Curable composition

Abstract

To ensure excellent coatability and sag resistance, while also enabling the sufficient improvement of coating film properties such as elongation and strength, in a curable composition including a first liquid comprising an isocyanate group-containing compound and a second liquid comprising an active hydrogen-containing compound.SOLUTION: A curable composition of the present invention comprises a first liquid comprising an isocyanate group-containing compound and a second liquid comprising an active hydrogen-containing compound. The first liquid and / or the second liquid comprises scaly particles as a filler, and the active hydrogen-containing compound comprises a hydrazide group-containing compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a novel curable composition. [Background technology]

[0002] Conventionally, as a two-liquid type curable composition, one having a first liquid containing an isocyanate group-containing compound and a second liquid containing an active hydrogen-containing compound is known. Such a curable composition can exhibit excellent physical properties such as extensibility, and is therefore applied to, for example, surface coating materials for buildings, civil engineering structures, and the like. In particular, it is preferably used as a coating waterproofing material that enhances waterproofing on the rooftops, verandas, and the like of buildings. Such coating waterproofing materials are generally often applied with trowels, spatulas, rollers, brushes, and the like, and good coating workability is required. In particular, in the rising parts of buildings, etc., it is necessary to ensure not only coating workability but also sagging resistance, etc.

[0003] In response to such problems, for example, Patent Document 1 (JP 2018-44068 A) discloses a two-liquid type urethane waterproofing material composition consisting of a first component containing an isocyanate group-terminated prepolymer having a specific isocyanate skeleton, and a second component containing a specific aromatic amine, and describes that it can impart sufficient extensibility, etc. It also describes that the viscosity can be increased by blending an inorganic filler, making it applicable to rising parts (vertical surfaces), etc. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2018-44068 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the above-mentioned composition, when an inorganic filler is blended to impart viscosity and increase sagging resistance, the strength of the coating film may become insufficient.

[0006] The present invention has been made in view of such problems, and has an object to provide a curable composition having a first liquid containing an isocyanate group-containing compound and a second liquid containing an active hydrogen-containing compound, which ensures excellent coating workability, sagging resistance, etc., while sufficiently improving coating film properties such as extensibility and strength. [Means for solving the problem]

[0007] Means for Solving the Problems The present inventors conducted intensive research to solve the above problems, and came up with the idea of ​​making a specific active hydrogen-containing compound and a filler essential components in a curable composition having a first liquid containing an isocyanate group-containing compound and a second liquid containing an active hydrogen-containing compound, thereby completing the present invention.

[0008] That is, the present invention has the following features. 1. A curable composition having a first liquid containing an isocyanate group-containing compound and a second liquid containing an active hydrogen-containing compound, The active hydrogen-containing compound includes a hydrazide group-containing compound, The first liquid and / or the second liquid contain scaly particles as a filler. A curable composition comprising: 2. The curable composition according to 1, wherein the active hydrogen-containing compound comprises a hydrazide group-containing compound and an aromatic amine compound. Effect of the Invention

[0009] The curable composition of the present invention can ensure excellent coating workability, sagging resistance, etc., and can also sufficiently improve coating film properties such as extensibility and strength. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, an embodiment of the present invention will be described.

[0011] The curable composition of the present invention has a first liquid containing an isocyanate group-containing compound and a second liquid containing an active hydrogen-containing compound. In such a curable composition, the first liquid and the second liquid are packaged separately during distribution, and are mixed together when used (when applying). In the present invention, the active hydrogen-containing compound contains a hydrazide group-containing compound, and the scaly particles are contained as a filler, thereby ensuring excellent coating workability, sagging resistance, etc., and further sufficiently improving coating film properties such as extensibility and strength.

[0012] (Isocyanate group-containing compound) The isocyanate group-containing compound in the first liquid is a compound that is reactive with the active hydrogen-containing compound in the second liquid. As the isocyanate group-containing compound, a polyisocyanate compound having two or more isocyanate groups in one molecule can be used. Specific examples of the polyisocyanate compound include 4,4-diphenylmethane diisocyanate (pure-MDI), polymeric MDI, xylylene diisocyanate (XDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, etc., or derivatives thereof by allophanation, biuretization, dimerization (uretidione formation), trimerization (isocyanurate formation), adductization, carbodiimide formation, etc. Also usable are isocyanate group-terminated urethane prepolymers. As the isocyanate group-containing compound, one or more of these can be used.

