was then peeled off to produce synthetic leather for sports shoes.

[0057] [Example 4] The polyol compound (OH-1b, liquid temperature 25°C) of Production Example 2 as the OH component, calcium carbonate (CaCO3) as a filler, and a tertiary amine catalyst (SA1102, temperature-sensitive catalyst, manufactured by San-Apro Co., Ltd.) were mixed and stirred to form a base resin, and NCO-2 (25°C) of Production Example 6 as a curing agent (NCO component) was added, and the mixture was mixed and stirred using an instantaneous mixer. The mixture was then applied to release paper with a roll coater (Comma Coater: registered trademark) at a concentration of 400 g / m. 2 was applied.

[0058] This was pre-dried for 2 minutes at 120°C to semi-harden it, and then a nonwoven fabric impregnated with a water-based polyurethane resin, which had been prepared separately, was placed on top of it and post-dried for 6 minutes at 120°C. The release paper was then peeled off to produce synthetic leather for sports shoes.

[0059] [Example 5] The polyol compound (OH-1a, liquid temperature 25°C) of Production Example 1 was used as the OH component, and calcium carbonate (CaCO3) and a tertiary amine catalyst (SA1102, temperature-sensitive catalyst, manufactured by San-Apro Co., Ltd.) were mixed and stirred to form the main component. Carbodiimide-modified liquid MDI (Cosmonate LL, NCO 29.0%, manufactured by Mitsui Chemicals, Inc.) was added as the curing agent (NCO component). The mixture was mixed and stirred in an instantaneous mixer, and the mixture was applied to a release paper with a skin for sports shoes at a rate of 400 g / m using a roll coater (Comma Coater: registered trademark). 2 was applied.

[0060] This was pre-dried for 2 minutes at 120°C to semi-harden it, and then a nonwoven fabric impregnated with a water-based polyurethane resin, which had been prepared separately, was placed on top of it and post-dried for 5 minutes at 120°C. The release paper was then peeled off to produce a synthetic leather for sports shoes.

[0061] [Comparative Example 1] The OH component was prepared by mixing and stirring the above-mentioned (prepolymer: OH-R1, liquid temperature 50°C), tertiary amine catalyst (manufactured by Air Products; 33LV) and tertiary amine catalyst (manufactured by San-Apro; SA1102, temperature-sensitive catalyst) to form the main component. To this was added NCO-2 (25°C) from Production Example 6 as the curing agent (NCO component), and the mixture was mixed and stirred using an instantaneous mixer. The mixture was then applied to release paper at a rate of 400 g / m using a roll coater (Comma Coater: registered trademark). 2 was applied.

[0062] This was pre-dried for 2 minutes at 120 minutes to leave it in a semi-hardened state, and then a nonwoven fabric impregnated with a water-based polyurethane resin, which had been prepared separately, was placed on top of this and post-dried at 120°C for 98 minutes. The release paper was then peeled off to produce synthetic leather for sports shoes.

[0063] [Table 2]

[0064] As is clear from the polyol components in Table 1 and the test results shown in Table 2, Examples 1 to 5, which used polyols containing 2 to 5 mass% of an autocatalytic amine polyol (Production Examples 1 and 2), cured in 7 to 12 minutes at room temperature despite having a small amount of tertiary amine catalyst and a prepolymer component ratio of less than 50%. The resin coating of the resulting synthetic leather had a peel strength of 4.2 kg / cm or more, sufficient for sports shoes, and also showed durability of more than 150,000 room-temperature flex cycles. These results demonstrate that Examples 1 to 5 are two-component urethane resin compositions for synthetic leather that can be used with environmentally friendly raw materials and manufacturing conditions to produce high-quality synthetic leather that is durable and practical for sports shoes.

[0065] Next, Examples 6-10 or Comparative Example 2 of the two-component urethane resin composition for synthetic leather of the present invention were produced using the blending ratios (parts by mass) of raw materials shown in Table 3 below, and further synthetic leather for automobiles or furniture was produced using Examples 6-10. Table 3 also lists the manufacturing conditions (composition of ingredients, temperature conditions, etc.) and evaluation of the physical properties of the synthetic leather.

[0066] Among the physical property evaluations of the synthetic leather, the "peel strength" and "room temperature flexibility" were obtained using the same test methods as those shown in Table 2. In addition, hydrolysis resistance testing was performed using the Jungle Test, in which synthetic leather test pieces were exposed to a high-temperature, high-humidity environment of 70°C and 95% humidity for four weeks. Products that showed no deterioration and were of good quality with a property retention rate of 80% or more were rated as good.

