Urethane resin composition

Abstract

To provide a two-pack type urethane resin composition that has a sufficient pot life after a main agent and a curing agent have been mixed without separation and precipitation of a filler and a liquid component of a composition before reaction, prevents generation of odor before, during and after curing, and exhibits stable adhesion, which prevents leakage of an environmental load substance even after demolition.SOLUTION: A two-pack type urethane resin composition contains 10-40 pts.mass of castor oil polyol (A), 1-30 pts.mass of polyether-based polyol (B) having a number average molecular weight of more than 350, and 20-60 pts.mass of a filler (C) in 100 pts.mass of a main agent, contains 40-70 pts.mass of a polyether-based polyol modified isocyanate-terminated prepolymer (D), 20-50 pts.mass of a filler (C) and 0.05-5 pts.mass of a silane coupling agent (E) selected from an epoxy silane coupling agent or an isocyanate silane coupling agent in 100 pts.mass of the curing agent, does not contain a solvent, a catalyst and an amine compound in the composition, and does not contain aldehydes as a raw material in the composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a two-component urethane resin composition in which the filler and liquid components do not separate and settle before reaction, which has a sufficient pot life after mixing of the base agent and curing agent, which does not emit odors before, during, or after curing, and which exhibits stable adhesive properties, and which does not leak environmentally hazardous substances even after dismantling. [Background technology]

[0002] A hydroxyl group-containing compound reacts with an isocyanate group-containing compound to produce a urethane bond. The composition before the reaction, the reaction, and the product are sometimes collectively referred to as urethane resin. Urethane resin is liquid before the reaction, but may solidify after the reaction. Taking advantage of this phenomenon, urethane resin is used in various industrial products such as adhesives, films, artificial leather materials, and foam materials.

[0003] When urethane resins are used as adhesives for laminating and assembling indoor items, low odor urethane resin compositions are desired. In order to achieve low odor, there has been a demand for compositions that are solvent-free, do not contain amine compounds, and do not contain aldehydes as raw materials in the composition. There has also been a demand for compositions that do not leak environmentally hazardous substances even after dismantling indoor items, that is, compositions that do not use catalysts.

[0004] Urethane resins may consist of reactive components, liquid components consisting of non-reactive components such as plasticizers, silane coupling agents, antioxidants, and other additives, and fillers. There has been a demand for a two-component urethane resin composition that does not separate and settle out of the fillers and liquid components before the reaction, has a sufficient pot life after mixing the base resin and curing agent, and exhibits stable adhesion.

[0005] Patent Document 1 is a publication relating to a moisture-curable coating composition suitable for use as a surface coating. Since a solvent is used in the urethane resin composition, there is room for improvement in terms of odor. Patent Document 2 is a publication relating to a curable resin composition that cures in a short time by heating and has excellent storage stability. Since an amine compound is used as a urethane resin composition, there is room for improvement in terms of odor, as in Patent Document 1. Patent Document 3 is a publication on an injection repair method that has excellent workability during injection, the injection agent penetrates into the fine details of cracks and floating parts, and the leakage prevention effect is maintained for a long period of time. Since aldehydes are included as raw materials in the urethane resin composition, there is room for improvement in terms of odor, as in Patent Documents 1 and 2. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 3-070781 [Patent Document 2] JP 2015-209437 A [Patent Document 3] Japanese Patent Application Publication No. 7-048430 [Patent Document 4] Japanese Patent Application Publication No. 4-202283 [Patent Document 5] JP 2008-081541 A [Patent Document 6] JP 2006-124575 A

[0007] Patent Document 4 is a publication relating to a sealant for multilayer transparent panels that has high adhesive strength, low moisture permeability, excellent impact resistance, and low temperature dependency of elastic modulus, and a multilayer transparent panel using said sealant. Since a tin catalyst is used in the urethane resin composition, there is room for improvement in terms of leakage of environmentally hazardous substances after dismantling. Patent Document 5 is a publication about a curable resin composition using a urethane prepolymer, which has excellent adhesion to oiled steel sheets and chemically treated steel sheets. Since silicone is added to the urethane resin composition, there is a possibility that the liquid component itself will separate, rather than the filler and the liquid component separating and settling. Patent Document 6 is a publication relating to a low-VOC urethane resin composition that has a small environmental impact and is easy to apply and has excellent coating properties. The specification states that conventional pigment components can be added, but does not show any examples of such addition.

