Curable resin composition

Abstract

The present invention provides a curable composition that has a sufficient pot life, exhibits superior coatability and adhesion compared to conventional compositions in the absence of volatile organic solvents, and provides a coating film with superior physical properties compared to conventional compositions as a top coating. [Solution] A two-component curable composition having a first component A and a second component B, wherein the first component A comprises a polyamine compound A1, the polyamine compound A1 comprises aspartic acid ester amine A1A, the second component B comprises a polyisocyanate compound B1, the polyisocyanate compound B1 comprises a uretdione compound B1D having two isocyanate groups and a urethane prepolymer B1P, the aspartic acid ester amine A1A, the uretdione compound B1D and the urethane prepolymer B1P are present in predetermined amounts, and the first component A and the second component B are substantially solvent-free.

Description

Technical Field

[0001] The present invention relates to a curable composition suitable for forming a coating film having physical properties suitable as a top coating.

Background Art

[0002] In recent years, in large buildings such as commercial facilities and hospitals, the rooftops, middle floors, or basements are used as parking lots. Such parking lots are usually provided on the concrete constituting the building as a floor. It is common to apply a urethane coating waterproof material on the concrete floor and apply a top coating having weather resistance, abrasion resistance, etc. over the entire urethane coating waterproof material. One of the materials used for such a top coating is an acrylic urethane resin. Patent Document 1 discloses such an acrylic urethane resin paint.

[0003] On the other hand, Patent Document 2 discloses a curable polyurethane composition using a plurality of polyaspartic acid ester amines having a specific structure. This composition, unlike the technology using a conventional acrylic urethane resin as in Patent Document 1, exhibits good coating properties and adhesiveness even in the absence of a volatile organic solvent, and aims to provide a coating film having physical properties particularly suitable as a top coating for a roofing material including good elongation at break and good tensile strength.

[0004] Patent Document 3 discloses a paint composition containing a main component (I) containing a polyamine compound (A) and a curing agent (II) containing a polyisocyanate compound (B), wherein the polyamine compound (A) contains an aspartic acid ester amine (A1), and the polyisocyanate compound (B) contains an allophanate group-containing polyisocyanate compound (B1). This composition aims to achieve a coating film having good pot life and excellent water-tight adhesion, flexibility, and corrosion resistance.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, the present inventor considered that there is still room for further improvement in these conventional compositions in that they have a sufficient pot life, exhibit good coating properties and adhesiveness even in the absence of volatile organic solvents, and provide a coating film having more suitable physical properties as a top coating such as a roof.

[0007] Therefore, an object of the present invention is to provide a curable composition that has a sufficient pot life, exhibits better coating properties and adhesiveness than conventional ones in the absence of volatile organic solvents, and provides a coating film having better physical properties than conventional ones as a top coating.

Means for Solving the Problems

[0008] One aspect of the present invention for solving the above problems relates to a curable resin composition of the following [1] to [6]. [1] A two - component curable composition having a first component A and a second component B, where the first component A contains a polyamine compound A1, the polyamine compound A1 contains an aspartic acid ester amine A1A, the second component B contains a polyisocyanate compound B1, The polyisocyanate compound B1 comprises a uretdione compound B1D having two isocyanate groups and a urethane prepolymer B1P. The aspartic acid ester amine A1A is present in an amount of 70 to 100 parts by mass relative to 100 parts by mass of the total weight of the polyamine compound A1. The uretdione compound B1D is present in an amount of 10 to 30 parts by mass per 100 parts by weight of the total weight of the polyisocyanate compound B1. The urethane prepolymer B1P is present in an amount of 70 to 90 parts by mass relative to 100 parts by weight of the total weight of the polyisocyanate compound B1. Both the first component A and the second component B are substantially free of organic solvents. Curable composition. [2] The aforementioned aspartic acid ester amine A1A is The following equation (I): [ka] [In formula (I), R 1 It is a divalent hydrocarbon group having 1 to 80 carbon atoms. R 2 This represents a hydrocarbon group having 1 to 20 carbon atoms, either identical or different. The curable composition described in [1], represented by [1]. [3] The uretdione compound B1D having the two isocyanate groups is given by the following formula (II): [ka] [In formula (II), R 201 and R 202 These terms represent a linear or branched alkylene group, a linear or branched unsaturated hydrocarbon group, or an alicyclic hydrocarbon group, respectively. It is represented as, The urethane prepolymer B1P is a reaction product of an isocyanate compound mainly composed of hexamethylene diisocyanate and a polyol, as described in [2], a curable composition. [4] A top coating obtained by curing a curable composition described in any one of items [1] to [3]. [5] A production method for producing a top coating that is placed on and exposed to the floor of a parking lot having a parking area for parking vehicles, The steps include preparing a curable composition as described in any of [1] to [4], The steps include: laminating a primer layer and a waterproof layer on the aforementioned floor in that order; A production method comprising the step of forming a top coating on the waterproof layer by curing a mixture of the curable composition and aggregate. [Effects of the Invention]

[0009] The curable composition of the present invention has a sufficient pot life, exhibits superior applicability and adhesion compared to conventional compositions in the absence of volatile organic solvents, and can provide a coating film with superior physical properties compared to conventional compositions as a top coating. [Brief explanation of the drawing]

[0010] [Figure 1] Figure 1 is a photograph showing an example of a parking lot with parking areas for parking vehicles. [Figure 2] Figure 2 is a photograph illustrating an example where the ramps connecting each floor of a building are used as vehicle access areas. [Figure 3] Figure 3 is a schematic cross-sectional view showing a preferred example of a parking lot floor and a waterproof membrane having the top coating of the present invention placed thereon. [Modes for carrying out the invention]

[0011] [Curable composition] The curable composition of the present invention comprises a first component A and a second component B. These two components are stored separately in containers and not mixed with each other until immediately before application of the curable composition. Such a curable composition is also referred to as a two-component curable composition having a first liquid (main component) and a second liquid (curing agent). The curable composition of the present invention may also have a third component (third liquid) or more components, including other additives described later.

