Raw material for producing polyurea resin composition, polyurea resin composition, and coating material

Abstract

To provide a raw material for producing a polyurea resin composition having a pot life suitable for hand coating and capable of obtaining a coating film satisfying all of transparency, elongation, water resistance and chemical resistance required for practical use, and to provide a polyurea resin composition.SOLUTION: The polyurea resin composition production material of the present invention includes a component (A) containing a polyisocyanate compound (a) and a component (B) containing a polyamine compound (b), wherein the polyamine compound (b) contains an aspartic acid ester compound (b1) and an aromatic polyamine compound (b2), and the content of the aspartic acid ester compound (b1) is more than 50 mass% relative to the total mass of the aspartic acid ester compound (b1) and the aromatic polyamine compound (b2).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a raw material for producing a polyurea resin composition, a polyurea resin composition, and a paint. [Background technology]

[0002] Polyurea resins have excellent physical properties and can be used without solvents, making them useful as reinforcement materials for aging buildings and structures, or as materials that provide durability against natural disasters such as earthquakes. For these applications, highly transparent coatings are required so that cracks in the substrate can be visually detected through the coating. In addition, high strength, moderate elongation, water resistance, and chemical resistance are required to protect structures and prevent their collapse.

[0003] Furthermore, since the polyisocyanate component and polyamine component, which are the raw materials for polyurea resin, react extremely quickly, in coating a polyurea resin composition, these two raw materials are generally mixed using an impingement mixing type spray device and then spray coated.

[0004] Furthermore, since spraying equipment cannot be used for coating enclosed spaces or complex shapes, there is a need for the development of a polyurea resin composition that can be applied by hand (hereinafter also referred to as "hand coating") and has a long pot life.

[0005] For example, Patent Document 1 discloses a method for producing a compound comprising: (A) an aspartic acid ester compound having a specific structure; (B) a polyisocyanate component obtained from one or more diisocyanate monomers selected from the group consisting of aliphatic and alicyclic diisocyanates and a polyol containing a polycaprolactone polyol having a number average molecular weight of 500 to 1500, the ratio of the polycaprolactone polyol to the total amount of the polyol is 20% by mass or more; The document discloses a polyaspartic coating composition in which the polyisocyanate component contains 10.0 mass% or less of an isocyanurate trimer based on the total amount of the polyisocyanate component. The document describes that the polyaspartic coating composition maintains drying and curing properties, while providing coating films with excellent scratch resistance, chemical resistance, and weather resistance. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2018 / 163959 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the polyaspartic coating composition described in Patent Document 1 has room for improvement in the elongation of the resulting coating film, since it is used as a reinforcing material for buildings.

[0008] A commonly known method for improving the elongation of a coating film is to use a urethane prepolymer as a polyisocyanate component, but an increase in the number of urethane bonds tends to result in a decrease in the water resistance and chemical resistance of the coating film.

[0009] The present invention aims to provide a raw material for producing a polyurea resin composition, and a polyurea resin composition, which can give a coating film that has a pot life suitable for hand application and satisfies all of the transparency, elongation, water resistance, and chemical resistance required for practical use. The present invention also aims to provide a paint containing the polyurea resin composition, a coating film obtained from the paint, a laminate having the coating film, and a coating method for applying the paint. [Means for solving the problem]

[0010] The present inventors have conducted extensive research to solve the above-mentioned problems and have found that the above-mentioned problems can be solved by using a combination of an aspartic acid ester compound and an aromatic polyamine compound as polyamine compounds and adjusting the compounding ratio of these compounds within a specific range, thereby arriving at the present invention.