[0008] Summary of the Invention [Problem to be solved by the invention]

[0009] The object of the present invention is to obtain a two-component urethane resin composition which does not separate and settle out of the filler and liquid components in the composition before reaction, has a sufficient pot life after mixing of the base resin and the curing agent, does not emit odors before, during and after curing, and exhibits stable adhesive properties, and does not leak environmentally hazardous substances even after dismantling. [Means for solving the problem]

[0010] The present invention provides a two-component urethane resin composition, which is characterized in that, out of 100 parts by mass of the base agent, it contains 10 to 40 parts by mass of castor oil polyol (A), 1 to 30 parts by mass of polyether polyol (B) having a number average molecular weight exceeding 350, and 20 to 60 parts by mass of filler (C); out of 100 parts by mass of the curing agent, it contains 40 to 70 parts by mass of polyether polyol modified isocyanate-terminated prepolymer (D), 20 to 50 parts by mass of filler (C), and 0.05 to 5 parts by mass of silane coupling agent (E) selected from epoxy silane coupling agents and isocyanate silane coupling agents; and the composition does not contain a solvent, a catalyst, or an amine compound, and further does not contain aldehydes as a raw material in the composition. Effect of the Invention

[0011] The composition before the reaction does not separate or settle out of the filler and liquid components, has a sufficient pot life after the base agent and curing agent are mixed, does not emit odors before, during, or after curing, and is a two-component urethane resin composition that exhibits stable adhesive properties.It is also a two-component urethane resin composition that does not leak environmentally hazardous substances even after dismantling, so it can be used both indoors and outdoors, and can be used for purposes other than as an adhesive. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] In the two-liquid urethane resin composition of the present application, the castor oil polyol (A) in 100 parts by mass of the main agent can be a commercially available product. Specific product names include trade name: LAV (hydroxyl value: 156-165), trade name: Marutoku A (hydroxyl value: 156-165), trade name: Kaktoku A (hydroxyl value: 156-165), trade name: Daiya (hydroxyl value: 156-165), trade name: Kakukoichi (hydroxyl value: 156-165), and trade name: Koichi (hydroxyl value: 156-165), all manufactured by Ito Oil Mills. A more preferred material is Koichi, and the amount of addition is 10-40 parts by mass out of 100 parts by mass of the main agent, and more preferably 15-35 parts by mass out of 100 parts by mass of the main agent.

[0013] In the two-component urethane resin composition of the present invention, a commercially available product can be used as the polyether polyol (B) having a number average molecular weight of more than 350 per 100 parts by mass of the main component. Specifically, the product names are: ADEKA's product name: P-400, product name: P-700, product name: P-1000, product name: P-3000, product name: BPX-11, product name: BPX-21, product name: BPX-33, product Product name: BPX-55, product name: BPX-1000, product name: BPX-2000, product name: G-400, product name: G-700, product name: G-1500, product name: G-3000B, product name: G-4000, etc. A more preferred material is G-700, and the amount added is 1 to 30 parts by mass per 100 parts by mass of the base material, and more preferably 3 to 20 parts by mass per 100 parts by mass of the base material.