[0012] [First component A] The first component A of the curable composition of the present invention comprises polyamine compound A1. Polyamine compound A comprises aspartate esteramine A1A.

[0013] [Polyamine compound A1] Polyamine compound A1 is preferably the main component of the first component A. In this specification, a particular component is called a "main component" if it is present in an amount of 50% by mass or more relative to 100% by mass of all components of the agent containing the particular component. In other preferred embodiments, the particular component may be present in an amount of 70% by mass or more, 80% by mass or more, or 90% by mass or more relative to 100% by mass of the agent containing the particular component.

[0014] [Aspartic acid ester amine A1A] The amount of aspartic acid ester amine A1A added is preferably 70 to 100 parts by mass, more preferably 80 to 100 parts by mass, even more preferably 90 to 100 parts by mass, and particularly preferably 95 to 100 parts by mass, based on 100 parts by mass of the total weight of polyamine compound A1.

[0015] The aforementioned aspartic acid ester amine A1A is preferably, The following equation (I): [ka] [In formula (I), R 1is a divalent hydrocarbon group having 1 to 80 carbon atoms, R 2 which, being the same or different, each represents a hydrocarbon group having 1 to 20 carbon atoms.] is represented by

[0016] Furthermore, in the compound represented by formula (I), when R 1 has a ring structure (particularly, an alicyclic structure), the secondary amino group in formula (I) is -CH(COOR 2 )-CH2-COOR 2 and is surrounded by the ring structure (particularly, an alicyclic structure) of R 1 . Therefore, it is considered that the effect of suppressing the nucleophilic reaction of the amino group due to steric hindrance is more likely to be exerted.

[0017] R 1 The divalent hydrocarbon group represented by is preferably a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, or a group combined with two or more selected from a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. Also, the C 1 hydrocarbon group represented by is preferably a C 1-80 hydrocarbon group, more preferably a C 1-30 hydrocarbon group, still more preferably a C 1-20 hydrocarbon group.

[0018] R 1 The divalent aliphatic hydrocarbon group represented by is preferably an alkylene group or an alkenylene group, more preferably an alkylene group. The divalent aliphatic hydrocarbon group represented by R 1 may be either linear or branched, and is preferably branched. The number of carbon atoms of the divalent aliphatic hydrocarbon group represented by R 1 is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 10.

[0019] R 1Examples of divalent aliphatic hydrocarbon groups represented by include -CH2-, -CH2CH2-, -CH2CH2CH2-, CH(CH3)CH2-, -C(CH3)2-, -CH2CH2CH2CH2-, -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-, -C(CH3)2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)CH2CH2CH2-, -CH2C H(CH3)CH2CH2-, -C(CH3)2CH2CH2-, CH2C(CH3)2CH2-, -CH2CH2CH2CH2CH2CH2-, -CH(CH3)CH2CH2CH2CH2-, -CH2CH(CH3)CH2CH2CH2-, -CH2CH2CH(CH3)CH2CH2-, -C(CH3)2CH2CH2CH2-, -CH2C(CH3)2CH2CH2-, and the like.

[0020] R 1 The divalent alicyclic hydrocarbon group represented by may be monocyclic or polycyclic, and in the case of polycyclic, it may form a bridging ring. 1 The divalent alicyclic hydrocarbon group represented by is preferably a cycloalkylene group or a cycloalkenylene group, and more preferably a cycloalkylene group. 1 The number of carbon atoms in the divalent alicyclic hydrocarbon group represented by can preferably be 3 to 30, more preferably 4 to 20, and even more preferably 5 to 10.

[0021] R 1 Examples of divalent alicyclic hydrocarbon groups represented by include cyclohexanediyl group, methylcyclohexanediyl group, and isophoronediyl group.

[0022] R 1 The divalent aromatic hydrocarbon group represented by may be monocyclic or polycyclic, and in the case of polycyclic, two or more rings may be fused. 1 The number of carbon atoms in the divalent aromatic hydrocarbon group represented by can preferably be 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10.

[0023] R 1Examples of divalent aromatic hydrocarbon groups represented by include phenylene, torylene, xylylene, and naphthylene groups.

[0024] divalent C 1-80 Aliphatic hydrocarbon group, divalent C 3-80 Alicyclic hydrocarbon groups and divalent C 6-20 Divalent groups, which are formed by combining two or more aromatic hydrocarbon groups, include divalent C 1-80 Aliphatic hydrocarbon group and divalent C 3-80 A divalent group combined with an alicyclic hydrocarbon group; divalent C 1-80 Aliphatic hydrocarbon group and divalent C 6-80 A divalent group combined with an aromatic hydrocarbon group is preferred.