[0067] [Example 6] The OH component was a mixture of the polyol compound (OH-2a, liquid temperature 25°C) from Production Example 3 and a tertiary amine catalyst (SA1102, temperature-sensitive catalyst, manufactured by San-Apro Co., Ltd.), which was used as the main component. To this mixture was added NCO-1 (25°C) from Production Example 5 as the curing agent (NCO component), and the mixture was mixed and stirred using an instantaneous mixer. The mixture was then applied to automotive release paper with a surface finish at a rate of 250 g / m using a roll coater (Comma Coater: registered trademark). 2 It was applied.

[0068] This was pre-dried for 2 minutes at 120°C to semi-harden it, then a knitted base fabric for automobiles was placed on top of it and post-dried for 7 minutes at 120°C, and the release paper was peeled off to produce synthetic leather for automobiles or furniture.

[0069] [Example 7] The OH component was a mixture of the polyol compound (OH-2a, liquid temperature 25°C) from Production Example 3, calcium carbonate (CaCO) as a filler, and a tertiary amine catalyst (SA1102, temperature-sensitive catalyst, manufactured by San-Apro Co., Ltd.), which was used as the main component. To this mixture was added NCO-1 (25°C) from Production Example 5 as a curing agent (NCO component), and the mixture was mixed and stirred using an instantaneous mixer. The mixture was then applied to automotive release paper with a surface finish at a rate of 250 g / m using a roll coater (Comma Coater: registered trademark). 2 was applied.

[0070] This was pre-dried for 2 minutes at 120°C to semi-harden it, and then a nonwoven fabric impregnated with a water-based polyurethane resin, which had been prepared separately, was placed on top of it and post-dried for 6 minutes at 120°C. The release paper was then peeled off to produce synthetic leather for automobiles or furniture.

[0071] [Example 8] The OH component was a mixture of the polyol compound (OH-2b, liquid temperature 25°C) from Production Example 4 and a tertiary amine catalyst (SA1102, temperature-sensitive catalyst, manufactured by San-Apro Co., Ltd.), which was used as the main component. To this mixture was added NCO-1 (25°C) from Production Example 5 as the curing agent (NCO component), and the mixture was mixed and stirred using an instantaneous mixer. The mixture was then applied to automotive release paper with a surface finish at a rate of 400 g / m using a roll coater (Comma Coater: registered trademark). 2 was applied.

[0072] This was pre-dried for 2 minutes at 120°C to semi-harden it, and then a nonwoven fabric impregnated with a water-based polyurethane resin, which had been prepared separately, was placed on top of it and post-dried for 5 minutes at 120°C. The release paper was then peeled off to produce synthetic leather for automobiles or furniture.

[0073] [Example 9] The polyol compound (OH-2b, liquid temperature 25°C) of Production Example 4 as the OH component, calcium carbonate (CaCO3) as a filler, and a tertiary amine catalyst (SA1102, temperature-sensitive catalyst, manufactured by San-Apro Co., Ltd.) were mixed and stirred to form the main component, to which NCO-1 (25°C) of Production Example 5 as the curing agent (NCO component) was added, and the mixture was mixed and stirred using an instantaneous mixer. The mixture was then applied to automotive release paper with a surface finish at a rate of 250 g / m using a roll coater (Comma Coater: registered trademark). 2 was applied.

[0074] This was pre-dried for 2 minutes at 120°C to semi-harden it, and then a nonwoven fabric impregnated with a water-based polyurethane resin, which had been prepared separately, was placed on top of it and post-dried for 5 minutes at 120°C. The release paper was then peeled off to produce synthetic leather for automobiles or furniture.

[0075] [Example 10] The OH component was a mixture of the polyol compound (OH-2a, liquid temperature 25°C) from Production Example 3, calcium carbonate (CaCO3) as a filler, and a tertiary amine catalyst (SA1102, temperature-sensitive catalyst, manufactured by San-Apro Co., Ltd.), which was used as the main component. To this mixture was added carbodiimide-modified liquid MDI (Cosmonate LL, NCO 29.0%, manufactured by Mitsui Chemicals, Inc.) as a curing agent (NCO component). The mixture was mixed and stirred using an instantaneous mixer, and applied to automotive surface release paper at a rate of 250 g / m using a roll coater (Comma Coater: registered trademark). 2 was applied.