[0013] As the isocyanate group-containing compound in the first liquid, an isocyanate group-terminated urethane prepolymer (hereinafter also referred to as "urethane prepolymer") is suitable. The urethane prepolymer is a polymer containing a plurality of isocyanate groups at the molecular end in the molecule. As such a urethane prepolymer, a known one can be used, for example, a reaction product obtained by reacting a polyol compound with a polyisocyanate compound so that the isocyanate group is in excess relative to the hydroxyl group can be used. The isocyanate group content (NCO group content) in the urethane prepolymer is preferably 0.3 to 10 mass% (more preferably 0.5 to 5 mass%). In the present invention, "α to β" is synonymous with "α or more and β or less".

[0014] As the polyol compound constituting the urethane prepolymer, those having two or more hydroxyl groups in one molecule can be used, and examples thereof include polyether polyol, polyester polyol, polymer polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, acrylic polyol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, etc. Among these, examples of the polyether polyol include polypropylene ether diol (polypropylene glycol), polypropylene ether triol, etc.

[0015] The polyisocyanate compound constituting the urethane prepolymer may be one having two or more isocyanate groups in one molecule, such as the various polyisocyanate compounds described above. The amount of the polyisocyanate compound and the polyol compound used in producing the urethane prepolymer is preferably such that the NCO / OH equivalent ratio is 1.2 to 10, more preferably 1.2 to 5.

[0016] (Active hydrogen-containing compounds) Examples of the active hydrogen-containing compound in the second liquid include hydroxyl group-containing compounds and amino group-containing compounds. Of these, examples of the hydroxyl group-containing compound include various polyol compounds. Examples of the polyol compound include polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyester polyol, polybutadiene polyol, castor oil polyol, low molecular weight diols, trimethylolpropane, glycerin, sorbitol, mannitol, and dulcitol. These compounds can be used alone or in combination of two or more.

[0017] Examples of the amino group-containing compound include compounds having two or more primary or secondary amino groups in one molecule. Examples of such amino group-containing compounds include aliphatic polyamine compounds, alicyclic polyamine compounds, aromatic polyamine compounds, heterocyclic amine compounds, aliphatic polyamidoamine compounds, alicyclic polyamidoamine compounds, aromatic polyamidoamine compounds, and hydrazide group-containing compounds. These compounds can be used alone or in combination of two or more.

[0018] The active hydrogen-containing compound may be mixed so that the equivalent ratio (NCO equivalent number / active hydrogen equivalent number) between the isocyanate group of the isocyanate group-containing compound in the first liquid and the active hydrogen (hydroxyl group, amino group, etc.) of the active hydrogen-containing compound in the second liquid is preferably 0.5 to 3 (more preferably 1.1 to 2.5). The amount of the active hydrogen compound mixed is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and even more preferably 3 to 10 parts by mass, relative to 100 parts by mass of the isocyanate group-containing compound (solid content) in the first liquid. In such a case, it is preferable in terms of being able to sufficiently secure the pot life, and it is also possible to further improve performance such as sagging resistance, strength, and extensibility.

[0019] The second liquid may contain either one or both of a hydroxyl group-containing compound and an amino group-containing compound as the active hydrogen-containing compound. The amount of the hydroxyl group-containing compound mixed is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the isocyanate group-containing compound (solid content) in the first liquid. The amount of the amino group-containing compound mixed is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the isocyanate group-containing compound (solid content) in the first liquid.

[0020] The curable composition of the present invention is characterized in that it contains a hydrazide group-containing compound as the active hydrogen-containing compound in the second liquid. In the present invention, by using a hydrazide group-containing compound, which is a type of amino group-containing compound, as an essential component, it is possible to form a coating film with high strength and ensure the coating film properties such as extensibility.

[0021] The hydrazide group-containing compound is preferably a compound having two or more hydrazide groups in one molecule, such as malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and maleic acid dihydrazide. These can be used alone or in combination of two or more. The amount of the hydrazide group-containing compound mixed is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, and even more preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the isocyanate group-containing compound (solid content) in the first liquid.

[0022] The curable composition of the present invention preferably contains an aromatic polyamine compound together with the hydrazide group-containing compound as the active hydrogen-containing compound in the second liquid. In this way, when the active hydrogen-containing compound contains a hydrazide group-containing compound and an aromatic polyamine compound, more advantageous effects can be obtained in terms of pot life, sagging resistance, strength, etc.