[0011] That is, the present invention provides the following aspects. <1> A raw material for producing a polyurea resin composition, comprising a component (A) containing a polyisocyanate compound (a) and a component (B) containing a polyamine compound (b), The polyamine compound (b) contains an aspartic acid ester compound (b1) and an aromatic polyamine compound (b2), A raw material for producing a polyurea resin composition, characterized in that the content of the aspartic acid ester compound (b1) is more than 50 mass% based on the total mass of the aspartic acid ester compound (b1) and the aromatic polyamine compound (b2). <2> The aspartic acid ester compound (b1) is a compound represented by the following general formula (1): <1> A raw material for producing the polyurea resin composition described in claim 1. X(-NH-CH(CHCOOR 2 )COOR 1 ) n (1) (wherein X is an organic group, and R 1 and R 2 are the same or different organic groups, and n is an integer of 2 or more. <3> The aromatic polyamine compound (b2) is a compound represented by the following general formula (2): <1> or <2> A raw material for producing the polyurea resin composition described in claim 1. [ka] (In the formula, R 1 is a polyoxyalkylene group having alkylene oxide having 2 to 20 carbon atoms as a constituent unit. <4> The polyisocyanate compound (a) includes an aliphatic polyisocyanate and / or a derivative thereof. <1> ~ <3> A raw material for producing a polyurea resin composition according to any one of the preceding claims. <5> The aliphatic polyisocyanate is 1,6-hexamethylene diisocyanate. <4> A raw material for producing the polyurea resin composition described in claim 1. <6> the total content of isocyanate groups contained in the aliphatic polyisocyanate and / or its derivative is more than 50 mol% based on the total content of isocyanate groups contained in all polyisocyanates in the polyisocyanate compound (a); <4> or <5> A raw material for producing the polyurea resin composition described in claim 1. <7> <1> ~ <6> A polyurea resin composition obtained from the raw material for producing a polyurea resin composition according to any one of the preceding items. <8> The pot life is 10 minutes or more. <7> The polyurea resin composition according to claim 1. <9> <7> or <8> A paint containing the polyurea resin composition according to claim 1. <10> <9> A coating film obtained from the paint described in . <11> The haze value at a thickness of 1 mm is less than 40%. <10> The coating film described in <12> <10> or <11> A laminate having the coating film according to claim 1. <13> <9> A coating method for applying the coating material according to claim 1, wherein the coating material is applied by brush coating, roller coating, or trowel coating. [Effects of the Invention]

[0012] The polyurea resin composition obtained from the raw material for producing the polyurea resin composition of the present invention has a sufficient pot life even when applied by hand to large areas for civil engineering and construction applications, and is therefore extremely easy to work with by hand. Furthermore, the coating film obtained from the polyurea resin composition of the present invention satisfies all of the transparency, elongation, water resistance, and chemical resistance required for practical use, and can therefore visually and physically maintain, reinforce, and protect the substrate for a long period of time. DETAILED DESCRIPTION OF THE INVENTION

[0013] 1. Raw materials for manufacturing polyurea resin compositions The raw material for producing the polyurea resin composition of the present invention comprises a component (A) containing a polyisocyanate compound (a) and a component (B) containing a polyamine compound (b), The polyamine compound (b) contains an aspartic acid ester compound (b1) and an aromatic polyamine compound (b2), The content of the aspartic acid ester compound (b1) is characterized by being more than 50% by mass based on the total mass of the aspartic acid ester compound (b1) and the aromatic polyamine compound (b2).

[0014] <Polyisocyanate compound (a)> The polyisocyanate compound (a) used in the present invention is a compound having two or more isocyanate groups per molecule, and may be in the form of a monomer, oligomer, or polymer. The polyisocyanate compound (a) is not particularly limited, but examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, polycyclic aliphatic polyisocyanates, aromatic ring-containing aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives thereof (e.g., isocyanate-terminated prepolymers obtained by reacting the polyisocyanates with polyamines or polyols, allophanate-modified compounds, urea-modified compounds, carbodiimide-modified compounds, biuret-modified compounds, uretdione-modified compounds, isocyanurate-modified compounds, and water-dispersible modified compounds). These compounds may be used alone or in combination. These compounds are appropriately selected depending on the usable time suitable for hand application and the physical properties of the desired coating film.

[0015] Examples of aliphatic polyisocyanates include 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, lysine diisocyanate, trioxyethylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, and trimethylhexamethylene diisocyanate. These may be used alone or in combination of two or more. Among these, 1,6-hexamethylene diisocyanate is preferred from the viewpoint of suppressing reactivity with the polyamine compound (b) and making it easier to ensure a usable time (pot life) suitable for hand application.

[0016] Examples of alicyclic polyisocyanates include isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated methylene bisphenyl diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, 4,4'-methylene bis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatoethyl)cyclohexane, 1,4-bis(isocyanatoethyl)cyclohexane, 2,5- or 2,6-bis(isocyanatomethyl)norbornane (NBDI), and isocyanates derived from amines obtained by hydrogenating aromatic compounds. These may be used alone or in combination of two or more.

