Coating composition and coating film forming method

Abstract

To provide a coating composition which can give a coating film having excellent durability and is easy to apply. [Solution] A coating composition comprising a main agent (I) and a curing agent (II), at least one of the main agent (I) and the curing agent (II) containing a pigment (C), the main agent (I) containing a polyamine compound (A), the curing agent (II) containing a polyisocyanate compound (B), the polyamine compound (A) containing an aspartic acid ester amine (A1), the polyisocyanate compound (B) containing an allophanate group-containing polyisocyanate compound (B1) and a prepolymer type isocyanate compound (B2), the allophanate group-containing polyisocyanate compound (B1) having an isocyanate group content of more than 15.0 mass%, the prepolymer type isocyanate compound (B2) being obtained by reacting some of the isocyanate groups with a polyol, the number average molecular weight being 500 to 3,000, and the isocyanate group content being 3.0 mass% or more and 15.0 mass% or less.

Description

[Technical Field]

[0001] The present invention relates to a coating composition and a method for forming a coating film. [Background technology]

[0002] Road marking coatings deteriorate and wear due to vehicle traffic, etc., and therefore require periodic maintenance such as repainting and repair. From a sustainability perspective, there is a demand for further improvements in the durability of coatings, such as reducing the frequency and / or extending the period of repainting and repair.

[0003] Patent Document 1 discloses a melt-type road paint containing a thermoplastic resin, a pigment, and cellulose nanofibers with a number average fiber diameter of 2 nm to 500 nm. However, it is difficult to obtain the required durability from the paint obtained from the paint described in Patent Document 1.

[0004] In recent years, there has been growing expectation for the application of resins containing urea bonds in the fields of coating materials and paints, as urea bonds (formed by the reaction of polyamine compounds with polyisocyanate compounds) have strong bonding strength and excellent durability.

[0005] Patent Document 2 discloses a method for painting roads with a coating composition containing a base agent containing a polyol resin and an amine, and a curing agent containing an isocyanate.

[0006] Patent Document 3 discloses a two-component polyurea-based heat-shielding coating material having a base agent containing a polyamine, a heat-shielding material, and a filler, and a curing agent containing a polyisocyanate. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2019-157112 [Patent Document 2] Patent No. 6047256 [Patent Document 3] Patent No. 7121959 Summary of the Invention [Problem to be solved by the invention]

[0008] The coating films obtained from the coating compositions described in Patent Documents 2 and 3 do not have sufficient adhesion to the asphalt pavement to be coated. As a result, they are inferior in durability as coating films for road markings. Furthermore, the coating compositions tend to have high viscosity, which requires heating and / or dilution during application, resulting in poor workability.

[0009] The present invention has been made to solve the above-mentioned problems of the prior art, and has as its object to provide a coating composition which not only gives a coating film with excellent durability but also has excellent workability. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention provides the following aspects. [1] Contains a base agent (I) and a curing agent (II), At least one of the base agent (I) and the curing agent (II) contains a pigment (C), The main component (I) contains a polyamine compound (A), The curing agent (II) contains a polyisocyanate compound (B), The polyamine compound (A) contains an aspartic acid ester amine (A1), the polyisocyanate compound (B) includes an allophanate group-containing polyisocyanate compound (B1) and a prepolymer-type isocyanate compound (B2); The allophanate group-containing polyisocyanate compound (B1) has an isocyanate group content of more than 15.0% by mass, The coating composition is such that the prepolymer type isocyanate compound (B2) is obtained by reacting some of the isocyanate groups with a polyol, has a number average molecular weight of 500 to 3,000, and has an isocyanate group content of 3.0 mass % or more and 15.0 mass % or less. [2] The coating composition according to [1] above, wherein the mass ratio (B1) / (B2) of the content of the allophanate group-containing polyisocyanate compound (B1) to the content of the prepolymer-type isocyanate compound (B2) is greater than 3.0 and not more than 35.0. [3] The aspartic acid ester amine (A1) is represented by the following formula (I): [ka] [In formula (I), R 1 is a divalent C 1-80 represents a hydrocarbon group, R 2 are independent of each other, C 1-20 represents a hydrocarbon group.] The coating composition according to [1] or [2] above, [4] The coating composition of any one of the above [1] to [3], wherein the content of the aspartic acid ester amine (A1) is 80% by mass or more and 100% by mass or less, based on 100% by mass of the total amount of the polyamine compound (A). [5] The coating composition of any one of the above [1] to [4], wherein the content of the prepolymer type isocyanate compound (B2) is 1.0 mass % or more and 50.0 mass % or less in 100 mass % of the total amount of the polyisocyanate compound (B). [6] The coating composition according to any one of the above [1] to [5], wherein the pigment (C) contains at least one of an inorganic pigment and an organic pigment. [7] The coating composition of any one of the above [1] to [6], wherein the pigment volume concentration of the pigment (C) in the coating composition is 3% by volume or more and 10% by volume or less. [8] The coating composition of any one of the above [1] to [7], wherein the ratio (NCO / NH) of the total equivalent weight of isocyanate groups contained in the polyisocyanate compound (B) to the total equivalent weight of amino groups contained in the polyamine compound (A) is 0.40 or more and 2.20 or less. [9] The coating composition according to any one of the above [1] to [8], further comprising a dehydrating agent.

[10] The coating composition of any one of the above [1] to [9], wherein the amount of the organic solvent is 10% by mass or less of the coating composition.

[11] The shear rate of the main agent (I) at 25°C is 10,000 s -1 and the shear viscosity of the curing agent (II) measured at a shear rate of 10,000 s at 25 °C. -1 The coating composition of any one of [1] to

[10] above, wherein the shear viscosity measured by the above method is 1,000 mPa·s or less.

[12] The coating composition according to any one of [1] to

[11] above, which is used for one or more selected from a roadway, a road structure, a railway structure, an internal facility of a building structure, an interior of a building structure, an article worn by pedestrians, and a utility pole.

[13] Mixing a base agent (I) and a curing agent (II) to prepare a coating composition; and applying the coating composition to an object to be coated. At least one of the base agent (I) and the curing agent (II) contains a pigment (C), The main component (I) contains a polyamine compound (A), The curing agent (II) contains a polyisocyanate compound (B), The polyamine compound (A) contains an aspartic acid ester amine (A1), the polyisocyanate compound (B) includes an allophanate group-containing polyisocyanate compound (B1) and a prepolymer-type isocyanate compound (B2); The allophanate group-containing polyisocyanate compound (B1) has an isocyanate group content of more than 15.0% by mass, The method for forming a coating film, wherein the prepolymer type isocyanate compound (B2) is obtained by reacting some of the isocyanate groups with a polyol, has a number average molecular weight of 500 to 3,000, and has an isocyanate group content of 3.0% by mass or more and 15.0% by mass or less. [Effects of the Invention]

[0011] According to the present invention, a coating composition is provided which not only gives a coating film with excellent durability but also has excellent workability. DETAILED DESCRIPTION OF THE INVENTION

[0012] paint composition The coating composition of the present disclosure is a multi-component coating composition containing a base agent (I) and a curing agent (II). The coating composition of the present disclosure may be a two-component coating composition. At least one of the base agent (I) and the curing agent (II) contains a pigment (C). The base agent (I) contains a polyamine compound (A), and the curing agent (II) contains a polyisocyanate compound (B). The polyamine compound (A) contains an aspartic acid ester amine (A1). The polyisocyanate compound (B) contains an allophanate group-containing polyisocyanate compound (B1) and a prepolymer-type isocyanate compound (B2).

[0013] The reaction between the polyamine compound (A) and the polyisocyanate compound (B) forms a polyurea compound and a coating film. The reaction between the polyamine compound (A) and the polyisocyanate compound (B) is thought to be initiated by a nucleophilic reaction of the amino group with the carbon atom of the isocyanate group. The high reactivity between the polyamine compound (A) and the polyisocyanate compound (B) results in a strong bond, which can result in the resulting coating film having good hardness and abrasion resistance.

[0014] The prepolymer type isocyanate compound (B2) is a compound obtained by reacting some of the isocyanate groups with a polyol, and has a number average molecular weight of 500 to 3,000 and an isocyanate group content of 3.0 to 15.0%. The prepolymer type isocyanate compound (B2) has a low isocyanate group content relative to the number average molecular weight and has few crosslinking points. In other words, the prepolymer type isocyanate compound (B2) imparts flexibility to the crosslinked structure. This imparts flexibility to the resulting coating film, and the coating film has a high elongation at break.