[0023] Examples of aromatic polyamine compounds include diethyltoluenediamine, 4,4'-methylene-bis(2-alkylaniline), 4,4'-methylene-bis(2,6-dialkylaniline), 1,3,5-alkyl-2,4-diaminobenzene, methylthiotoluenediamine, tetraalkyldiaminodiphenylmethane, and t-butyltoluenediamine. These compounds can be used alone or in combination of two or more. The amount of the aromatic polyamine compound mixed is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, and even more preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the isocyanate group-containing compound (solid content) in the first liquid. The mixing ratio of the hydrazide group-containing compound and the aromatic polyamine compound is preferably 5:95 to 80:20, more preferably 10:90 to 70:30, and even more preferably 20:80 to 60:40, in terms of mass ratio (hydrazide group-containing compound:aromatic polyamine compound).

[0024] (Filler) The composition of the present invention contains a filler in the first liquid and / or the second liquid. Examples of the embodiment include an embodiment in which the filler is contained in both the first liquid and the second liquid, and an embodiment in which the filler is contained in either the first liquid or the second liquid. In the present invention, an embodiment in which the filler is contained in at least the second liquid is preferable.

[0025] The composition of the present invention is characterized by containing scaly particles (hereinafter also referred to as "component (r)") as a filler. In the present invention, by using the above-mentioned hydrazide group-containing compound in combination with the scaly particles, it is possible to improve the coating workability, sagging resistance, etc., and the strength of the coating film, etc.

[0026] The component (r) is a scaly (also called thin or flake) particle, and its average particle size is preferably 20 μm or less, more preferably 0.01 to 10 μm, even more preferably 0.03 to 3 μm, and particularly preferably 0.05 to 1 μm. The aspect ratio (average particle size / average thickness) is preferably 1 to 100, more preferably 2 to 80.

[0027] As the (r) component, both inorganic particles and organic particles can be used. Examples of scaly inorganic particles include scaly particles of metals or metal oxides, scaly minerals, and scaly glass. Specifically, examples of scaly particles of metals or metal oxides include metals such as aluminum, silver, gold, platinum, nickel, chromium, zinc, indium, titanium, and copper, alloys containing these metals, and oxides of these metals. Examples of scaly minerals include micas such as muscovite, biotite, phlogopite, and synthetic mica, talc, hydrous kaolin clay, and calcined kaolin clay, and examples of scaly organic particles include various resin flakes. These can be used alone or in combination of two or more. Of these, the component (r) is preferably scaly inorganic particles, and more preferably one or more selected from the group consisting of muscovite, biotite, phlogopite, synthetic mica and other micas, talc, hydrous kaolin clay, calcined kaolin clay, and the like.

[0028] The amount of component (r) mixed is preferably 100 parts by mass or less, more preferably 1 to 50 parts by mass, even more preferably 3 to 40 parts by mass, and particularly preferably 5 to 30 parts by mass, per 100 parts by mass of the isocyanate group-containing compound (solid content) in the first liquid.

[0029] The filler may contain calcium carbonate (hereinafter also referred to as "component (s)") having an average particle size of less than 1 μm as a component other than the above-mentioned component (r). The average particle size of component (s) is less than 1 μm, preferably 0.8 μm or less, more preferably 0.001 to 0.5 μm, and even more preferably 0.005 to 0.3 μm. Such component (s) can impart appropriate viscosity (thixotropy, etc.) to the cured composition, thereby contributing to improved performance such as coating workability and sagging resistance. The average particle size of the filler can be measured by a laser diffraction particle size distribution analyzer.

[0030] As the component (s), precipitated calcium carbonate such as colloidal calcium carbonate can be preferably used. Examples of colloidal calcium carbonate that can be used include colloidal fine particles having a shape such as a cube, the particle surface of which is treated with an organic substance such as a fatty acid or a resin acid (e.g., rosin acid).

[0031] While component (s) is an effective component for improving paint workability and sagging resistance, it may have a detrimental effect on strength. In contrast, in the present invention, even when component (s) is contained, the use of the above-mentioned scale-like particles and hydrazide group-containing compound makes it possible to ensure sufficient strength while also ensuring paint workability, sagging resistance, etc.

[0032] The amount of component (s) mixed is preferably 10 to 300 parts by mass, more preferably 30 to 250 parts by mass, further preferably 40 to 200 parts by mass, and particularly preferably 50 to 150 parts by mass, relative to 100 parts by mass of the isocyanate group-containing compound (solid content) in Liquid 1. Such an amount of component (s) mixed is suitable in terms of coating workability, sagging resistance, and the like.