[0025] divalent C 1-80 Aliphatic hydrocarbon group and divalent C 3-80 Examples of divalent groups combined with alicyclic hydrocarbon groups include dicyclohexylmethane-4,4'-diyl group and 2,2'-dimethylmethylenebiscyclohexane-4,4'-diyl group. 1-80 Aliphatic hydrocarbon group and divalent C 6-80 Examples of divalent groups combined with aromatic hydrocarbon groups include the diphenylmethane-4,4'-diyl group and the 2,2-diphenylpropane-4,4'-diyl group.

[0026] R 1 For example, divalent C 1-80 Aliphatic hydrocarbon group, divalent C 3-80 Alicyclic hydrocarbon group, or divalent aliphatic hydrocarbon group and divalent C 3-80 A divalent group combined with an alicyclic hydrocarbon group is preferred. The number of carbon atoms in such a divalent group may be preferably 4 to 80, more preferably 4 to 30, and even more preferably 4 to 20. 1 If the above-mentioned base is present, light resistance (resistance to yellowing of the coating film) is good. Also, R 1 If it is an aliphatic hydrocarbon group, the drying properties of the coating film may be good, R 1 If the group contains an alicyclic hydrocarbon group, the pot life may be improved.

[0027] R 2 The hydrocarbon group represented by is preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a group consisting of two or more selected from aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. 2 C represented by 1-20 The hydrocarbon group is preferably C 1-10 hydrocarbon group, more preferably C 1-5 It can be a hydrocarbon group.

[0028] R 2 The aliphatic hydrocarbon group represented by is preferably an alkyl group. 2 The aliphatic hydrocarbon group represented by may be either a straight chain or a branched chain. 2 The number of carbon atoms in the aliphatic hydrocarbon group required is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.

[0029] R 2 The aliphatic hydrocarbon group represented by can be, for example, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH(CH3)2, or -CH(CH3)CH2CH3.

[0030] R 2 The alicyclic hydrocarbon group represented by may be monocyclic or polycyclic, and in the case of polycyclic, it may form a bridging ring. 2 The alicyclic hydrocarbon group represented by is preferably a cycloalkyl group or a cycloalkenyl group, and more preferably a cycloalkyl group. 2 The number of carbon atoms in the alicyclic hydrocarbon group represented by is preferably 3 to 20, more preferably 3 to 15, and even more preferably 4 to 10.

[0031] R 2 Examples of alicyclic hydrocarbon groups represented by this formula include cyclohexyl groups and methylcyclohexyl groups.

[0032] R 2The aromatic hydrocarbon group represented by may be monocyclic or polycyclic, and in the case of polycyclic, two or more rings may be fused. 2 The number of carbon atoms in the aromatic hydrocarbon group represented by can preferably be 6 to 20, more preferably 6 to 150, and even more preferably 6 to 10.

[0033] R 2 Examples of divalent aromatic hydrocarbon groups represented by include phenyl groups, tolyl groups, xylyl groups, and naphthyl groups.

[0034] The groups, which are combinations of two or more groups selected from aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, are preferably divalent groups combining an aliphatic hydrocarbon group and an alicyclic hydrocarbon group, or groups combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in such groups, which are combinations of two or more groups selected from aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, is preferably 4 to 30, more preferably 4 to 10.

[0035] Examples of groups combining an aliphatic hydrocarbon group and an alicyclic hydrocarbon group include the cyclohexylmethyl group and the methylcyclohexylmethyl group. Examples of divalent groups combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group include the benzyl group and the phenylethyl group.

[0036] R 2 C 1-20 Aliphatic hydrocarbon group or C 3-20 It is preferably an alicyclic hydrocarbon group, C 1-20 It is more preferable that the group be an aliphatic hydrocarbon group.

[0037] Examples of compounds represented by formula (I) include the following:

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] Commercially available products may be used as aspartate esteramine A1A. Commercially available products include, for example, Desmofen NH1523LF (Covestro), Desmofen NH1420 (Covestro), Desmofen NH1220 (Covestro), Desmofen NH1723LF (Covestro), FEISPARTIC F520 (Cas No. 136210-32-7, manufactured by Feiyang), FEISPARTIC F420 (Cas No. 136210-30-5, manufactured by Feiyang), FEISPARTIC F220 (Cas No. 168253-59-6, manufactured by Feiyang), Teraspartic 292 (Cas No. 136210-32-7, manufactured by Pflaumer Brothers), Teraspartic 277 (Cas No. 136210-30-5, manufactured by Pflaumer Brothers), Teraspartic 230 (Cas No. Examples include 168253-59-6 (manufactured by Pflaumer Brothers) and TERASPARTIC295 (Cas No. 152637-10-0, manufactured by Pflaumer Brothers). Among these, NH1420 is preferred. Aspartate ester amine A1A may be a single compound or a combination of two or more compounds.

[0042] The weight-average molecular weight of aspartate ester amine A1A is preferably 150 to 10,000, more preferably 200 to 10,000, and even more preferably 220 to 4,000. In this specification, the weight-average molecular weight is the value converted to polystyrene by gel permeation chromatography (GPC).

[0043] The curable composition of the present invention forms a top coating with a polyurea resin produced by the reaction of polyamine compound A1 and polyisocyanate compound B1. Because the reactivity between polyamine compound A1 and polyisocyanate compound B1 is high, the bonding force is strong, and the resulting top coating may have good durability. On the other hand, polyurethane compounds can be formed by the reaction of polyol compound and polyisocyanate compound, but the reactivity between polyol compound and polyisocyanate compound is lower compared to polyamine compound and polyisocyanate compound, resulting in a slightly weaker layer strength.