[0015] The allophanate group-containing polyisocyanate compound (B1) used in combination has a low viscosity. Furthermore, due to its structure, the allophanate group is expected to interact with substrates (e.g., asphalt) that have even slight polarity. Therefore, the allophanate group-containing polyisocyanate compound (B1) does not increase the viscosity of the coating composition, improving application at room temperature (20 to 30°C) and enhancing adhesion to the substrate. Additionally, the allophanate group-containing polyisocyanate compound (B1) can exert cohesive force due to the interaction between the hydrogen atoms and oxygen atoms contained in the allophanate group. Therefore, the allophanate group-containing polyisocyanate compound (B1) improves the hardness of the resulting coating film.

[0016] The aspartic acid ester amine (A1) used as the polyamine compound (A) contains two ester groups, which can suppress the nucleophilicity of the amino group. This improves the pot life. Additionally, the aspartic acid ester amine (A1) has a low viscosity, which improves the application of the coating composition. Furthermore, the aspartic acid ester amine (A1) has a structure that is easily polarized, allowing it to interact with substrates (e.g., asphalt) that have even slight polarity, thereby improving the adhesion of the coating film.

[0017] A coating composition containing an aspartic acid ester amine (A1), an allophanate group-containing polyisocyanate compound (B1), a prepolymer-type isocyanate compound (B2), and a pigment (C) can form a coating film that has high hardness, elongation at break, and abrasion resistance while maintaining adhesion. As a result, the coating film exhibits excellent durability. Furthermore, the coating composition also has excellent workability at room temperature.

[0018] Durability is a property that combines adhesion to the substrate, hardness, elongation at break, and abrasion resistance.

[0019] In this disclosure, the nonvolatile content of the coating composition means the sum of the solid content of the main component (I) and the nonvolatile content of the curing agent (II). Also, in this disclosure, the nonvolatile content of the main component (I) and the curing agent (II) means the heating residue as defined in JIS K 5601-1-2:2008, and the proportion of the nonvolatile content is calculated by measuring the percentage of the mass of the residue after heating at 105°C for 60 minutes to the original mass.

[0020] In the present disclosure, the content is calculated based on the non-volatile content.

[0021] In this disclosure, the nonvolatile resin content refers to the nonvolatile content of the polyamine compound (A) and the polyisocyanate compound (B). The amount of the nonvolatile resin content is calculated as the mass of the residue after heating the coating composition at 105°C for 60 minutes, and the proportion of the nonvolatile resin content is calculated by measuring the percentage of the mass of the residue to the original mass.

[0022] [Polyamine compound (A)] The polyamine compound (A) refers to a compound having two or more amino groups in one molecule. The amino groups may be one or more types selected from primary amino groups and secondary amino groups, with a total of two or more types. The polyamine compound (A) includes an aspartic acid ester amine (A1).

[0023] Aspartic acid ester amine (A1) The aspartic acid ester amine (A1) is an amine compound containing a structure in which the carboxy group of aspartic acid is esterified. The aspartic acid ester amine (A1) may be a compound in which two aspartic acids are each esterified and the nitrogen atoms of the amino groups are each bonded to a divalent organic group.

[0024] Such aspartic acid ester amine (A1) is, for example, represented by the following formula (I): [ka]

[0025] [In formula (I), R 1 is a divalent C 1-80 represents a hydrocarbon group, R 2 are independent of each other, C 1-20 represents a hydrocarbon group.] It is expressed as:

[0026] R 1 may have a ring structure (particularly an alicyclic structure). In this case, the secondary amino group may be -CH(COOR 2 )-CH2-COOR 2 and R 1 Since the ring structure is surrounded by the ring structure, the effect of inhibiting the nucleophilic reaction of the amino group due to steric hindrance can be more easily exerted.

[0027] R 1 Divalent C represented by 1-80 Examples of the hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. 1 Divalent C represented by 1-80 The hydrocarbon group may be a combination of two or more selected from the group consisting of a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. 1 The number of carbon atoms in the hydrocarbon group may be 1 to 30, or may be 1 to 20. When two or more types of hydrocarbon groups are combined, the total number of carbon atoms in all of the hydrocarbon groups is 1 to 80.

[0028] R 1 The divalent aliphatic hydrocarbon group represented by the formula (I) may be, for example, an alkylene group or an alkenylene group, and more preferably an alkylene group. The aliphatic hydrocarbon group may be either a straight chain or a branched chain, and is preferably a branched chain. The number of carbon atoms in the aliphatic hydrocarbon group may be preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.

[0029] Examples of the aliphatic hydrocarbon group include -CH2-, -CH2CH2-, -CH2CH2CH2-, CH(CH3)CH2-, -C(CH3)2-, -CH2CH2CH2CH2-, -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-, -C(CH3)2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)CH2CH2CH2-, -CH(CH2CH2CH2CH2CH2-, -CH2CH(CH 3)CH2CH2-, -C(CH3)2CH2CH2-, CH2C(CH3)2CH2-, -CH2CH2CH2CH2CH2CH2-, -CH(CH3)CH2CH2CH2CH2-, -C Examples include H2CH(CH3)CH2CH2CH2-, -CH2CH2CH(CH3)CH2CH2-, -C(CH3)2CH2CH2CH2-, and -CH2C(CH3)2CH2CH2-.

[0030] R 1 The divalent alicyclic hydrocarbon group represented by the formula (R) may be monocyclic or polycyclic, and in the case of polycyclic, it may form a bridged ring. 1 The divalent alicyclic hydrocarbon group represented by R is preferably a cycloalkylene group or a cycloalkenylene group, and more preferably a cycloalkylene group. 1 The divalent alicyclic hydrocarbon group represented by the following formula may preferably have 3 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, and even more preferably 5 to 10 carbon atoms.

[0031] R 1 Examples of the divalent alicyclic hydrocarbon group represented by the formula (I) include a cyclohexanediyl group, a methylcyclohexanediyl group, and an isophoronediyl group.

[0032] R 1 The divalent aromatic hydrocarbon group represented by R may be monocyclic or polycyclic, and in the case of polycyclic, two or more rings may be condensed. 1 The divalent aromatic hydrocarbon group represented by the formula (I) may preferably have 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.

[0033] R 1Examples of the divalent aromatic hydrocarbon group represented by the formula (I) include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group.

[0034] Divalent C 1-80 Aliphatic hydrocarbon radical, divalent C 3-80 Alicyclic hydrocarbon groups and divalent C 6-20 The divalent group formed by combining two or more aromatic hydrocarbon groups includes divalent C 1-80 Aliphatic hydrocarbon group and divalent C 3-80 A divalent group combining an alicyclic hydrocarbon group; a divalent C 1-80 Aliphatic hydrocarbon group and divalent C 6-80 A divalent group in combination with an aromatic hydrocarbon group is preferred.

[0035] Divalent C 1-80 Aliphatic hydrocarbon group and divalent C 3-80 Examples of the divalent group combined with an alicyclic hydrocarbon group include a dicyclohexylmethane-4,4'-diyl group and a 2,2'-dimethylmethylenebiscyclohexane-4,4'-diyl group.

[0036] Divalent C 1-80 Aliphatic hydrocarbon group and divalent C 6-80 Examples of the divalent group combined with an aromatic hydrocarbon group include a diphenylmethane-4,4'-diyl group and a 2,2-diphenylpropane-4,4'-diyl group.

[0037] R 1 As for divalent C 1-80 Aliphatic hydrocarbon radical, divalent C 3-80 Alicyclic hydrocarbon group, or divalent aliphatic hydrocarbon group and divalent C 3-80 A divalent group in combination 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. R 1 When R is the above group, the light resistance (yellowing resistance of the coating film) is good. 1 When R is an aliphatic hydrocarbon group, the drying properties of the coating film can be good, 1When is a group containing an alicyclic hydrocarbon group, the pot life can be further improved.

[0038] R 2 The hydrocarbon group represented by R may preferably be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by combining two or more groups selected from the group consisting of 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 groups, more preferably C 1-5 It may be a hydrocarbon group.

[0039] R 2 The aliphatic hydrocarbon group represented by R may preferably be an alkyl group. 2 The aliphatic hydrocarbon group represented by R may be either a straight chain or a branched chain. 2 The aliphatic hydrocarbon group required in the above may preferably have 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms.

[0040] R 2 Examples of the aliphatic hydrocarbon group represented by the formula include -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, and the like.