[0033] The composition of the present invention may contain calcium carbonate (hereinafter also referred to as "component (t)") having an average particle size of 1 μm or more as a filler. The average particle size of component (t) is 1 μm or more, preferably 1.1 to 50 μm, more preferably 1.2 to 30 μm. The amount of component (t) mixed is preferably 300 parts by mass or less, more preferably 10 to 200 parts by mass, and even more preferably 20 to 150 parts by mass, relative to 100 parts by mass of the isocyanate group-containing compound (solid content) in the first liquid. The mixing ratio of component (s) to component (t) is preferably 100:0 to 10:90, more preferably 90:10 to 30:70, and even more preferably 80:20 to 50:50 by mass (component (s) : component (t)). In the present invention, the use of such component (t) can enhance the mixability and dispersibility of the filler in the curable composition, which is suitable in terms of the manifestation of the effects of the present invention.

[0034] In the present invention, fillers other than those mentioned above can also be used. Examples of such fillers include calcium oxide, magnesium carbonate, barium sulfate, magnesium sulfate, diatomaceous earth, zeolite, silica gel, glass balloons, shirasu balloons, resin beads, resin powder, rubber powder, wood powder, and resin balloons. These may be subjected to some surface treatment. The average particle size of these is preferably 0.01 to 50 μm, more preferably 0.05 μm to 30 μm. These can be used alone or in combination of two or more.

[0035] (Other Ingredients) The composition of the present invention, in the first liquid and / or the second liquid, may contain, in addition to the above-mentioned components, for example, plasticizers, coloring pigments, dispersants, antifoaming agents, deterioration inhibitors, diluents, thickeners, wetting agents, antifreeze agents, solvents, aggregates, catalysts, preservatives, antifungal agents, anti-algae agents, antibacterial agents, ultraviolet absorbers, light stabilizers, antioxidants, etc.

[0036] Among these, examples of the plasticizer include phthalates such as dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, and butyl benzyl phthalate; and aliphatic carboxylates such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate. These can be used alone or in combination of two or more. In the present invention, the use of such a plasticizer adjusts the viscosity of the composition, and ensures stable coating workability, and also effectively acts in terms of improving the strength of the coating film. The amount of the plasticizer to be mixed is preferably 10 to 200 parts by mass, more preferably 30 to 100 parts by mass, based on 100 parts by mass of the isocyanate group-containing compound (solid content) in the first liquid.

[0037] The first liquid and the second liquid can each be produced by uniformly mixing the above-mentioned components.

[0038] (Curable composition) The curable composition of the present invention has the above-mentioned first liquid and second liquid, which are mixed together when used (when applied). As a specific example of the embodiment, for example, the first liquid contains an isocyanate group-containing compound, and the second liquid contains an active hydrogen-containing compound and a filler. If necessary, a third liquid containing a catalyst and the like can be prepared separately, and these can be mixed together when used (when applied).

[0039] The viscosities of the first liquid and the second liquid can be appropriately set. The viscosity of the first liquid is preferably 1 to 200 Pa·s, more preferably 2 to 100 Pa·s. The viscosity of the second liquid is preferably 50 to 2000 Pa·s, more preferably 100 to 1500 Pa·s. The viscosity referred to here is a value determined by measuring the viscosity at 2 rpm (the indicator value at the second rotation) using a BH type viscometer (at 25°C).

[0040] The mixing ratio (mass ratio) of the first liquid and the second liquid can be appropriately set depending on the composition of the first liquid and the second liquid, but is preferably 50 to 500 parts by mass (more preferably 100 to 300 parts by mass) of the second liquid per 100 parts by mass of the first component. The viscosity of the curable composition after mixing the first liquid and the second liquid is preferably 50 to 2000 Pa s, more preferably 100 to 1500 Pa s.

[0041] Such a curable composition can be used as a surface coating material for buildings, civil engineering structures, etc., and can be used, for example, as a coating waterproofing material for the roofs, verandas, balconies, open corridors, etc. of buildings. It can also be preferably used as a material for the rising parts of such parts. For the substrate to which the composition is applied, pretreatment such as substrate preparation, primer application, and wallpaper application can be performed.