[0044] Therefore, in the curable composition of the present invention, the content of the polyol compound is preferably less than or equal to a predetermined value. For example, the content of the polyol compound may be preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass, even more preferably 0 to 5 parts by mass, and most preferably 0 parts by mass, per 100 parts by mass of polyamine compound A1.

[0045] The first component A of the curable composition of the present invention may include a monoamine compound having only one amino group, to the extent that it does not impair the purpose of the present invention. Examples of monoamine compounds include dipropylamine, dibutylamine, diisobutylamine, N-methylhexylamine, di-N-octylamine, tetra(aminomethyl)methane, and aspartic acid.

[0046] [Second component B] The second component B of the curable composition of the present invention comprises a polyisocyanate compound B1. Preferably, the polyisocyanate compound B1 is the main component of the second component B.

[0047] [Polyisocyanate compound B1] Polyisocyanate compound B1 comprises uretdione compound B1D having two isocyanate groups and urethane prepolymer B1P. Uretdione compound B1D and urethane prepolymer B1P may be conventionally known or commercially available products, or they may be synthesized.

[0048] [Uretdione compound B1D] Uretdione is obtained by a cyclodimerization reaction of a compound having multiple isocyanate groups. The uretdione compound B1D is preferably a dimer of a diisocyanate having two isocyanate groups. The uretdione compound B1D is preferably a compound represented by the following chemical formula (II). [ka] In the above equation (II), R 201 and R 202 It is more preferable that each of these be a linear or branched alkylene group, a linear or branched unsaturated hydrocarbon group, or an alicyclic hydrocarbon group. Also, in the above chemical formula (B1), R 201 and R 202 However, it is even more preferable that each is a linear or branched alkylene group having 1 to 6 carbon atoms, a linear or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms, or an alicyclic hydrocarbon group having 5 to 24 carbon atoms. The "linear or branched unsaturated hydrocarbon group" is not particularly limited, but examples include linear or branched alkenylene groups and linear or branched alkylylene groups.

[0049] R 201 and R 202In this context, the "linear or branched alkylene group" is, for example, a methylene group, a dimethylene group (ethylene group), a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. The "linear or branched unsaturated hydrocarbon group" is, for example, a group in which one or more single bonds in the "linear or branched alkylene group" are unsaturated bonds, specifically a vinylene group. In addition, the "alicyclic hydrocarbon group" is, for example, a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, and the like.

[0050] The amount of uretdione compound B1D is preferably 10 to 30 parts by mass, more preferably 12 to 28 parts by mass, even more preferably 14 to 26 parts by mass, particularly preferably 16 to 24 parts by mass, particularly more preferably 18 to 22 parts by mass, and most preferably 19 to 21 parts by mass, based on 100 parts by mass of the total weight of polyisocyanate compound B1.

[0051] The method for synthesizing uretdione compound B1D is not particularly limited and may be a known method. For example, the method described in U.S. Patent Application Publication 2007 / 0032594 can be used. Alternatively, commercially available products such as Desmodur® N3400 (uretdione of hexamethylene-1,6-diisocyanate, manufactured by Covestro) can be used.

[0052] [Urethane Prepolymer B1P] It is preferable that the urethane prepolymer B1P is obtained by reacting a diisocyanate monomer having two or more isocyanate groups in one molecule with an active hydrogen compound having two or more active hydrogen-containing groups in one molecule, such that the isocyanate groups of the diisocyanate monomer are in excess of the active hydrogen-containing groups of the active hydrogen compound.

[0053] The urethane prepolymer B1P can preferably be produced by using diisocyanate monomers such that 5.0 to 10.0 moles of isocyanate groups react with 1 mole of active hydrogen-containing groups of the active hydrogen compound, mixing and reacting these to synthesize a urethane prepolymer, and then removing the remaining diisocyanate monomers by evaporation.

[0054] The urethane prepolymer B1P is preferably 70 to 90 parts by mass, more preferably 72 to 88 parts by mass, even more preferably 74 to 86% by mass, particularly more preferably 76 to 84 parts by mass, and most preferably 78 to 82 parts by mass, based on 100 parts by mass of the total mass of the polyisocyanate compound B1.

[0055] Diisocyanate monomers used to manufacture urethane prepolymer B1P include, for example, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(isocyanate-methyl)cyclohexane (H6XDI), and dicyclohexylmethane diisocyanate (H6XDI). 12 This may be an aliphatic polyisocyanate (including alicyclic polyisocyanates) such as MDI. Among these, hexamethylene diisocyanate (HDI) or norbornane diisocyanate (NBDI) is more preferred.

[0056] The active hydrogen compounds having two or more active hydrogen-containing groups in a single molecule that can be used to produce urethane prepolymers are not particularly limited. The active hydrogen-containing groups may be hydroxyl (OH) groups, amino groups, or imino groups.

[0057] The polyol compounds used to produce the urethane prepolymer B1P may be polyether polyols; polymer polyols having carbon-carbon bonds in their main chain structure, such as polyester polyols, acrylic polyols, lactone polyols, polycarbonate polyols, polybutadiene diols, and hydrogenated polybutadiene polyols; low molecular weight polyhydric alcohols; or mixtures thereof.

[0058] Polyether polyols can be polyoxyethylenediol (polyethylene glycol), polyoxypropylenediol (polypropylene glycol: PPG), polyoxypropylene triol, ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), polytetraethylene glycol, or sorbitol-based polyols.