[0041] R 2 The alicyclic hydrocarbon group represented by R may be monocyclic or polycyclic, and in the case of polycyclic, it may form a bridged ring. 2 The alicyclic hydrocarbon group represented by R is preferably a cycloalkyl group or a cycloalkenyl group, and more preferably a cycloalkyl group. 2 The alicyclic hydrocarbon group represented by the following formula may preferably have 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and even more preferably 4 to 10 carbon atoms.

[0042] R 2Examples of the alicyclic hydrocarbon group represented by the formula (I) include a cyclohexyl group and a methylcyclohexyl group.

[0043] R 2 The aromatic hydrocarbon group represented by R may be monocyclic or polycyclic, and in the case of polycyclic, two or more rings may be condensed. 2 The aromatic hydrocarbon group represented by the formula (I) may preferably have 6 to 20 carbon atoms, more preferably 6 to 150 carbon atoms, and even more preferably 6 to 10 carbon atoms.

[0044] R 2 Examples of the divalent aromatic hydrocarbon group represented by the formula (I) include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0045] The group formed by combining two or more groups selected from aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups is preferably a divalent group formed by combining an aliphatic hydrocarbon group with an alicyclic hydrocarbon group, or a group formed by combining an aliphatic hydrocarbon group with an aromatic hydrocarbon group. The number of carbon atoms in such a group formed by combining two or more groups selected from aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups may be preferably 4 to 30, and more preferably 4 to 10.

[0046] Examples of the group combining an aliphatic hydrocarbon group and an alicyclic hydrocarbon group include a cyclohexylmethyl group and a methylcyclohexylmethyl group. Examples of the divalent group formed by combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group include a benzyl group and a phenylethyl group.

[0047] R 2 As for C 1-20 Aliphatic hydrocarbon group or C 3-20 Alicyclic hydrocarbon groups are preferred, and C 1-20 An aliphatic hydrocarbon group is more preferred. 2 When R is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, the light resistance (yellowing resistance of the coating film) can be good. 2 When R is an aliphatic hydrocarbon group, the drying properties of the coating film can be improved, 2When is an alicyclic hydrocarbon group, the pot life may be even better.

[0048] Examples of the compound represented by formula (I) include the following compounds (1) to (3).

[0049] Compound (1): [ka]

[0050] Compound (2): [ka]

[0051] Compound (3): [ka]

[0052] The aspartic acid ester amine (A1) may be a commercially available product, such as Desmophen NH1220, NH1420, or NH1520 (all manufactured by Sumika Covestro Urethane Co., Ltd.).

[0053] The mass average molecular weight of the aspartic acid ester amine (A1) may be preferably 150 to 10,000, more preferably 200 to 10,000, and even more preferably 220 to 4,000. When the mass average molecular weight of the aspartic acid ester amine (A1) is within the above range, the reaction rate of the resulting coating composition can be further suppressed. In the present disclosure, the mass average molecular weight is a value calculated in terms of polystyrene by gel permeation chromatography (GPC).

[0054] The content of the aspartic acid ester amine (A1) may be 80% by mass or more and 100% by mass or less, based on 100% by mass of the total amount of the amine compound (A). The content may be 90% by mass or more and 100% by mass or less, or 95% by mass or more and 100% by mass or less.

[0055] The aspartic acid ester amine (A1) may be used alone or in combination of two or more kinds.

[0056] In the present disclosure, an aliphatic polyamine compound refers to a polyamine compound that does not have a ring structure in its molecular structure, such as alkylene polyamines, polyalkylene polyamines, and other aliphatic polyamines.

[0057] Examples of the alkylene polyamine compound include methylene diamine, ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane.

[0058] Examples of the polyalkylene polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexamethylenetetramine.

[0059] Examples of the other aliphatic polyamines include polyamine compounds having an oxyalkylene group, such as tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethyl)amine, bishexamethylenetriamine, polyoxypropylenediamine, trimethylolpropanepoly(oxypropylene)triamine, and glycerylpoly(oxypropylene)triamine.

[0060] In the present disclosure, an alicyclic polyamine compound means a polyamine compound having an alicyclic structure in its molecular structure.

[0061] Examples of such alicyclic polyamine compounds include 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylidenebiscyclohexylamine, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane (e.g., norbornadiamine), bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane (e.g., 4,4'-diaminodicyclohexylmethane, etc.), isophoronediamine, menthenediamine (MDA), 1,4-bis-(8-aminopropyl)-piperazine, piperazine-1,4-diazacycloheptane, 1-(2'-aminoethylpiperazine), 1-[2'-(2''-aminoethylamino)ethyl]piperazine, 1,11-diazacycloeicosane, and 1,15-diazacyclooctacosane.

[0062] Examples of aromatic polyamine compounds include bis(aminoalkyl)benzenes, bis(aminoalkyl)naphthalenes, aromatic polyamine compounds having two or more primary amino groups bonded to a benzene ring, and other aromatic polyamine compounds.

[0063] The aromatic polyamine compound is not particularly limited, but examples thereof include bis(cyanoethyl)diethylenetriamine, o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, phenylenediamine, naphthylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, bis(aminomethyl)naphthalene, bis(aminoethyl)naphthalene, and polytetramethyleneoxide-di-p-aminobenzoate.

[0064] The content of polyamine compound (A) in the coating composition of the present disclosure may be preferably 10 parts by mass or more and 80 parts by mass or less, more preferably 15 parts by mass or more and 70 parts by mass or less, and even more preferably 20 parts by mass or more and 60 parts by mass or less, per 100 parts by mass of the nonvolatile content of the coating composition.

[0065] Other amine compounds The polyamine compound (A) may contain other polyamine compounds (A2) in addition to the aspartic ester amine (A1).

[0066] Such polyamine compound (A2) may be any polyamine compound different from the aspartic acid ester amine (A1), and examples thereof include aliphatic polyamine compounds, alicyclic polyamine compounds, aromatic polyamine compounds, etc. These polyamine compounds may be used alone or in combination of two or more.

[0067] The coating composition of the present disclosure (specifically, the main component (I)) may contain a monoamine compound having one amino group, provided that the effects of the present invention are not impaired.

[0068] The monoamine compound is not particularly limited, but examples thereof include dipropylamine, dibutylamine, diisobutylamine, N-methylhexylamine, di-N-octylamine, tetra(aminomethyl)methane, aspartic acid, etc. These monoamine compounds may be used alone or in combination of two or more.

[0069] Other film-forming compounds The coating composition of the present disclosure may contain a polyol compound, but the content thereof is desirably small, because polyol compounds and polyisocyanate compounds have lower reactivity than polyamine compounds and polyisocyanate compounds, and the strength (tensile strength) of the resulting coating film tends not to be fully satisfactory.

[0070] The content of the polyol compound is, for example, 20 parts by mass or less, or may be 10 parts by mass or less, or may be 5 parts by mass or less, relative to 100 parts by mass of the polyamine compound (A).

[0071] [Polyisocyanate compound (B)] The polyisocyanate compound (B) means a compound having two or more isocyanate groups in one molecule, and includes an allophanate group-containing polyisocyanate compound (B1) and a prepolymer type isocyanate compound (B2).

[0072] The isocyanate groups contained in the polyisocyanate compound (B) may be modified, and the polyisocyanate compound (B) may also contain modified products of such polyisocyanate compounds. Furthermore, a crosslinking reaction may occur due to the isocyanate groups contained in the polyisocyanate compound (B). Since the polyisocyanate compound is a polymer and has three or more functionalities, at least one of the multiple isocyanate groups may be modified, or a crosslinking reaction may occur due to at least two isocyanate groups.

[0073] Allophanate group-containing polyisocyanate compound (B1) The allophanate group (—O—CO—N(—)—CO—NH—)-containing polyisocyanate compound (B1) increases the cohesive strength of the resulting coating film and improves its hardness.

[0074] The allophanate group-containing polyisocyanate compound (B1) is a compound having an allophanate group and two or more isocyanate groups in one molecule, and has an isocyanate group content of more than 15.0% by mass.

[0075] The isocyanate group content is the mass ratio of isocyanate groups (NCO) to the mass (100%) of the polyisocyanate compound. The isocyanate group content may be a catalog value.

[0076] As the allophanate group-containing polyisocyanate compound (B1), commercially available products can be used, such as Coronate 2770 (manufactured by Tosoh Corporation), Desmodur N31100 (manufactured by Sumika Covestro Urethane Co., Ltd.), and Duranate A201H (manufactured by Asahi Kasei Corporation).

[0077] The allophanate group-containing polyisocyanate compound (B1) may be used alone or in combination of two or more kinds.