[0014] In the two-liquid urethane resin composition of the present application, the filler (C) in 100 parts by mass of the main component can be an inorganic filler such as calcium carbonate, talc, silica, kaolin, calcined kaolin, clay, calcium silicate, calcium sulfate, aluminum oxide (alumina), aluminum hydroxide, aluminum silicate, titanium oxide, zinc oxide, magnesium carbonate, magnesium silicate, zeolite, glass beads, shirasu balloons, etc. Also, an organic filler such as polyethylene, polypropylene, polymethyl methacrylate, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-vinyl acetate copolymer, nylon, polyethylene terephthalate, polybutylene terephthalate, polystyrene, ABS resin, acrylonitrile-styrene copolymer, polycarbonate, etc. can be added. A more preferred material is calcium carbonate, which is commercially available from Nitto Funka Kogyo, Shiraishi Calcium, Maruo Calcium, Inoue Seki Kogyo, Shimizu Kogyo, and the like. As for the type of calcium carbonate, there are heavy calcium carbonate obtained by crushing limestone, light calcium carbonate obtained by reacting slaked lime with carbon dioxide, etc., and any of them may be used. As for the surface treatment of calcium carbonate, either an untreated product or a product treated with a silane coupling agent or the like can be used. The amount added is 20 to 60 parts by mass per 100 parts by mass of the base material, and more preferably 30 to 55 parts by mass per 100 parts by mass of the base material.

[0015] In the two-liquid urethane resin composition of the present application, zeolite can be added to the base material in order to remove carbon dioxide generated at the beginning of the reaction. Commercially available zeolite can be used. Examples of commercially available zeolite include Molecular Sieve 5A and Molecular Sieve 13X, both of which are trade names of Union Showa Co., Ltd. A more preferred material is Molecular Sieve 5A, and the amount added is 0.5 to 5 parts by mass per 100 parts by mass of the base material, and more preferably 1 to 4 parts by mass per 100 parts by mass of the base material.

[0016] In the two-component urethane resin composition of the present application, a commercially available product can be used as the polyether-based polyol-modified isocyanate-terminated prepolymer (D) in 100 parts by mass of the curing agent. Examples of commercially available products include Huntsman's product names: SUPRASEC1004, SUPRASEC1007, SUPRASEC1306, SUPRASEC1412, SUPRASEC2004, SUPRASEC2008, SUPRASEC2020, SUPRASEC2024, SUPRASEC2026, 2029, SUPRASEC2045, SUPRASEC2054, SUPRASEC2058, SUPRASEC2060, SUPRASEC2067, SUPRASEC2344, and SUPRASEC2405. These can be used alone or in combination. More preferred materials are SUPRASEC1007 and SUPRASEC2060, and the amount added is 40 to 70 parts by mass, and more preferably 45 to 65 parts by mass, per 100 parts by mass of the curing agent.

[0017] In the two-component urethane resin composition of the present application, the filler (C) in 100 parts by mass of the curing agent may be the same as the filler described in paragraph 0014. The amount added is 20 to 50 parts by mass per 100 parts by mass of the curing agent, and more preferably 35 to 45 parts by mass per 100 parts by mass of the base agent.

[0018] The curing agent of the two-liquid urethane resin composition of the present application contains a silane coupling agent (E) selected from an epoxy silane coupling agent or an isocyanate silane coupling agent. These can be commercially available products. Examples of the epoxy silane coupling agent include KBM-303, KBM-402, KBM-403, KBE-402, and KBE-403, both of which are manufactured by Shin-Etsu Chemical Co., Ltd. Examples of the isocyanate silane coupling agent include KBE-9007N, both of which are manufactured by Shin-Etsu Chemical Co., Ltd. A more preferred material is KBM-403, and the amount of addition is 0.05 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the curing agent.

[0019] In the two-liquid urethane resin composition of the present application, a dehydrating agent can be added to the curing agent to remove moisture in the system. Examples of the dehydrating agent include paratoluenesulfonyl isocyanate (PTSI). The amount of the dehydrating agent added is 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the curing agent.

[0020] In order to impart flexibility to the two-liquid urethane resin composition of the present application, a plasticizer can be added to the curing agent. Examples of the plasticizer include diisononyl adipate (DINA). The amount of the plasticizer added is 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the curing agent.

[0021] In the two-component urethane resin composition of the present application, the ratio of the number of moles of hydroxyl groups (-OH) reactive with the isocyanate component of the main agent to the number of moles of isocyanate groups (-NCO) reactive with the hydroxyl groups of the polyether-based polyol-modified isocyanate-terminated prepolymer of the curing agent is (-NCO / -OH) = 0.5 to 3, more preferably (-NCO / -OH) = 1.0 to 2.0.