[0059] From the viewpoint of excellent compatibility with polyisoanates, polyether polyols such as polypropylene glycol and polyoxypropylene triol are preferred. The weight-average molecular weight of the polyether polyol may be between 500 and 20,000, from the viewpoint of ensuring that the urethane prepolymer obtained by reaction with isocyanate has appropriate fluidity at room temperature (23°C). In the present invention, the above weight-average molecular weight is the polystyrene equivalent value obtained by the GPC method (solvent: tetrahydrofuran (THF)).

[0060] The urethane prepolymer B1P may have an average of 1.9 to 4.5 isocyanate groups (NCO) per molecule. More preferably, the urethane prepolymer B1P has an average of 2.0 to 3.0 isocyanate groups (NCO) per molecule.

[0061] The urethane prepolymer B1P may have an isocyanate group equivalent of 300 to 1100.

[0062] The urethane prepolymer B1P has an isocyanate group (NCO) content of preferably 5% to 30% by mass, preferably 10% to 20% by mass, more preferably 8% to 17% by mass, and particularly preferably 10% to 15% by mass, based on the total weight of the urethane prepolymer B1P.

[0063] The urethane prepolymer B1P preferably has a viscosity of 1000 to 10000 mPa·s, more preferably 1000 to 5000 mPa·s, and most preferably 1000 to 2500 mPa·s.

[0064] The urethane prepolymer B1P is preferably a reaction product of an isocyanate compound and a polyol.

[0065] The above isocyanate compounds preferably have 2 to 6 isocyanate groups, more preferably 2 to 3 isocyanate groups, and most preferably 2 isocyanate groups. The above isocyanate compounds include pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(isocyanate-methyl)cyclohexane (H6XDI), and dicyclohexylmethane diisocyanate (H 12 It may be an aliphatic polyisocyanate such as MDI. Among these, HDI is more preferred. In other words, the urethane prepolymer B1P is preferably obtained from an isocyanate compound mainly composed of an aliphatic polyisocyanate, and more preferably from an isocyanate compound mainly composed of HDI.

[0066] The polyol is preferably one or more selected from polyether polyols, polyester polyols, and polycarbonate polyols, and more preferably a polyester polyol. The polyol preferably contains 2 to 6 functional hydroxyl groups, most preferably 2 to 3 functional hydroxyl groups.

[0067] The weight ratio (B1P / B1D) of urethane prepolymer B1P to uretdione compound B1D is preferably 1 to 20, more preferably 2 to 15, even more preferably 3 to 12, and most preferably 4 to 9. The effect is more pronounced when the above weight ratio satisfies the more preferable upper limit.

[0068] The ratio of active hydrogen groups [H] in the first component A to isocyanate groups [NCO] in the second component B (NCO / H) is preferably in the range of 0.95 to 1.5, more preferably in the range of 1.0 to 1.4, more preferably in the range of 1.05 to 1.3, more preferably in the range of 1.05 to 1.2, and particularly preferably in the range of 1.1 to 1.15.

[0069] [Filler] The curable composition of the present invention may further contain a filler. The filler may be contained in either or both of the first component A or the second component B. The filler may be heavy calcium carbonate or precipitated calcium carbonate, surface-treated or untreated with fatty acids, barite, quartz powder, quartz sand, dolomite, wollastonite, kaolin, calcined kaolin, sheet silicate, for example mica or talc, zeolite, aluminum hydroxide, magnesium hydroxide, silica including pulverized silica from a pyrolysis process, cement, gypsum, fly ash, industrially produced carbon black, graphite, for example metal powder of aluminum, copper, iron, silver or steel, PVC powder or hollow beads.

[0070] The amount of the above-mentioned filler is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, and even more preferably 10 to 15 parts by mass, when the total mass of the first component (curing agent) of the curable composition of the present invention is 100 parts by mass.

[0071] [organic solvent] The curable composition of the present invention is substantially free of organic solvents. More specifically, it is more preferable that the total amount of organic solvents contained in the first component A and the second component B of the curable composition of the present invention is less than 3% by mass, less than 2% by mass, less than 1% by mass, less than 0.5% by mass, and less than 0.1% by mass, based on the total weight of the curable composition of the present invention.

[0072] The above organic solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, acetylacetone, mesityl oxide, cyclohexanone, methylcyclohexanone, ethyl acetate, propyl acetate, butyl acetate, n-butyl propionate, diethyl malonate, 1-methoxy-2-propyl acetate, ethyl 3-ethoxypropionate, diisopropyl ether, diethyl ether, dibutyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, and ethylene glycol diethyl ether. Coal monopropyl ether, ethylene glycol mono(2-ethylhexyl) ether, acetals, for example, particularly methylal, ethylal, propyral, butyral, 2-ethylhexylal, dioxolane, glycerol formal or 2,5,7,10-tetraoxaundecane (TOU), and toluene, xylene, heptane, octane, naphtha, gasoline, petroleum ether or diesel fuel, particularly selected from the list consisting of Solvesso® products (from Exxon), methylene chloride, propylene carbonate, butyrolactone, N-methylpyrrolidone and N-ethylpyrrolidone.

[0073] [Other Additives] The curable composition of the present invention may contain other additives commonly used for polyurea compositions. The following auxiliary agents and additives may be present: - Inorganic or organic pigments, particularly titanium dioxide, chromium oxide, or iron oxide; - Rheological modifiers; - Additives, particularly wetting agents, leveling agents, defoaming agents, deaeration agents, stabilizers against oxidation, heat, light or ultraviolet irradiation, or biocides; Or further substances commonly used in such compositions. Other additives may be included in either or both of the first component A or the second component B.