[0078] Prepolymer type isocyanate compound (B2) The prepolymer type isocyanate compound (B2) is obtained by reacting some of the isocyanate groups with a polyol, and has a number average molecular weight of 500 to 3,000 and an isocyanate group content of 3.0% by mass or more and 15.0% by mass or less.

[0079] The number average molecular weight of the prepolymer type isocyanate compound (B2) may be 800 or more, or may be 1,000 or more. The number average molecular weight of the prepolymer type isocyanate compound (B2) may be 800 to 3,000, or may be 1,000 to 3,000. When the number average molecular weight is within the above range, the elongation at break of the obtained coating film is improved.

[0080] In the present disclosure, the number average molecular weight can be measured by gel permeation chromatography as a polystyrene equivalent value.

[0081] The isocyanate group content of the prepolymer type isocyanate compound (B2) may be 5.0% by mass or more. The isocyanate group content may be 5.0% by mass or more and 15.0% by mass or less. When the isocyanate group content is within the above range, the breaking elongation of the resulting coating film is improved.

[0082] The prepolymer type isocyanate compound (B2) is obtained by reacting a polyol with an amount of polyisocyanate such that the isocyanate groups are in excess relative to the hydroxyl groups contained in the polyol. The prepolymer type isocyanate compound (B2) is obtained by reacting some of the isocyanate groups with the polyol. The prepolymer type isocyanate compound (B2) can typically be a reaction product of a polyol with a low-molecular-weight polyisocyanate. The prepolymer type isocyanate compound (B2) has an isocyanate group at the molecular terminal and a urethane bond in the molecule.

[0083] The polyol has two or more hydroxy groups in one molecule. Examples of the polyol include low-molecular-weight polyols and polymer polyols. Examples of the low-molecular-weight polyols include aliphatic polyols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,4-pentanediol, neopentyl glycol, 1,5-hexanediol, and 1,6-hexanediol; alicyclic polyols such as hydrogenated bisphenol A and 1,4-cyclohexanedimethanol; bis Examples of the polyols include aromatic polyols such as phenol A and hydroxyalkylated bisphenol A (particularly, bisphenol hydroxypropyl ether); polyols having a carboxy group such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvaleric acid; and tri- or higher functional polyols such as glycerin, mannitol, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol, and dipentaerythritol.

[0084] Examples of the polymer polyol include polyether polyol, acrylic polyol, polyurethane polyol, polyester polyol, polyesteramide polyol, etc. (e.g., polyols having a mass average molecular weight of 800 or more), with polyether polyol and polyester polyol being preferred. The polyether polyol may be a polyether polyol obtained by addition polymerization of one or more alkylene oxides selected from ethylene oxide, propylene oxide, etc. to one or more initiators selected from water, ethylene glycol, propylene glycol, etc. The polyester polyol may be a polyester polyol obtained by condensation polymerization of one or more polyhydric alcohols selected from ethylene glycol, propylene glycol, glycerin, etc. with one or more polycarboxylic acids or anhydrides thereof selected from adipic acid, phthalic acid, etc.

[0085] Examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI); alicyclic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), and hydrogenated xylylene diisocyanate; and aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate (XDI), 2,4-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 2,2'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, metaphenylene diisocyanate, polymethylene polyphenyl diisocyanate, naphthylene diisocyanate, and 3,3'-dimethyl-4,4'-biphenylene diisocyanate.

[0086] Examples of the prepolymer type isocyanate compound (B2) include hexamethylene diisocyanate (HDI)-based urethane prepolymers, isophorone diisocyanate (IPDI)-based urethane prepolymers, xylylene diisocyanate (XDI)-based urethane prepolymers, 2,4-tolylene diisocyanate (TDI)-based urethane prepolymers, and 4,4'-diphenylmethane diisocyanate (MDI)-based urethane prepolymers. The prepolymer type isocyanate compound (B2) may be an HDI-based urethane prepolymer. The HDI-based urethane prepolymer is a reaction product of a polyol and HDI.

[0087] As the prepolymer type isocyanate compound (B2), commercially available products can be used, such as Desmodur N3800, Desmodur E30600, Desmodur E30700 (all manufactured by Sumika Covestro Urethane Co., Ltd.), AE700-100, TSE-100 (all manufactured by Asahi Kasei Corporation), Coronate HL (manufactured by Tosoh Corporation), and Burnock DN-955-S (manufactured by DIC Corporation).

[0088] The prepolymer type isocyanate compound (B2) may be used alone or in combination of two or more kinds.

[0089] The content of the prepolymer isocyanate compound (B2) is, for example, 1.0% by mass or more and 50.0% by mass or less, based on 100% by mass of the total amount of the polyisocyanate compound (B). The content of the prepolymer isocyanate compound (B2) may be 2.0% by mass or more, 3.0% by mass or more, 8.0% by mass or more, or 10.0% by mass or more. The content of the prepolymer isocyanate compound (B2) may be 40.0% by mass or less, 25.0% by mass or less, or 15.0% by mass or less. The content of the prepolymer isocyanate compound (B2) may be 2.0% by mass or more and 40.0% by mass or less, 3.0% by mass or more and 25.0% by mass or less, 8.0% by mass or more and 15.0% by mass or less, or 10.0% by mass or more and 15.0% by mass or less.

[0090] The mass ratio (B1) / (B2) of the allophanate group-containing polyisocyanate compound (B1) to the prepolymer-type isocyanate compound (B2) is, for example, greater than 3.0 and not greater than 35.0. The mass ratio (B1) / (B2) may be greater than 3.0 and not greater than 20.0, or may be 4.0 or greater and 15.0 or less. When the mass ratio is within this range, the resulting coating film can achieve both appropriate elongation and hardness, and also has excellent abrasion resistance. In other words, when the mass ratio is within this range, the durability of the coating film is further improved.

[0091] Other polyisocyanate compounds (B3) The polyisocyanate compound (B) may contain other polyisocyanate compounds (B3) to the extent that the physical properties of the coating film are not affected. Examples of such polyisocyanate compounds (B3) include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and polymers of aliphatic polyisocyanates, alicyclic polyisocyanates, or aromatic polyisocyanates, and the polyisocyanate compound (B3) may contain one or more of them.

[0092] Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), and trimethylhexamethylene diisocyanate.

[0093] Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), and norbornane diisocyanate methyl.

[0094] Examples of the aromatic polyisocyanate include aromatic isocyanates such as xylylene diisocyanate (XDI), 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), and metaxylylene diisocyanate (MXDI).

[0095] Examples of the polymers include biuret, isocyanurate, and uretdione derivatives of aliphatic polyisocyanates, alicyclic polyisocyanates, or aromatic polyisocyanates.

[0096] The ratio (NCO / NH) of the total equivalent weight of isocyanate groups contained in the polyisocyanate compound (B) (NCO) to the total equivalent weight of amino groups contained in the polyamine compound (A) (NH) may be 0.40 or more and 2.20 or less. When the equivalent ratio is within the above range, the hardness of the resulting coating film can be improved. The ratio (NCO / NH) may be 0.50 or more, or 0.80 or more. The ratio (NCO / NH) may be 2.00 or less, or 1.40 or less. The ratio (NCO / NH) may be 0.50 or more and 2.00 or less, or 0.80 or more and 1.40 or less.

[0097] In the coating composition of the present disclosure, the total content of the polyamine compound (A) and the polyisocyanate compound (B) may be, for example, 25 to 97 parts by mass per 100 parts by mass of the nonvolatile content of the coating composition. By being within this range, the hardness and abrasion resistance of the resulting coating film are improved. The total content may be 40 to 97 parts by mass, or 50 to 97 parts by mass.

[0098] Pigment The coating composition of the present disclosure contains a pigment (C). The inclusion of the pigment (C) can improve the adhesion of the resulting coating film. The pigment (C) is contained in at least one of the main agent (I) and the curing agent (II), and is preferably contained in the main agent (I).

[0099] Examples of the pigment (C) include at least one of inorganic pigments and organic pigments. Examples of the inorganic pigment include calcium carbonate, titanium oxide, zinc oxide, precipitated barium sulfate, talc, silica, zirconia, alumina silicate, zirconia silicate, kaolin, bentonite, smectite, glass flakes (silica filler), iron oxide, acicular titanium oxide, anthraquinone, bismuth vanadate, carbon black, composite oxide pigments, seashell chalk, and eggshell calcium.

[0100] Examples of the organic pigment include quinophthalone pigments, benzimidazolone pigments, isoindoline pigments, isoindolineone pigments, dioxazine pigments, phthalocyanine pigments (copper phthalocyanine pigments, chlorinated copper phthalocyanine, brominated copper phthalocyanine, etc.), indanthrene pigments, perylene pigments, diketopyrrolopyrrole pigments, azo pigments, azomethine azo pigments, quinacridone pigments, and aniline pigments.