[0022] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Note that all parts are by weight. EXAMPLES

[0023] Preparation of base material in Example 1 28 g of Koichi, 12 g of G-700, 25 g of heavy calcium carbonate manufactured by Bihoku Funka Kogyo Co., Ltd. (trade name: BF-200), 32 g of heavy calcium carbonate manufactured by Maruo Calcium Co., Ltd. (trade name: M-300J), and 3 g of molecular sieves were weighed into the kettle of a planetary mixer (trade name: PLM-2) manufactured by Inoue Seisakusho Co., Ltd., and stirred and mixed at 70°C under reduced pressure to obtain a uniform composition.

[0024] Preparation of hardener for Example 1 20 g of SUPRASEC1007, 39 g of SUPRASEC2060, 1 g of DINA, 23.5 g of BF-200, 15 g of M-300J, 1 g of PTSI, and 0.5 g of KBM-403 were weighed into the kettle of an Inoue Seisakusho planetary mixer (trade name: PLM-2), and stirred and mixed at 23°C under reduced pressure to obtain a uniform composition.

[0025] Preparation of base materials for Examples 2 to 6 and Comparative Examples 1 to 6 The base materials of Examples 2 to 6 and Comparative Examples 1 to 6 were obtained in the amounts shown in Tables 1 and 2 by the same procedure as in the preparation of the base material of Example 1. GP-250 is a trifunctional polyether polyol having a number average molecular weight of 300 or less, manufactured by Sanyo Chemical Industries, Ltd.

[0026] Preparation of hardeners for Examples 2 to 6 and Comparative Examples 1 to 6 The curing agents of Examples 2 to 6 and Comparative Examples 1 to 6 were obtained in the amounts shown in Tables 1 and 2 by the same procedure as in the preparation of the curing agent of Example 1. KBM-903 and KBM-1003 are an aminosilane coupling agent and a vinylsilane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. The viscosity of each composition was measured at 20 rpm for 1 minute using a Brookfield viscometer, BH, No. 6. The measurement temperature was 23±1° C. The measurement results are shown in Tables 1 and 2.

[0027] Check the odor of the hardener Both the base agent and the hardener were checked for odor, but the base agent did not fail the odor test, while the hardener did, so only the results for the hardener are shown. The results are shown in Tables 3 and 4, and the evaluation method was to fan the composition with the hand up to the nose. If no odor was detected, it was marked as a pass (◯), and if an odor was detected, it was marked as a fail (×). In addition, for Comparative Examples 5 and 6, which failed the odor check, the pot life and adhesive strength were not checked thereafter.

[0028] Check for separation of hardener Both the base agent and the hardener were checked for separation of the filler and liquid components, and while there were no failures in the base agent, only the hardener was found to have failed, so only the results for the hardener are shown. The results are shown in Tables 3 and 4, and the evaluation method was to fill a film case 40mm in diameter and 108mm in height with the liquid, incubate it in a constant temperature bath at 50℃ for 14 days, and then remove it from the constant temperature bath and measure the depth of the liquid component, which was visible in the transparent state. Less than 3mm is a pass, and more than 3mm is a fail.

[0029] Preparation of compositions of Examples 1 to 6 and Comparative Examples 1 to 4 75 g of each of the base resin and hardener in Examples 1 to 6 and the base resin and hardener in Comparative Examples 1 to 6 was weighed out and uniformly stirred with a stirring spring-loaded motor while taking care not to introduce bubbles. The ratio of the number of moles of hydroxyl groups (-OH) that can react with the isocyanate component of the base resin to the number of moles of isocyanate groups (-NCO) that can react with the hydroxyl groups of the curing agent prepolymer, (-NCO / -OH), and the viscosity measured in the same manner as for the preparation of each base resin and curing agent are shown in Tables 5 and 6. Using this liquid, the pot life and adhesive strength were confirmed.