[0074] When the two components of the curable composition of the present invention are mixed at 1000 rpm for 30 seconds, and then measured at 5 rpm for 30 seconds with a No. 5 spindle, and determined using a Brookfield viscometer at 23°C, they preferably have a viscosity of 2200 mPa·s or less. The viscosity is more preferably 100 to 2050 mPa·s, and even more preferably 500 to 180 mPa·s. Having the above preferred viscosity allows for more suitable application by roller or brush.

[0075] The first component A and the second component B of the curable composition of the present invention are separate components. The first component A and the second component B of the curable composition of the present invention are produced separately from each other. The components of each component are mixed together here, preferably with the water removed, in order to obtain a visually uniform liquid. Each component is preferably stored in separate waterproof containers. Suitable containers include, in particular, drums, bulk containers, hobocks, pails, cans, pouches, canisters, or bottles.

[0076] When using the curable composition of the present invention, the two components are mixed immediately before application. The mixing ratio is preferably selected such that the active hydrogen groups are present in an appropriate ratio to the isocyanate groups as described above. By weight, the mixing ratio of the first component A to the second component B is preferably about 1:2 to 2:1.

[0077] The two components described above are mixed using an appropriate stirring mechanism, such as a double-shaft mixer, and the individual components are properly pre-mixed in the correct mixing ratio. Equally possible is continuous mechanical processing using a two-component measuring unit with static or dynamic mixing of the components. During mixing, it should be ensured that the two components are mixed with maximum uniformity. If mixing precedes application, it must be ensured that the time elapsed between mixing the components and applying the mixture is not too long. This is because too long a time can result in confusion, such as poor flow or delayed or incomplete adhesion to the substrate. Mixing is carried out at ambient temperatures, preferably around 10 to 35°C, typically in the range of about 5 to 50°C.

[0078] Chemical curing is initiated by mixing two components. Available NCO reactive groups, particularly amino groups, react with available isocyanate groups. As a result of these reactions, the composition hardens, producing a solid material. This process is also called crosslinking.

[0079] The present invention further relates to a composition obtained by mixing the two components described above, and to a cured product obtained by curing the mixed composition.

[0080] In application, the curable composition immediately after mixing is applied to the surface of the substrate. Then, it is preferable to apply the curable composition by distributing it over the target area using, for example, a roller, brush, or painting brush until the desired layer thickness is achieved. However, this can also be applied by spray application with a spray pressure of over 50 bar, particularly over 100 bar.

[0081] In a further embodiment, the present invention relates to a method for applying the above-described mixed curable composition as a top coating to a substrate (object). The substrate is preferably a substrate for roofing applications.

[0082] The top coating formed by the coating method of the present invention preferably has a thickness of 50 to 300 μm (after drying). More preferably, this thickness is 75 to 250 μm, and even more preferably 100 to 200 μm.

[0083] The top coating formed from the curable composition of the present invention is used in environments exposed to the atmosphere. "Exposed to the atmosphere" means being in an environment exposed to air pollution and weathering. The curable composition of the present invention is preferably used to form a top coating (outermost layer) for roofs and the like. Particularly preferably, the curable composition of the present invention is used to form the outermost layer of a waterproof membrane that is placed on and exposed on the floor of a parking lot having a parking area for parking vehicles. The waterproof membrane is formed by laminating a primer layer, a waterproof layer, and an anti-slip layer in that order on the floor, with the anti-slip layer being the outermost layer of the waterproof membrane, and the anti-slip layer may be composed of a mixture of the curable composition of the present invention and aggregate.

[0084] By using such a waterproof membrane, it is possible to provide a waterproof membrane with excellent weather resistance and abrasion resistance, as well as a method for producing the same, without having to apply a conventional acrylic top coating as the outermost layer. In other words, the curable composition of the present invention is advantageous in that it eliminates the process of forming a conventional acrylic top coating.

[0085] [parking] The parking lot on which the waterproof membrane of the present invention is installed can be any parking lot having a parking area for parking vehicles. The parking lot may be, for example, a parking lot located on the roof, middle floors, or underground of a large building such as a commercial facility or a hospital.

[0086] [Parking area] In this invention, a parking area is an area for parking vehicles. In this invention, a parking area is a broad concept that includes an area where vehicles can be parked (for example, the floor in the case where a parking lot occupies the entire floor of a large building), and a single parking space for parking one vehicle.

[0087] (Driving area) The above-mentioned parking lot may further have a driving area for vehicles to travel on. Examples of the above-mentioned driving area include at least one or all of the area surrounding the above-mentioned parking area, and ramps connecting each floor of the building. If the above-mentioned parking area further includes a driving area for vehicles to travel on, the parking area and the driving area may be integrated to form the floor (substrate) of the parking area. Examples of cases where the parking area and the driving area are integrated include cases where the parking area and the driving area are integrated to form a parking area on the rooftop or on each floor of a building, and cases where, in addition to the rooftop or on-floor parking area where the parking area and driving area are integrated as described above, a ramp connecting each floor of the building is connected as a driving area, and these are integrated. The floor (substrate) of the parking lot may be made of concrete, mortar, or the like.

[0088] [Waterproof membrane] The top coating formed from the curable composition of the present invention can constitute the outermost layer of a waterproof membrane that is placed on and exposed on the floor of the parking lot.