[0101] In one embodiment, the pigment may include an extender pigment, such as at least one selected from the group consisting of calcium carbonate, titanium oxide, zinc oxide, precipitated barium sulfate, talc, silica, zirconia, alumina silicate, zirconia silicate, kaolin, seashell chalk, and eggshell calcium.

[0102] The pigment (C) may be used alone or in combination of two or more kinds.

[0103] The pigment volume concentration (PVC) of the coating composition is, for example, 3% by volume or more and 10% by volume or less. When the PVC is within the above range, the adhesion of the resulting coating film is improved. The PVC may be 4% by volume or more, or 5% by volume or more. The PVC may be 10% by volume or less. The PVC may be 4% by volume or more and 10% by volume or less, or 5% by volume or more and 10% by volume or less.

[0104] The pigment volume concentration (PVC) in this specification can be calculated from the following formula using the volume of all pigments (P) calculated from the specific gravity and blending amount of each pigment contained in the paint composition, and the volume of resin (R) calculated from the specific gravity and blending amount of each resin nonvolatile content. PVC (volume%) = P / (P+R) x 100

[0105] [Dehydrating agent] The coating composition of the present disclosure may further contain a dehydrating agent. The dehydrating agent can improve the pot life of the coating composition. Although not intended to be limited to a particular theory, it is believed that the dehydrating agent inhibits reaction between the isocyanate group of the polyisocyanate compound (B) and water that may be contained in the coating composition or moisture in the surrounding environment.

[0106] The dehydrating agent may be either a physical dehydrating agent or a chemical dehydrating agent, and may be a physical dehydrating agent. Examples of the physical dehydrating agent include synthetic zeolites such as molecular sieves, silica gel, and porous materials such as deciclay. Examples of the chemical dehydrating agent include calcium sulfate, calcium chloride, and calcium oxide.

[0107] The content of the dehydrating agent is, for example, 0.0 parts by mass or more and 15.0 parts by mass or less per 100 parts by mass of the resin nonvolatile content. The content of the dehydrating agent may be 0.3 parts by mass or more. The content of the dehydrating agent may be 10.0 parts by mass or less. The content of the dehydrating agent may be 0.3 parts by mass or more and 10.0 parts by mass or less.

[0108] [Organic solvents] The coating composition of the present disclosure may further contain an organic solvent. It is more preferable to use an organic solvent in an amount that takes into consideration recent trends in environmental conservation and environmental impact. The amount of organic solvent may be 10% by mass or less, based on a total of 100% by mass of the coating composition (based on a total of 100% by mass of the main component (I) and the curing agent (II)). By having the amount of organic solvent within the above range, the amount of volatile organic compounds (VOCs) and odor of the coating can be reduced. The drying time is also reduced, improving application ease. Particularly when used for road markings, the traffic control time during application can be shortened. The amount of organic solvent may be 5% by mass or less, 3% by mass or less, or even 0% by mass.

[0109] The organic solvent may include those commonly used in solvent-based paints, such as methyl ethyl ketone, cyclohexanone, Solvesso 100 (manufactured by Exxon Chemical Co.), methoxybutyl acetate, 1-methoxy-2-propyl acetate, cellosolve acetate, butyl cellosolve acetate, methyl acetate, ethyl acetate, butyl acetate, toluene, xylene, petroleum ether, and petroleum naphtha.

[0110] [Viscosity adjuster] The coating composition of the present disclosure may contain a viscosity modifier. The use of a viscosity modifier can impart thixotropy to the coating composition. Furthermore, deterioration of the coating appearance due to interlayer mixing, sagging, etc. can be reduced. From the viewpoint of achieving both drying properties and coating appearance, it is preferable to use a body pigment and a viscosity modifier in combination. The use of a body pigment and a viscosity modifier makes it possible to reduce the viscosity of the coating under high shear and slow the viscosity recovery, thereby obtaining an excellent coating appearance.

[0111] As the viscosity modifier, generally, a substance exhibiting thixotropy can be used, and examples thereof include polyolefin-based viscosity modifiers such as colloidal swollen dispersions of polyolefins, polyamide-based viscosity modifiers such as swollen dispersions of fatty acid amides, amide-based fatty acids, and phosphates of long-chain polyaminoamides, organic bentonite-based viscosity modifiers such as organic acid smectite clay and montmorillonite, inorganic pigments such as aluminum silicate and barium sulfate, flat pigments whose viscosity is developed depending on the shape of the pigment, crosslinked resin particles, and non-crosslinked resin particles.

[0112] Examples of polyolefin viscosity modifiers include polyethylene, polypropylene, ethylene-propylene copolymer, polyethylene oxide obtained by contacting polyethylene with oxygen or the like, polypropylene oxide obtained by contacting polypropylene with oxygen or the like, ethylene oxide-propylene copolymer obtained by contacting ethylene-propylene copolymer with oxygen or the like, ethylene-(meth)acrylic acid copolymer, ethylene-maleic anhydride copolymer, and propylene-maleic anhydride copolymer, of which polyethylene oxide, polypropylene oxide, and ethylene oxide-propylene copolymer are preferred, and polyethylene oxide is more preferred.

[0113] Specific examples of polyethylene oxide that can be used as a viscosity adjuster include Disparlon PF-911, Disparlon 4200-10, and Disparlon 4200-20 (manufactured by Kusumoto Chemicals Co., Ltd.).

[0114] As a polyamide-based viscosity modifier that can be used as a viscosity modifier, for example, fatty acid amides can be used. Commercially available fatty acid amides are known to be in powder form or paste form. Paste-form products are generally diluted with a solvent such as xylene or alcohol.

[0115] An example of the fatty acid amide is a diamide having the general structure shown in formula (IV) below.

[0116] [ka]

[0117] [In formula (IV), R 5 is a residue obtained by removing a hydroxyl group and a carboxyl group from a hydroxyl-containing fatty acid, and preferably C 1-20 represents an alkylene group, more preferably a straight or branched C 1-20 Alkylene groups, more preferably straight or branched C 1-10 Alkylene groups, more preferably straight or branched C 1-5 Represents an alkylene group. R 6 is a residue obtained by removing an amino group from a diamine, and is preferably C 1-20 represents an alkylene group, more preferably a straight or branched C 1-20 alkyl groups, more preferably straight or branched C 1-10 Alkylene groups, more preferably straight or branched C 1-5 represents an alkylene group.]

[0118] The diamide is a diamine (NH2-R 6 -NH2) to a hydroxyl group-containing fatty acid (HO-R 5 In the formula (IV), R 5 Fatty acid amides in which an OH group is not bonded to either of the above are also known as viscosity control agents and can be used in the present invention.

[0119] The fatty acid amides used in the coating material of the present invention include the above-mentioned diamides and polyamides alone or in mixtures, and specific examples include Disparlon NS-5025, Disparlon 6900-10X, Disparlon 6900-20X, Disparlon 6840-10X (all manufactured by Kusumoto Chemicals Co., Ltd.), Flonon HR-2 (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0120] [Compounds having anionic and cationic groups] The coating composition of the present disclosure may contain a compound having an anionic group and a cationic group. The inclusion of this compound can improve the pot life of the coating composition. While not intended to be limited to a particular theory, it is believed that the inclusion of a compound having an anionic group and a cationic group can suppress association between the amino group of the amine compound (A) and the isocyanate group of the polyisocyanate compound (B), as well as suppress the nucleophilicity of the amino group of the amine compound (A), thereby improving the pot life of the coating composition. According to the inventors' investigations, the above-mentioned effects are difficult to achieve with compounds having only anionic groups or only cationic groups.

[0121] The anionic group includes acid groups such as carboxyl groups, sulfonic acid groups, and phosphoric acid groups, as well as esters of such acid groups (i.e., carboxylic acid esters, sulfonic acid esters, and phosphoric acid esters), with phosphoric acid groups and phosphate esters being preferred. The anionic group in the compound may be in the form of a salt such as an ammonium salt, lithium salt, sodium salt, or potassium salt.

[0122] Examples of the cationic group include an unsubstituted amino group, a mono- or di-substituted amino group, and a quaternary ammonium group.

[0123] The compound having an anionic group and a cationic group is preferably a polymer such as polyester, polyether, or polyacrylic polymer, or a polymer compound such as a copolymer of two or more types of polymers selected from the above polymers, to which the anionic group and the cationic group are bonded.