[0076] This was pre-dried for 2 minutes at 120°C to semi-harden it, and then a nonwoven fabric impregnated with a water-based polyurethane resin, which had been prepared separately, was placed on top of it and post-dried for 4 minutes at 120°C. The release paper was then peeled off to produce synthetic leather for automobiles or furniture.

[0077] Comparative Example 2 The OH component was prepared by mixing and stirring the above-mentioned (prepolymer: OH-R2, liquid temperature 50°C), tertiary amine catalyst (manufactured by Air Products Co., Ltd.; 33LV) and tertiary amine catalyst (manufactured by San-Apro Co., Ltd.; SA1102, temperature-sensitive catalyst) to form the base resin. To this was added NCO-1 (25°C) from Production Example 5 as the curing agent (NCO component), and the mixture was mixed and stirred using an instantaneous mixer. The mixture was then applied to automotive surface release paper at a rate of 250 g / m using a roll coater (Comma Coater: registered trademark). 2 was applied.

[0078] This was pre-dried for 2 minutes at 120°C to semi-harden it, and then a nonwoven fabric impregnated with a water-based polyurethane resin, which had been prepared separately, was placed on top of it and post-dried at 120°C for 58 minutes. The release paper was then peeled off to produce synthetic leather for automobiles or furniture.

[0079] [Table 3]

[0080] As is clear from the polyol components in Table 1 and the test results shown in Table 3, Examples 6 to 10, which used polyols containing 2 to 3% by weight of an autocatalytic amine polyol (Production Examples 3 and 4), cured in 6 to 9 minutes at room temperature despite having a small amount of tertiary amine catalyst and a prepolymer component ratio of 35.0% or less. The resin coating of the resulting synthetic leather had a peel strength of 1.7 kg / cm or more, which is sufficient for synthetic leather for automobiles or furniture, and also showed durability of more than 150,000 bending cycles at room temperature. Based on these findings, Examples 6 to 10 were evaluated as two-component urethane resin compositions for synthetic leather that can be used to produce high-quality, durable synthetic leather for automobiles or furniture using environmentally friendly raw materials and manufacturing conditions. [Industrial Applicability]

[0081] The industrial application fields of this invention include not only sports shoes but also general shoes, automobiles, furniture, bags, sacks, miscellaneous goods, clothing, industrial materials, and other synthetic leathers in general. By appropriately selecting and combining the polyols, chain extenders, and isocyanate compounds used in the production, the invention can be used to produce high-quality synthetic leathers depending on the purpose.

Claims

1. A two-component urethane resin composition for synthetic leather comprises a liquid base agent containing a polyol compound and a chain extender, and a liquid curing agent containing an isocyanate compound, wherein the polyol compound is a liquid polyol compound containing 1 to 15 mass% of an autocatalytic amine polyol containing two or more tertiary amine groups and three or more hydroxyl groups, based on 100 mass% of the polyol compound, and the prepolymer component ratio is less than 50%.

2. 2. The two-component urethane resin composition for synthetic leather according to claim 1, wherein the amine-based polyol is an amine-based polyether polyol having a hydroxyl value of 300 to 1,000 KOH mg / g, which is obtained by addition polymerization of propylene oxide (PO) or propylene oxide (PO) and ethylene oxide (EO) together with one or more amines selected from ethylenediamine, diethylenetriamine, toluenediamine, and tetraethylenepentamine.

3. 3. The two-component urethane resin composition for synthetic leather according to claim 1, wherein the base agent contains a biopolyol, a biochain extender, or both of them.

4. 3. The two-component urethane resin composition for synthetic leather according to claim 1, wherein the equivalent ratio of isocyanate groups to hydroxyl groups in the two-component urethane resin composition is 1.0 to 1.

4.

5. 4. The two-component urethane resin composition for synthetic leather according to claim 3, wherein the equivalent ratio of isocyanate groups to hydroxyl groups in the two-component urethane resin composition is 1.0 to 1.

4.

6. 3. A synthetic leather comprising a base fabric surface coated with the two-component urethane resin composition for synthetic leather according to claim 1.

7. 4. Synthetic leather obtained by coating the surface of a base fabric with the two-component urethane resin composition for synthetic leather according to claim 3.

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