[0042] The curable composition of the present invention can be applied to form a coating film by mixing the first and second liquids and then applying the mixture using a coating tool such as a brush, roller, trowel, spatula, spray, etc. The amount of coating may be appropriately determined depending on the application base, etc., but is preferably 1 to 5 kg / m 2It is also possible to apply the coating in several separate steps. When applying the coating, a reinforcing cloth or the like can be interposed as necessary. The coating and drying can be preferably carried out at room temperature (5 to 40° C.).

[0043] After applying the curable composition, a topcoat material can be applied. By applying the topcoat material, the weather resistance of the formed coating film can be improved. The amount of the topcoat material applied is preferably 0.1 to 0.5 kg / m 2 It is. EXAMPLES

[0044] The features of the present invention will be more clearly described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0045] The following materials were used to constitute the curable composition. Isocyanate group-containing compound [Isocyanate group-terminated urethane prepolymer (NCO%: 3% by mass) Active hydrogen-containing compounds 1 [Hydrazide group-containing compounds (adipic dihydrazide)] Active hydrogen-containing compounds 2 [Hydrazide group-containing compounds (glutaric dihydrazide)] Active hydrogen-containing compounds 3 [Hydrazide group-containing compounds (sebacic acid dihydrazide)] Active hydrogen-containing compounds 4 [Aromatic polyamine compounds (diethyltoluenediamine)] Active hydrogen-containing compounds 5 [Polyol compounds (polyoxypropylene glycol)] Filler 1 [scale-like inorganic particles (hydrous kaolin clay), average particle size 0.2 μm] Filler 2 [Precipitated calcium carbonate (colloidal calcium carbonate (fatty acid treated), average particle size 0.05 μm)] Filler 3 [heavy calcium carbonate, average particle size 2 μm] Color pigment [titanium dioxide] Plasticizer [Diisononyl phthalate] Additives [dispersants, defoamers, deterioration inhibitors, etc.]

[0046] (Examples 1 to 13, Comparative Examples 1 to 3) The components were mixed uniformly by a conventional method to prepare the second liquid. The obtained second liquid was mixed with the first liquid to prepare a curable composition. The raw materials used in the first and second liquids and their mixing ratios are shown in Table 1 (the numbers in the table are parts by mass).

[0047] The following tests were carried out for each curable composition. The results are shown in Table 1. The production and testing of each curable composition were carried out under standard conditions (air temperature 23°C, relative humidity 50%). For each test, the curable composition was used 30 minutes after mixing the first and second liquids.

[0048] <Painting workability> A slate board coated with a waterproofing primer was placed vertically, and each curable composition was applied to the surface with a wool roller at a rate of 2.5 kg / m. 2 The coating workability was evaluated from the viewpoint of the adhesion during roller coating. The evaluation was done on a three-level scale (A>B>C: poor), with "A" being excellent coating workability.

[0049] <Sag resistance> Each curable composition was tested according to JIS A6021:2022 "Waterproof coating materials for architecture" 7.13 "Sag resistance performance test". The evaluation was as follows: "A" for a sag length of 1 mm or less, "B" for a sag length of more than 1 mm and less than 2 mm, and "C" for a sag length of more than 2 mm.

[0050] <Stretchability> Each curable composition was tested according to JIS A6021:2022 "Waterproof coating materials for architecture" 7.6.1 "Tensile performance test at 23°C". The evaluation was as follows: "A" indicates that the elongation rate at break was 550% or more, "B" indicates that the elongation rate at break was 500% or more and less than 550%, and "C" indicates that the elongation rate at break was less than 500%.

[0051] <Coating strength> Each curable composition was tested according to JIS A6021:2022 "Waterproof coating materials for architecture" 7.7 "Tear performance test". The evaluation was as follows: "A" indicates that the tear strength was 15 N / mm or more, "B" indicates that the tear strength was 14 N / mm or more and less than 15 N / mm, and "C" indicates that the tear strength was less than 14 N / mm.

[0052] The evaluation results of each test are shown in Table 1. Examples 1 to 13 showed excellent results in all of coating workability, sagging resistance, extensibility, and coating film strength.

[0053] [Table 1]

Claims

1. A curable composition comprising a first liquid containing an isocyanate group-containing compound and a second liquid containing an active hydrogen-containing compound, The active hydrogen-containing compound includes a hydrazide group-containing compound, The first liquid and / or the second liquid contain scaly particles as a filler. A curable composition comprising:

2. 2. The curable composition according to claim 1, wherein the active hydrogen-containing compound comprises a hydrazide group-containing compound and an aromatic amine compound.

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