[0124] The acid value of the compound having an anionic group and a cationic group may be 5 mgKOH / g or more and 200 mgKOH / g or less, more preferably 10 mgKOH / g or more and 150 mgKOH / g or less.

[0125] The amine value of the compound having an anionic group and a cationic group is preferably 5 mgKOH / g or more, more preferably 5 mgKOH / g or more and 200 mgKOH / g or less, and more preferably 20 mgKOH / g or more and 150 mgKOH / g or less.

[0126] The mass average molecular weight of the compound having an anionic group and a cationic group may be, for example, 200 or more and 500,000 or less, preferably 200 or more and 100,000 or less, and more preferably 200 or more and 70,000 or less.

[0127] The compound having an anionic group and a cationic group may be a commercially available product. Examples of such commercially available products include DISPARLON PW-36 and DISPARLON AQ-330 (manufactured by Kusumoto Chemicals Co., Ltd.); BYK-381, BYK-ES80, DISPERBYK-103, DISPERBYK-111, DISPERBYK-142, DISPERBYK-145, DISPERBYK-2001, DISPERBYK-2025, DISPERBYK-9076, and ANTI-TERRA-203 (manufactured by BYK-Chemie Co., Ltd.). Solsperse 24000GR, Solsperse 32000, Solsperse 33000, Solsperse 34750, Solsperse 35100, Solsperse 35200, Solsperse 37500, Solsperse 39000 (manufactured by The Lubrizol Japan Corporation); Ajisper PB821, Ajisper PB822, Ajisper PB824, Ajisper PB881 (manufactured by Ajinomoto Fine-Techno Co., Inc.), etc. may be used.

[0128] [Other ingredients] In addition to the above components, the coating composition of the present disclosure may contain other components as needed. Examples of such other components include various additives commonly used in coating compositions. Examples of such additives include resin particles, resin components, anti-sagging and anti-settling agents, curing catalysts (organometallic catalysts), color-shift inhibitors, dispersants, anti-foaming and anti-popping agents, thickeners, viscosity modifiers, leveling agents, matting agents, UV absorbers, light stabilizers, antioxidants, anti-foaming agents, surface conditioners, plasticizers, pinhole inhibitors, rust inhibitors, film-forming aids, dehydrating agents, surfactants, and compounds having anionic and cationic groups. The amounts of these components may be appropriately adjusted within a range that does not impair the effects of the present invention.

[0129] The optional components may be contained in either the main agent (I) or the curing agent (II), and are preferably contained in the main agent (I).

[0130] [Method for preparing base agent (I) and curing agent (II)] The main component (I) and the curing agent (II) can be prepared by mixing the components contained therein by a method known to those skilled in the art, such as a kneading / mixing method using a kneader or a roll, or a dispersing / mixing method using a sand grind mill or a disperser.

[0131] [Shear viscosity] Main agent (I) at a shear rate of 10,000 s at 25°C -1 The shear viscosity of the curing agent (II) measured at a shear rate of 10,000 s at 25°C may be 1,000 mPa·s or less. -1 The shear viscosity measured by the method may be 1,000 mPa·s or less. The shear viscosity of the base agent (I) and the curing agent (II) may both be 1,000 mPa·s or less.

[0132] Shear rate 10,000 s -1is a value that assumes the strain imparted to the coating composition during application. The shear viscosity within the above range indicates that the coating composition has a low viscosity during application. Such a coating composition has excellent workability and improves the adhesion of the resulting coating film to asphalt. The shear viscosity may be 800 mPa·s or less, or 500 mPa·s or less, respectively.

[0133] The shear viscosity was measured, for example, using a stress-controlled rheometer MCR-301 (manufactured by Anton Paar) with a jig: cone plate CP50 and a shear rate of 10,000 s -1 The viscosity is obtained by measuring the steady flow at a measurement temperature of 25°C and measuring the viscosity 60 seconds after the start of the measurement.

[0134] [Elongation at break] The elongation at break of the coating film obtained from the coating composition of the present disclosure is, for example, 10% or more. This further improves durability. The elongation at break of the coating film can be adjusted, for example, by the content of the prepolymer type isocyanate compound (B2) in 100% of the total mass of the polyisocyanate compound (B). The elongation at break may be 15% or more.

[0135] The elongation at break can be determined as follows. First, a free film (300 μm thick) of the coating is prepared using the coating composition of the present disclosure. Using a tensile tester (for example, a Tensilon tensile / extension universal tester manufactured by A&D Co., Ltd.), the length of the free film at break is measured at a tensile speed of 5 mm / min and a measurement temperature of 23°C. The elongation at break is calculated from the length at break using the following formula: Breaking elongation of coating film (%) = 100 x (length at break of free film / original length)

[0136] [Object to be coated] Examples of substrates to be coated include asphalt, concrete, and composite substrates thereof, as well as metals, plastics, wood, glass, fabrics, ceramic materials, and the like.

[0137] Examples of the metal sheet include zinc-plated steel sheets, zinc-aluminum alloy-plated steel sheets, aluminum alloy-plated steel sheets, hot-dip zinc-aluminum-magnesium alloy-plated steel sheets, stainless steel sheets, and cold-rolled steel sheets, all of which are manufactured by a hot-dip process or an electrolytic process. In addition to these steel sheets or plated steel sheets, metal sheets such as aluminum sheets (including aluminum alloy sheets) can also be coated. The metal sheet is preferably surface-treated. Specifically, the metal sheet is preferably subjected to a pretreatment such as alkaline degreasing, hot water washing, or water washing, followed by a chemical conversion treatment. The chemical conversion treatment may be performed by a known method, and examples include non-chromate treatments such as chromate treatment and zinc phosphate treatment. The surface treatment can be appropriately selected depending on the steel sheet to be used, but a treatment that does not contain heavy metals is preferred.

[0138] Examples of the plastic member include an acrylic plate, a polyvinyl chloride plate, a polycarbonate plate, an ABS plate, a polyethylene terephthalate plate, and a polyolefin plate.

[0139] Examples of the inorganic member include ceramic building materials and glass substrates described in JIS A 5422, JIS A 5430, etc., such as calcium silicate boards, pulp cement boards, slag gypsum boards, magnesium carbonate boards, asbestos-perlite boards, wood chip cement boards, hard wood cement boards, concrete boards, and lightweight aerated concrete boards.

[0140] Examples of the wooden members include lumber, laminated lumber, plywood, particle board, fiber board, improved wood, chemically treated wood, and floorboards.

[0141] Examples of the pavement such as road surfaces include asphalt pavement, concrete pavement, and brick pavement.

[0142] Specific examples of the substrate include roads, road structures, various building structures and their internal equipment, railway structures, various protective facilities, various vehicles and their accessories, pedestrian wear, utility poles, and the interior walls of various building structures.

[0143] The substrate may be, for example, one or more selected from a roadway, a road structure, a railway structure, an internal facility of a building structure, an interior of a building structure, an article worn by pedestrians, and a utility pole.

[0144] Examples of road structures include pavements, road markings, sidewalks, crosswalks, drainage facilities, at-grade intersections, bridges, earthworks, tunnels, turnouts, traffic safety facilities, traffic islands, bus stops, parking lanes, and parking lots. Examples of traffic safety facilities include grade separation facilities, guardrails, guard poles, protective fences, lighting facilities, delineators, and road reflectors.

[0145] Coating film formation method The method for forming a coating film of the present disclosure comprises mixing a base agent (I) and a curing agent (II) to prepare a coating composition, and applying the coating composition to an object to be coated.

[0146] [Method for preparing coating composition] The coating composition can be prepared by mixing the base component (I) and the curing agent (II) using the same mixing means as for each component. Alternatively, the base component (I) and the curing agent (II) may be delivered to a two-component mixing gun and mixed at the tip of the gun.

[0147] [Painting method] The coating composition can be applied by a conventional coating method, such as immersion, brushing, roller coating, roll coating, air spraying, airless spraying, curtain flow coating, roller curtain coating, die coating, etc. The coating method can be appropriately selected depending on the substrate.

[0148] The coating film is formed by applying the coating composition to an object to be coated to form a coating film, and then curing the coating film. The coating composition of the present disclosure can be cured at a relatively low temperature in a short time.

[0149] The temperature during curing may be preferably 5° C. or higher and 60° C. or lower, more preferably 10° C. or higher and 40° C. or lower. The curing time may be, for example, 10 minutes or higher and 3 hours or lower.

[0150] The thickness of the coating film can be, for example, 10 to 1,000 μm.