[0089] [Placement] A waterproof membrane having a top coating formed from the curable composition of the present invention may be placed in the parking area of ​​the parking lot, and if the parking lot further has a driving area, the waterproof membrane of the present invention may be placed in both the parking area and the driving area. Alternatively, the waterproof membrane of the present invention may be placed over the entire floor of a parking lot having a parking area.

[0090] [Exposure] A waterproof membrane having a top coating formed from the curable composition of the present invention is placed on the floor of the parking lot and exposed. Exposure of the waterproof membrane means that there is no further topcoat on top of the waterproof membrane. Therefore, in this invention, the anti-slip layer becomes the outermost layer of the waterproof layer of the present invention. In other words, the anti-slip layer is directly exposed to, for example, sunlight, rain, and contact with tires.

[0091] The above-mentioned parking lot will be described below using the attached drawings. Note that the present invention is not limited to the attached drawings. (Figure 1) Figure 1 is a photograph showing an example of a parking lot with parking areas for parking vehicles. In Figure 1, parking lot 1 has multiple parking areas 11, each accommodating one vehicle. Adjacent parking areas 11 are separated by lines 13. In addition, parking lot 1 has a driving area 15 in addition to the parking area 11. The parking area 11 and the driving area 15 are integrated to form parking lot 1. Arrows 17 indicating the direction of vehicle travel are painted on the driving area 5. A waterproof membrane has already been laid over the entire floor surface of parking lot 1, and lines 13, arrows 17, etc., have been applied on top of the waterproof membrane. In Figure 1, the waterproof membrane (specifically the anti-slip layer) is exposed in the areas other than those where lines 13, arrows 17, etc., have been applied and the wheel stops.

[0092] (Figure 2) Figure 2 is a photograph illustrating an example where the ramps connecting each floor of a building are used as vehicle access areas. In Figure 2, the ramp 25 connects to the rooftop or floor-level parking area, which integrates the parking and driving areas, as a driving area, and further connects each floor of the building. The ramp 25 slopes downward from the foreground of the photograph to the left in the background. The ramp 25 has a driving area 21 and collision prevention poles 27, and the driving area 21 is demarcated by lines 23. The waterproof membrane of the present invention is already laid over the entire floor of the slope 25, and the line 23 is applied on top of the waterproof membrane. In the slope 25 (floor), the waterproof membrane (more specifically, the anti-slip layer) is exposed in areas other than where the line 23 and pole 27 are installed.

[0093] [Lamination of waterproof membrane] The above-mentioned waterproof membrane is constructed by layering a primer layer, a waterproof layer, and an anti-slip layer in that order on top of the parking lot floor (substrate).

[0094] The waterproof membrane described above will be explained below with reference to the attached drawings. However, the waterproof membrane of the present invention is not limited to those shown in the attached drawings. (Figure 3) Figure 3 is a schematic cross-sectional view showing an example of a parking lot floor and the waterproof membrane of the present invention placed thereon. In Figure 3, a waterproof membrane 30 is placed on the floor 31 of a parking lot with a parking area for parking vehicles. The waterproof membrane 30 is exposed. The waterproof membrane 30 is constructed by laminating a primer layer 35, a waterproof layer 37, and an anti-slip layer 39 on the floor 31 in that order. The anti-slip layer 39 is the outermost layer of the waterproof membrane 30.

[0095] Furthermore, lines indicating parking areas, the direction a vehicle should travel, and stopping positions can be partially displayed on the waterproof membrane of the present invention. Furthermore, the above-mentioned waterproof membrane may be placed on areas other than the parking lot floor, such as on the walls.

[0096] When the curable composition of the present invention is used to form the outermost layer of the waterproof membrane of the parking lot, the curable composition of the present invention may contain aggregate.

[0097] [aggregate] The aggregate may be, for example, natural silicate materials such as silica sand, minerals (basalt, etc.), river sand, or ceramics. The average particle size of the aggregate can be, for example, 0.1 mm to 2 mm, and more preferably 0.2 to 1 mm. The average particle size can be measured by laser diffraction / scattering, for example, using a particle size distribution analyzer SALD-2000J manufactured by Shimadzu Corporation. The amount of the aggregate can be 10 to 200 parts by mass per 100 parts by mass of the solid content (hardened product) of the curable composition of the present invention.

[0098] Articles can be obtained by the curable composition of the present invention and a production method using the curable composition. In a further embodiment, the present invention relates to such articles. [Examples]

[0099] Examples are presented below in this specification, which are intended to further clarify the invention described herein. The invention is, of course, not limited to these described examples.

[0100] [Preparation of curable compositions] In the examples and comparative examples, the components of the first mixture listed in Table 1 were dispersed at 1800 rpm for 30 minutes, and it was confirmed that the pigment particle size was less than 30 μm. Next, the components of the second mixture listed in Table 1 were added and stirred at 800 rpm for 10 minutes to obtain the first component A. Subsequently, the components shown in Table 2 were stirred at a speed of 800 rpm for 15 minutes to obtain the second component B. Then, the specified amounts of components A and B were measured and stirred at a speed of 800 rpm for 1 minute to prepare the cured composition liquid.