[0017] Examples of polycyclic aliphatic polyisocyanates include 2,5(6)-diisocyanate methyl bicyclo[2,2,1]heptane, 2-isocyanate methyl-5(6)-isocyanate ethyl bicyclo[2,2,1]heptane, 2-isocyanate methyl-5(6)-isocyanate propyl bicyclo[2,2,1]heptane, and 2-isocyanate methyl-5(6)-isocyanate butyl bicyclo[2,2,1]heptane. 2-isocyanatomethyl-5(6)-isocyanatopentylbicyclo[2,2,1]heptane, 2,5(6)-diisocyanatoethylbicyclo[2,2,1]heptane, 2,5(6)-diisocyanatopropylbicyclo[2,2,1]heptane, 2,5(6)-diisocyanatobutylbicyclo[2,2,1]heptane, 2,5(6)-diisocyanatopentylbicyclo[2,2,1]heptane, 5(6) -Diisocyanatomethylbicyclo[2,2,2]octane, 2-isocyanatomethyl-5(6)-isocyanatoethylbicyclo[2,2,2]octane, 2-isocyanatomethyl-5(6)-isocyanatopropylbicyclo[2,2,2]octane, 2-isocyanatomethyl-5(6)-isocyanatobutylbicyclo[2,2,2]octane, 2-isocyanatomethyl-5(6)-isocyanatopentyl Rubicylo[2,2,2]octane, 2,5(6)-diisocyanatoethylbicyclo[2,2,2]octane, 2,5(6)-diisocyanatopropylbicyclo[2,2,2]octane, 2,5(6)-diisocyanatobutylbicyclo[2,2,2]octane, 2,5(6)-diisocyanatopentylbicyclo[2,2,1]octane, 3(4),8(9)-diisocyanatomethyltricyclo[5,2,1,0 2,6 ]decane, 3(4)-isocyanatomethyl-8(9)-isocyanatoethyltricyclo[5,2,1,0 2,6 ]decane, 3(4)-isocyanatomethyl-8(9)-isocyanatopropyltricyclo[5,2,1,0 2,6 ]decane, 3(4)-isocyanatomethyl-8(9)-isocyanatobutyltricyclo[5,2,1,0 2,6]decane, 3(4)-isocyanatomethyl-8(9)-isocyanatopentyltricyclo[5,2,1,0 2,6 ]decane, 3(4),8(9)-diisocyanatoethyltricyclo[5,2,1,0 2,6 ]decane, 3(4),8(9)-diisocyanatepropyltricyclo[5,2,1,0 2,6 ]decane, 3(4),8(9)-diisocyanatobutyltricyclo[5,2,1,0 2,6 ]decane, 3(4),8(9)-diisocyanate pentyltricyclo[5,2,1,0 2,6 ]decane, 3(4),7(8)-diisocyanatomethylbicyclo[4,3,0 1,6 ]nonane, 3(4)-isocyanatomethyl-7(8)-isocyanatoethylbicyclo[4,3,0 1,6 ]nonane, 3(4)-isocyanatomethyl-7(8)-isocyanatopropylbicyclo[4,3,0 1,6 ]nonane, 3(4)-isocyanatomethyl-7(8)-isocyanatobutylbicyclo[4,3,0 1,6 ]nonane, 3(4)-isocyanatomethyl-7(8)-isocyanatopentylbicyclo[4,3,0 1,6 ]nonane, 3(4),7(8)-diisocyanatoethylbicyclo[4,3,0 1,6 ]nonane, 3(4),7(8)-diisocyanatopropylbicyclo[4,3,0 1,6 ]nonane, 3(4),7(8)-diisocyanatobutylbicyclo[4,3,0 1,6 ]nonane, and 3(4),7(8)-diisocyanatopentylbicyclo[4,3,0 1,6 ]nonane, etc. These may be used alone or in combination of two or more.

[0018] Examples of aromatic ring-containing aliphatic polyisocyanates include xylylene diisocyanate, tetramethylxylene diisocyanate, etc. These may be used alone or in combination of two or more.

[0019] Examples of aromatic polyisocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-methoxy-4,4'-biphenylene diisocyanate, 2,2',5,5'-tetramethyl-4,4'-biphenylene diisocyanate, 1,5-naphthylene diisocyanate, and 4,4'-diphenylpropane diisocyanate. These may be used alone or in combination of two or more.

[0020] As the polyisocyanate compound (a), from the viewpoint of suppressing reactivity with the polyamine compound (b) and making it easier to ensure a usable time (pot life) suitable for hand application, it is preferable to use an aliphatic polyisocyanate and / or a derivative thereof, and it is more preferable to use 1,6-hexamethylene diisocyanate and / or a derivative thereof. Furthermore, from the viewpoint of further improving the effects of the present invention and improving the physical properties such as tensile strength of the obtained coating film, it is preferable to use a derivative of an aliphatic polyisocyanate, and it is more preferable to use a derivative of 1,6-hexamethylene diisocyanate. When an aliphatic polyisocyanate and / or a derivative thereof is used, from the above viewpoint, the total content of isocyanate groups contained in the aliphatic polyisocyanate and / or a derivative thereof is preferably more than 50 mol%, more preferably 55 mol% or more, even more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 100 mol%, relative to the total content (100 mol%) of isocyanate groups contained in all polyisocyanates in the polyisocyanate compound (a).