[0151] Although a coating film formed from the coating composition of the present disclosure has good protective and decorative functions even in a single layer, the coating composition of the present disclosure may be applied as a topcoat paint on an undercoat paint film. In this case, known undercoat paints such as electrodeposition paints and primers can be used as the undercoat paint for forming the undercoat paint film. Furthermore, the coating composition of the present disclosure may be applied as an undercoat paint under a topcoat paint, and in this case, known topcoat paints such as intermediate paints, base paints, and clear paints can be used.

[0152] The coating composition of the present disclosure may be applied directly to an object to be coated, or, for example, the coating composition of the present disclosure may be applied as a topcoat on top of an undercoat film. [Example]

[0153] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the examples, "parts" and "%" are by weight unless otherwise specified.

[0154] Example 1 <Preparation of the main agent> 66.4 parts by mass of Desmophen NH1220 as polyamine compound (A-1), 25.0 parts by mass of Typec CR-97 as pigment (C-1), and 5.0 parts by mass of Super 2000 as pigment (C-2) were stirred and mixed in a disper to obtain a mixture.

[0155] Next, the entire mixture obtained and glass beads (equal to the total mass of the mixture) were placed in a tabletop SG Mill 1500W disperser (manufactured by Ohira Systems Co., Ltd.), and the pigment was dispersed until the particle diameter of the pigment reached 30 to 40 μm, thereby obtaining the main agent (I).

[0156] <Preparation of Curing Agent> 71.1 parts by mass of Coronate 2770 as the polyisocyanate compound (B1-1) and 7.9 parts by mass of Desmodur N3800 as the polyisocyanate compound (B2-1) were stirred and mixed using a disper to prepare a curing agent (II).

[0157] <Preparation of Coating Composition> 96.4 parts by mass of the base agent (I) and 79.0 parts by mass of the curing agent (II) were mixed using a disper and stirred until homogeneous, to obtain a coating composition. The ratio (NCO / NH) of the total equivalent weight of the isocyanate groups contained in the polyisocyanate compounds (B1-1) and (B2-2) to the total equivalent weight of the amino groups contained in the polyamine compound (A-1) was 1.20.

[0158] <Preparation of test plates for evaluation>

[0159] (Examples 2 to 22, Comparative Examples 1 to 3) Coating compositions were prepared in the same manner as in Example 1, except that the types and amounts of each component were as shown in Tables 1 to 3. The compositions and various characteristic values ​​are shown in Tables 1 to 3. The blending amounts in the tables include volatile components.

[0160] [Polyamine compound (A)] (Polyamine compound (A1)) (A1-1) Product name: Desmophen NH1220, manufactured by Sumika Covestro Urethane Co., Ltd., alicyclic secondary polyamine (aspartic acid ester amine); non-volatile content: 100% by mass; mass average molecular weight: 461; amine equivalent: 230 g / eq; R 1 =(CH2)3CH(CH3)CH2, R 2 =CH2CH3, equivalent to compound (3)

[0161] (A1-2) Product name: Desmophen NH1420, manufactured by Sumika Covestro Urethane Co., Ltd., alicyclic secondary polyamine (aspartic acid ester amine), non-volatile content: 100% by mass, mass average molecular weight: 555, amine equivalent: 279 g / eq, R 1 =C6H 10 CH2C6H 10 , R 2 =CH2CH3, equivalent to compound (1)

[0162] (A1-3) Product name: Desmophen NH1520, manufactured by Sumika Covestro Urethane Co., Ltd., aliphatic secondary polyamine (aspartic acid ester amine), non-volatile content: 100% by mass, mass average molecular weight: 585, amine equivalent: 290 g / eq, R 1 =(C6H9(CH3))CH2(C6H9(CH3)), R 2 =CH2CH3, equivalent to compound (2)

[0163] (Other polyamine compounds) (A2) Product name: Clrearlink 1000, manufactured by Dorf Ketal, alicyclic secondary diamine; non-volatile content: 100% by mass; mass average molecular weight: 322; amine equivalent: 157 to 166 g / eq

[0164] [Polyisocyanate compound (B)] (Allophanate group-containing polyisocyanate compound (B1)) (B1-1) Product name: Coronate 2770, manufactured by Tosoh Corporation, aliphatic isocyanate compound (HDI (hexamethylene diisocyanate) allophanate), non-volatile content: 100% by mass, NCO content: 19.2% by mass

[0165] (B1-2) Product name: Desmodur N31100, manufactured by Sumika Covestro Urethane Co., Ltd., aliphatic isocyanate compound (allophanate of HDI (hexamethylene diisocyanate)); non-volatile content: 100% by mass; NCO content: 19.5% by mass

[0166] (Prepolymer type isocyanate compound (B2)) (B2-1) Product name: Desmodur N3800, manufactured by Sumika Covestro Urethane Co., Ltd., aliphatic isocyanate compound (prepolymer of HDI (hexamethylene diisocyanate)), non-volatile content: 100% by mass, NCO content: 11.0% by mass, number average molecular weight: 1,800

[0167] (B2-2) Product name: Desmodur E30700, manufactured by Sumika Covestro Urethane Co., Ltd., aliphatic isocyanate compound (prepolymer of HDI (hexamethylene diisocyanate)); non-volatile content: 100% by mass; NCO content: 11.0% by mass; number average molecular weight: 1,200

[0168] (Other polyisocyanate compounds (B3)) (B3-1) Product name: TSA-100, manufactured by Asahi Kasei Corporation, aliphatic isocyanate compound (HDI (hexamethylene diisocyanate) isocyanurate); non-volatile content: 100% by mass; NCO content: 20.6% by mass (B3-2) Product name: 24A-100, manufactured by Asahi Kasei Corporation, aliphatic isocyanate compound (biuret form of HDI (hexamethylene diisocyanate)); non-volatile content: 100% by mass; NCO content: 23.5% by mass

[0169] Pigment (C-1) Product name: Typaque CR-97, manufactured by Ishihara Sangyo Kaisha, Ltd., inorganic pigment (titanium oxide) (C-2) Product name: Super 2000, manufactured by Maruo Calcium Co., Ltd., inorganic pigment (calcium carbonate) (C-3) Product name: FASTOGEN BLUE CDB31, manufactured by DIC, organic pigment (copper phthalocyanine) (C-4) Product name: Raven 420 Powder, manufactured by COLUMBIAN CHEMICALS COMPANY, organic pigment (carbon black)

[0170] [Additives] Product name: TVS Chinro, manufactured by Nitto Kasei Co., Ltd., organometallic catalyst, dibutyltin laurate (DBTL)

[0171] [Dehydrating agent] Product name: Zeolum A4, manufactured by Tosoh Corporation, dehydrating agent, zeolite

[0172] [Organic solvents] (organic solvent 1) Product name: Xylol, manufactured by Shoei Chemical Co., Ltd., organic solvent, xylene (organic solvent 2) Product name: PMA, manufactured by Sankyo Chemical Co., Ltd., organic solvent, methoxypropyl acetate

[0173] [Evaluation items] (Viscosity measurement of coating composition) Steady flow measurements were carried out for each of the base resins and curing agents obtained in the Examples and Comparative Examples using a stress-controlled rheometer MCR-301 (manufactured by Anton Paar) under the following conditions, and the viscosity was measured 60 seconds after the start of the measurement. The measurement conditions were: Jig: Cone Plate CP50-1, Shear Rate: 10,000 s -1 The measurement temperature was 25°C.

[0174] (Workability at room temperature) The resulting coating composition was applied at 25°C using an ADY static gun (manufactured by Sulzer) and the room temperature application property was evaluated. The evaluation criteria were as follows: Evaluation A was considered to be acceptable.

[0175] Evaluation criteria A: It can be painted. B: The coating composition is too viscous to be discharged from the nozzle, making coating impossible.

[0176] (adhesion) The resulting coating composition was applied to a dense asphalt mixture specimen (300 x 300 mm) at 23°C (ambient temperature) using an impact spray mixing gun to a thickness of 300 μm, and then cured at 23°C for 168 hours to obtain a test panel.

[0177] The adhesion of the coating to the test plate was evaluated using a torsion tester manufactured by Nakajima Gihan Co., Ltd. Specifically, a tire was brought into contact with the coating surface of the test plate, and the tire was rotated while a load was applied to the contact area in a direction perpendicular to the coating surface.

[0178] Test conditions: tire contact area: 10,000 mm 2 The test was performed at a temperature of 23°C, a load of 490N, a rotation speed of 15 rpm, and a test time of 30 minutes. The tire used was a Hyde Cart air tire with a diameter of 220mm, a width of 65mm, and an air pressure of 2.0 x 100kPa.