[0101] [Table 1]

[0102] [Table 2]

[0103] [Table 3]

[0104] The materials used in the examples and comparative examples are shown below. 1) Desmophen(registered trademark) NH1420: Amino-functional polyaspartate ester (aspartate ester amine A1A), amine value 199-203 mg KOH / g, equivalent weight 276, viscosity at 25°C 900-2000 mPa·s, manufactured by Covestro. 2) R-706 (Pigment): Rutile-type titanium dioxide (TiO2) pigment, manufactured by DuPont. 3) Molecular sieve 4A Molecular sieve powder (dehydrating agent): Manufactured by Resonaq Universal 4) Disperbyk 110 (dispersant): Dispersant, manufactured by BYK 5) Tego Airex 940 (antifoaming agent): Silicone-containing polymer solution, manufactured by Evonik. 6) BYK320 (Leveling agent): Silicone-based surface modifier, manufactured by BYK. 7) Tinuvin 292 (HALS): Hindered amine light stabilizer, manufactured by BASF. 8) Tinuvin PS (UVA): Benzotriazole-based UV absorber, manufactured by BASF. 9) Desmodur® N3400: Uretdione of hexamethylene-1,6-diisocyanate (HDI), (manufactured by Covestro) 10) Desmodur® N3600: Hexamethylene-1,6-diisocyanate (HDI) isocyanurate (manufactured by Covestro) 11) Desmodur® E30700: A prepolymer based on hexamethylene-1,6-diisocyanate (HDI), with a viscosity of approximately 1641 mPa·s at 20°C (manufactured by Covestro). 12) TLU-100: (HDI isocyanurate), manufactured by Asahi Kasei. 13) Duranate AE700-100: A trifunctional adduct of HDI, a compound having the structure represented by the following formula. Manufactured by Asahi Kasei. [ka]

[0105] [viscosity] In the examples and comparative examples, the first component A and the second component B were mixed using a stirring device (manufactured by IKA) at 2000 rpm for 30 seconds. Immediately after mixing, the viscosity was measured using a Brookfield viscometer at 23°C at 5 rpm for 30 seconds with a No. 5 spindle. The viscosity was similarly measured every 5 minutes after mixing to measure the change over time.

[0106] [density] The density (g / cm³) is calculated by dividing the weight of each cured product obtained from each curable composition prepared in the examples and comparative examples by the volume of each cured product measured by a pycnometer. 3 ) was calculated.

[0107] [Tensile strength (N / mm²)] 2 )] Tensile strength was measured in accordance with JIS A 6909 (200 mm / min). Tensile strength was evaluated according to the following criteria. ○: 20 N / mm 2 super △: 10~20 N / mm 2 ×: 10N / mm 2 less than

[0108] [Elongation between gauge lines (%)] The elongation between gauge marks was measured in accordance with JIS A 6909 (200 mm / min). The elongation between gauge marks was evaluated according to the following criteria. 〇: More than 115% △: 100%~115% ×: Less than 100%

[0109] [Tear strength (N / mm)] Tear strength was measured in accordance with JIS A6021 (angle type without cuts, 200 mm / min). Tear strength was evaluated according to the following criteria. 〇: More than 70N / mm △: 40~70N / mm ×: Less than 40N / mm

[0110] [Taber wear test] The abrasion resistance of the cured products obtained from the curable compositions prepared in the examples and comparative examples was measured in accordance with JIS K 7204 (1 kg / H-22 / 1000 rpm). Abrasion resistance was evaluated based on weight loss according to the following criteria. ○: Weight loss is less than 0.5g △: Weight loss of 0.3-0.5g ×: Weight loss exceeds 0.5g

[0111] [Hardness (Type D)] The hardness of the cured products obtained from the curable compositions prepared in the examples and comparative examples was measured using a durometer type D hardness tester in accordance with JIS K 6249:2003. Hardness was evaluated according to the following criteria. 〇:Over 60 △: 30~60 ×: Less than 30

Claims

[Claim 1] A method for producing a top coating to be placed on and exposed on the floor of a parking lot having a parking area for parking vehicles, A step of preparing a curable composition, The steps include: laminating a primer layer and a waterproof layer on the aforementioned floor in that order; The method comprises the step of forming a top coating on the waterproof layer by curing a mixture of the curable composition and aggregate, The curable composition is a two-component curable composition having a first component A and a second component B. The first component A comprises polyamine compound A1, The polyamine compound A1 comprises aspartic acid ester amine A1A, The second component B comprises a polyisocyanate compound B1. The polyisocyanate compound B1 comprises a uretdione compound B1D having two isocyanate groups and a urethane prepolymer B1P. The aspartic acid ester amine A1A is present in an amount of 70 to 100 parts by mass relative to 100 parts by mass of the total weight of the polyamine compound A1. The uretdione compound B1D is present in an amount of 10 to 30 parts by mass relative to 100 parts by weight of the total weight of the polyisocyanate compound B1. The urethane prepolymer B1P is in an amount of 70 to 90 parts by mass relative to 100 parts by weight of the total weight of the polyisocyanate compound B1. The organic solvent contained in the first component A and the second component B is less than 1% by mass relative to the total weight of the curable composition. The aforementioned aspartic acid ester amine A1A is The following equation (I): 【Chemistry 1】 [In formula (I), R1 is a divalent hydrocarbon group having 1 to 80 carbon atoms and a ring structure. R2 represents a hydrocarbon group having 1 to 20 carbon atoms, either identical or different. It is represented as, The uretdione compound B1D having the two isocyanate groups is given by the following formula (II): 【Chemistry 2】 [In formula (II), R 201 and R 202 represent a linear or branched alkylene group, a linear or branched unsaturated hydrocarbon group, or an alicyclic hydrocarbon group, respectively. It is represented as, The urethane prepolymer B1P is a reaction product of an isocyanate compound mainly composed of hexamethylene diisocyanate and a polyol, and is a method for producing it.

Images