[0021] When 1,6-hexamethylene diisocyanate and / or a derivative thereof is used, the polyisocyanate to be used in combination is preferably 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, from the viewpoint of compatibility with 1,6-hexamethylene diisocyanate and / or a derivative thereof and compatibility with the polyamine compound (b). The diisocyanate is at least one selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 1,5-pentamethylene diisocyanate.

[0022] The polyisocyanate compound (a) preferably has an isocyanate group content of 5 to 60 NCO%, more preferably 10 to 50 NCO%. By setting the isocyanate group content of the polyisocyanate compound (a) within this range, a pot life suitable for hand application can be obtained, and a coating film that satisfies all of the practical requirements of transparency, elongation, water resistance, and chemical resistance can be easily obtained.

[0023] <Polyamine compound (b)> The polyamine compound (b) used in the present invention is a compound having two or more amino groups in one molecule, and contains at least an aspartic acid ester compound (b1) and an aromatic polyamine compound (b2).

[0024] [Aspartic acid ester compound (b1)] The aspartic acid ester compound (b1) used in the present invention is not particularly limited as long as it has a monoester or diester structure of aspartic acid and has two or more amino groups in one molecule, but is preferably a compound represented by the following general formula (1): X(-NH-CH(CHCOOR 2 )COOR 1 ) n (1) (wherein X is an organic group, and R 1 and R 2 are the same or different organic groups, and n is an integer of 2 or more.

[0025] X, R 1 and R 2 Examples of the hydrocarbon group include saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups, organic groups in which some of the carbon atoms constituting the hydrocarbon group are substituted with heteroatoms (e.g., oxygen atoms, nitrogen atoms, sulfur atoms, etc.), and organic groups in which two or more of these are bonded together. The number of carbon atoms in the hydrocarbon group is, for example, 1 to 50, preferably 2 to 40, more preferably 2 to 30, and even more preferably 2 to 20. The hydrocarbon group and the organic group may have various substituents (e.g., halogen groups, hydroxy groups, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, etc.) or functional groups (e.g., ester bonds, amide bonds, ether bonds, thioether bonds, urethane bonds, etc.).

[0026] Also, X, R 1 and R 2 may be a polymer structure containing repeating units. Examples of the polymer structure include polyester, polyether, polyacrylic, polymethacrylic, polyolefin, and polyurethane.

[0027] X is preferably an aliphatic saturated hydrocarbon group, an alicyclic saturated hydrocarbon group, or an organic group in which an aliphatic saturated hydrocarbon group and an alicyclic saturated hydrocarbon group are bonded together. Examples of the organic group in which an aliphatic saturated hydrocarbon group and an alicyclic saturated hydrocarbon group are bonded together include organic groups in which two alicyclic saturated hydrocarbon groups (for example, alicyclic saturated hydrocarbon groups having 5 or 6 carbon atoms constituting the ring) are bonded together via an aliphatic saturated hydrocarbon group (for example, an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms).

[0028] R 1 and R 2 is preferably a saturated aliphatic hydrocarbon group.

[0029] The upper limit of n is not particularly limited, but is preferably an integer of 4 or less. n is preferably 2.

[0030] Commercially available aspartic acid ester compounds (b1) include, for example, "Amicure IC-221," "Amicure IC-321," and "Amicure IC-322" manufactured by Evonik, and "Feispartic F220," "Feispartic F420," and "Feispartic F520" manufactured by Feiyang.

[0031] [Aromatic polyamine compound (b2)] The aromatic polyamine compound (b2) used in the present invention is not particularly limited as long as it has an aromatic ring and two or more amino groups in one molecule.

[0032] Examples of the aromatic polyamine compound (b2) include aromatic ring-containing aliphatic polyamines, aromatic polyamines, aromatic polyamines having a nucleus-substituted alkyl group, aromatic polyamines having a nucleus-substituted electron-withdrawing group, and aromatic polyamines having a secondary amino group.

[0033] Examples of aromatic ring-containing aliphatic polyamines include xylylenediamine, tetrachloro-p-xylylenediamine, etc. These may be used alone or in combination of two or more.

[0034] Examples of aromatic polyamines include 1,2-, 1,3-, and 1,4-phenylenediamine, 2,4'- and 4,4'-diphenylmethanediamine, crude diphenylmethanediamine [polyphenylpolymethylenepolyamine], diaminodiphenylsulfone, benzidine, thiodianiline, bis(3,4-diaminophenyl)sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4',4''-triamine, naphthylenediamine, trimethylene-bis(4-aminobenzoate), and poly(1,4-butanediol)bis(4-aminobenzoic acid). These may be used alone or in combination of two or more.