[0179] The peeling area of ​​the coating was determined using binarization software (GIMP), and the peeling rate (%) of the coating was calculated using the following formula. Paint peeling rate (%) = 100 x paint peeling area / tire contact area The adhesion of the coating was evaluated based on the peeling rate of the coating. The evaluation criteria are as follows: A rating of C or higher was considered a pass.

[0180] Evaluation criteria A: The peeling rate of the coating is 0%. B: The peeling rate of the coating film is more than 0% and less than 5%. C: The peeling rate of the coating film is 5% or more and less than 10%. D: The peeling rate of the coating film is 10% or more.

[0181] (Hardness) Martens hardness The resulting coating composition was applied to the surface of a bonded steel plate (manufactured by TP Giken Co., Ltd.) as the substrate using an impingement spray mixing gun so that the dry film thickness was 300 μm, and the coating was cured at 23°C for 168 hours to obtain a test plate.

[0182] The Martens hardness of the coating film was measured using a Fischerscope HM2000XYp (manufactured by Fischer Instruments; test load: 300 mN / 20 seconds) and evaluated according to the following criteria. A rating of C or higher was considered to be acceptable.

[0183] Evaluation criteria A: Martens hardness is 70N / mm 2 That's all. B: Martens hardness is 50N / mm 2 More than 70N / mm 2 is less than. C: Martens hardness is 40N / mm 2 More than 50N / mm 2 is less than. D: Martens hardness is 40N / mm 2 is less than.

[0184] (wear resistance) The abrasion resistance of the coating film was evaluated according to the method specified in JIS K 5600-5-9 Abrasion Resistance (Abrasion Wheel Method). Test plates were prepared under the same conditions as those used for hardness measurement. A rotary abrasion tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used as the testing machine, and a CS-17 (manufactured by Taber) was used as the abrasion wheel. The abrasion loss after 1,000 rotations at 60 rpm under a load of 1 kg was calculated using the following formula. Abrasion loss (mg) = test plate mass before test - test plate mass after test The abrasion resistance of the coating film was evaluated based on the abrasion loss. The evaluation criteria were as follows: A rating of B or higher was considered to be acceptable.

[0185] Evaluation criteria A: The abrasion loss is 50 mg or less. B: The abrasion loss is more than 50 mg and 100 mg or less. C: Wear loss exceeds 100 mg.

[0186] (Elongation at break) The resulting coating composition was applied to the surface of a polypropylene plate (manufactured by TP Giken Co., Ltd.) using a 30-mil doctor blade to prepare a dry film with a thickness of 300 μm, which was then cut into 70 × 10 mm test pieces.

[0187] The test specimens were measured for breaking elongation of the coating film using a Tensilon tensile / extension universal testing machine (manufactured by A&D Corporation; tensile conditions: 5 mm / min, measurement temperature: 23°C), and evaluated according to the following criteria. The breaking elongation of the coating film was calculated using the following formula. A rating of B or higher was considered a pass. Breaking elongation of coating film (%) = (length at break of film / original length) x 100

[0188] Evaluation criteria A: The coating film has a breaking elongation of 15% or more. B: The coating film has a breaking elongation of 10% or more and less than 15%. C: The coating film has a breaking elongation of less than 10%.

[0189] (Durability: Overall rating) The evaluation results of the adhesion, hardness, elongation at break and abrasion resistance were taken into consideration and evaluated according to the following criteria.

[0190] A: All four items of adhesion, hardness, elongation at break, and abrasion resistance passed, and three or more items exceeded the pass criteria. B: All four items of adhesion, hardness, elongation at break, and abrasion resistance passed, and no more than two items exceeded the pass standard. C: At least one of the four items of adhesion, hardness, elongation at break and abrasion resistance is unacceptable.

[0191] [Table 1]

[0192] [Table 2]

[0193] [Table 3]

[0194] In Examples 1 to 22, the coating compositions had good room-temperature application properties, and the resulting coating films had good durability (adhesion, hardness, abrasion resistance, and elongation at break). Comparative Example 1 is an example that does not contain an allophanate group-containing polyisocyanate compound (B1). The coating composition of Comparative Example 1 was poor in room temperature application properties. In addition, the resulting coating film was poor in adhesion and hardness, and did not satisfy durability requirements. Comparative Example 2 is an example that does not contain the prepolymer type isocyanate compound (B2). The resulting coating film was poor in abrasion resistance and elongation at break, and did not satisfy durability requirements. Comparative Example 3 is an example that does not contain pigment (C). The resulting coating film had poor adhesion and did not satisfy the durability requirements. [Industrial Applicability]

[0195] The coating composition of the present invention provides a coating film having excellent durability and is also easy to apply.

Claims

1. Contains a base agent (I) and a curing agent (II), At least one of the base agent (I) and the curing agent (II) contains a pigment (C), The main component (I) contains a polyamine compound (A), The curing agent (II) contains a polyisocyanate compound (B), The polyamine compound (A) contains an aspartic acid ester amine (A1), the content of the aspartic acid ester amine (A1) is 80% by mass or more and 100% by mass or less, based on 100% by mass of the total amount of the polyamine compound (A); The polyisocyanate compound (B) includes an allophanate group-containing polyisocyanate compound (B1) and a prepolymer-type isocyanate compound (B2), The allophanate group-containing polyisocyanate compound (B1) has an isocyanate group content of more than 15.0 mass%, The coating composition, wherein the prepolymer type isocyanate compound (B2) is obtained by reacting a part of the isocyanate groups with a polyol, and has a number average molecular weight of 500 to 3,000 and an isocyanate group content of 3.0 mass% or more and 15.0 mass% or less.

2. 2. The coating composition according to claim 1, wherein the mass ratio (B1) / (B2) of the content of the allophanate group-containing polyisocyanate compound (B1) to the content of the prepolymer-type isocyanate compound (B2) is greater than 3.0 and not greater than 35.

0.

3. The aspartic acid ester amine (A1) is represented by the following formula (I): 【Chemistry 1】 [In formula (I), R １ is a divalent C １－８０ represents a hydrocarbon group, R ２ are, independently of each other, C １－２０ represents a hydrocarbon group.] The coating composition according to claim 1, wherein

4. 2. The coating composition according to claim 1, wherein the content of the prepolymer-type isocyanate compound (B2) is 1.0 mass% or more and 50.0 mass% or less in 100 mass% of the total amount of the polyisocyanate compound (B).

5. The coating composition according to claim 1 , wherein the pigment (C) comprises at least one of an inorganic pigment and an organic pigment.

6. 2. The coating composition according to claim 1, wherein the pigment volume concentration of the pigment (C) in the coating composition is 3% by volume or more and 10% by volume or less.

7. 2. The coating composition according to claim 1, wherein the ratio (NCO / NH) of the total equivalents of isocyanate groups contained in the polyisocyanate compound (B) to the total equivalents of amino groups contained in the polyamine compound (A) is 0.40 or more and 2.20 or less.

8. The coating composition of claim 1 further comprising a dehydrating agent.

9. 2. The coating composition according to claim 1, wherein the amount of the organic solvent is 10% by mass or less of the coating composition.

10. The shear rate of the main agent (I) at 25°C is 10,000 s －１ and the shear viscosity of the curing agent (II) measured at a shear rate of 10,000 s at 25 ° C. －１ 2. The coating composition according to claim 1, wherein the shear viscosity measured by the method is 1,000 mPa·s or less.

11. 2. The coating composition according to claim 1, which is used on one or more selected from roadways, road structures, railway structures, internal equipment of building structures, interior decoration of building structures, pedestrian wear, and utility poles.

12. Mixing a base agent (I) and a curing agent (II) to prepare a coating composition; and applying the coating composition to an object to be coated. At least one of the base agent (I) and the curing agent (II) contains a pigment (C), The main component (I) contains a polyamine compound (A), The curing agent (II) contains a polyisocyanate compound (B), The polyamine compound (A) contains an aspartic acid ester amine (A1), the content of the aspartic acid ester amine (A1) is 80% by mass or more and 100% by mass or less, based on 100% by mass of the total amount of the polyamine compound (A); The polyisocyanate compound (B) includes an allophanate group-containing polyisocyanate compound (B1) and a prepolymer-type isocyanate compound (B2), The allophanate group-containing polyisocyanate compound (B1) has an isocyanate group content of more than 15.0 mass%, The prepolymer type isocyanate compound (B2) is obtained by reacting a part of the isocyanate groups with a polyol, and has a number average molecular weight of 500 to 3,000 and an isocyanate group content of 3.0% by mass or more and 15.0% by mass or less.

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