[0030] Confirmation of pot life of compositions of Examples 1 to 6 and Comparative Examples 1 to 4 The viscosity of each of the compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 was measured, and the time it took for the viscosity to reach five times its original value when stored at 23° C. The results are shown in Tables 5 and 6. The judging criteria are: 80 minutes or more is a pass, and less than 80 minutes is a fail.

[0031] Confirmation of adhesive strength of compositions of Examples 1 to 6 and Comparative Examples 1 to 4 Two cold-rolled steel plates (SPCC plates) measuring 25 mm x 100 mm x 1 mm were prepared. The composition was applied to the edge of one of the SPCC plates so that the composition was 200 g / m2, and the edge of the other SPCC plate was placed on top of it, so that the adhesive area was 25 mm x 25 mm, and the plates were clamped with clips. The plates were incubated in a 23°C environment for 7 days to prepare test pieces for measuring adhesive strength. The shear strength was measured using a uniaxial testing machine at a tensile speed of 5 mm. The measurement environment was 23±1°C, and n=5 was used as an average.

[0032] In Examples 1 to 6, which are two-component urethane resin compositions characterized in that, out of 100 parts by mass of the base material, 10 to 40 parts by mass of castor oil polyol (A), 1 to 30 parts by mass of polyether polyol (B) having a number average molecular weight exceeding 350, and 20 to 60 parts by mass of filler (C) are contained, out of 100 parts by mass of the curing agent, 40 to 70 parts by mass of polyether polyol modified isocyanate terminated prepolymer (D), 20 to 50 parts by mass of filler (C), and 0.05 to 5 parts by mass of silane coupling agent (E) selected from epoxy silane coupling agents or isocyanate silane coupling agents are contained, and the composition does not contain a solvent, a catalyst, or an amine compound, and further does not contain aldehydes as a raw material in the composition, all passed the odor check of the curing agent, the separation check of the curing agent, the pot life check of the composition, and the adhesive strength check.

[0033] Comparative Examples 1 to 3, which did not contain epoxy silane in the curing agent, failed the test for checking the separation of the curing agent. Comparative Example 5, which used amino silane instead of epoxy silane, and Comparative Example 6, which used vinyl silane, failed the test for checking the odor. Comparative Example 4, in which a polyether polyol having a number average molecular weight of 350 or less was used as the base resin, failed the pot life confirmation.

[0034] [Table 1]

[0035] [Table 2]

[0036]

Table 3

[0037]

Table 4

[0038]

Table 5

[0039]

Table 6

Claims

1. A two-component urethane resin composition comprising: The composition contains 100 parts by mass of a base material, 10 to 40 parts by mass of a castor oil polyol (A), 1 to 30 parts by mass of a polyether polyol (B) having a number average molecular weight of more than 350, and 20 to 60 parts by mass of a filler (C), The composition contains, per 100 parts by mass of the curing agent, 40 to 70 parts by mass of a polyether-based polyol-modified isocyanate-terminated prepolymer (D), 20 to 50 parts by mass of a filler (C), 0.05 to 5 parts by mass of a silane coupling agent (E) selected from an epoxy silane coupling agent or an isocyanate silane coupling agent, and 0.1 to 5 parts by mass of paratoluenesulfonyl isocyanate (PTSI) as a dehydrating agent, and does not contain a phosphorus oxygen acid or a derivative thereof; A two-liquid type urethane resin composition, which is characterized in that it does not contain a solvent, a catalyst, or an amine compound, and further does not use an aldehyde itself as a raw material in the composition.

2. 2. The two-component urethane resin composition according to claim 1, wherein the base material contains 0.5 to 5 parts by mass of zeolite.

3. The two-component urethane resin composition according to claim 1 or 2, wherein the ratio of the number of moles (-OH) of hydroxyl groups reactive with the isocyanate component of the base resin to the number of moles (-NCO) of isocyanate groups reactive with hydroxyl groups of the polyether-based polyol-modified isocyanate-terminated prepolymer of the curing agent is (-NCO / -OH) = 0.5 to 3.

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