[0035] Examples of aromatic polyamines having a nucleus-substituted alkyl group (e.g., alkyl groups such as methyl, ethyl, n- and i-propyl, and butyl) include 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis(o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1, 4-Diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl propyl-1,5-diaminonaphthalene, 2,6-dibutyl-1,5-diaminonaphthalene, 3,3',5,5'-tetramethylbenzidine, 3,3',5,5'-tetraisopropylbenzidine, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetrabutyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'- Methyl-2',4-diaminodiphenylmethane, 3,5-diisopropyl-3'-methyl-2',4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3',5,5'-tetraisopropyl-4,4'-diaminobenzophenone, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3',5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone, and mixtures of these isomers in various proportions. These may be used alone or in combination of two or more.

[0036] Examples of aromatic polyamines having a nuclear-substituted electron-withdrawing group (e.g., halogens such as Cl, Br, I, and F; alkoxy groups such as methoxy and ethoxy; nitro group, etc.) include methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3,3-dichloro-4,4'-diaminodiphenylmethane, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline, 4,4'-diamino-3,3'-dimethyl-5,5'-dibromo-diphenylmethane, 3,3' -dichlorobenzidine, 3,3'-dimethoxybenzidine, bis(4-amino-3-chlorophenyl)oxide, bis(4-amino-2-chlorophenyl)propane, bis(4-amino-2-chlorophenyl)sulfone, bis(4-amino-3-methoxyphenyl)decane, bis(4-aminophenyl)sulfide, bis(4-aminophenyl)telluride, bis(4-aminophenyl)selenide, bis(4-amino-3-methoxyphenyl)disulfide, 4,4'-methylenebis(2-iodoaniline), 4,4'-methylenebis(2-bromoaniline), 4,4'-methylenebis(2-fluoroaniline), and 4-aminophenyl-2-chloroaniline. These may be used alone or in combination of two or more.

[0037] Examples of aromatic polyamines having a secondary amino group [the above aromatic polyamines in which some or all of the -NH2 groups have been replaced with -NH-R' (R' is an alkyl group, for example, a lower alkyl group such as methyl or ethyl)] include 4,4'-di(methylamino)diphenylmethane, 4,4'-di(sec-butylamino)diphenylmethane, and 1-methyl-2-methylamino-4-aminobenzene. These may be used alone or in combination of two or more.

[0038] As the aromatic polyamine compound (b2), a compound represented by the following general formula (2) may be used. [ka] (In the formula, R 1 is a polyoxyalkylene group having alkylene oxide having 2 to 20 carbon atoms as a constituent unit.

[0039] The alkylene oxide preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and particularly preferably 4 carbon atoms, from the viewpoint of improving the effects of the present invention.

[0040] The polyoxyalkylene group may contain one type of alkylene oxide or two or more types. When the polyoxyalkylene group contains two or more types of alkylene oxide, the two or more types of alkylene oxide may be added randomly or in blocks. Specific examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a polyoxyethylene polyoxypropylene group, a polyoxyethylene polyoxybutylene group, and a polyoxypropylene polyoxybutylene group.

[0041] The average number of moles of alkylene oxide added in the polyoxyalkylene group is not particularly limited and is, for example, 2 to 100, and from the viewpoint of improving the effects of the present invention, it is preferably 2 to 50, more preferably 2 to 30, even more preferably 2 to 20, still more preferably 2 to 15, and particularly preferably 2 to 15.

[0042] Commercially available products of the compound represented by the general formula (2) include, for example, "ELASMER 250P," "ELASMER 650P," "ELASMER 1000P," and "POREA SL-100A" manufactured by Kumiai Chemical Industry Co., Ltd., and "VERSALINK P-1000" manufactured by Air Products Japan Co., Ltd.

[0043] [Ratio of aspartic acid ester compound (b1) to aromatic polyamine compound (b2)] In order to obtain the effects of the present invention, the content of the aspartic acid ester compound (b1) in the polyamine compound (b) used in the present invention must be more than 50% by mass based on the total mass of the aspartic acid ester compound (b1) and the aromatic polyamine compound (b2). From the viewpoint of improving the effects of the present invention, the content of the aspartic acid ester compound (b1) is preferably 55 to 99% by mass, more preferably 60 to 98% by mass, even more preferably 70 to 97% by mass, and still more preferably 80 to 95% by mass based on the total mass of the aspartic acid ester compound (b1) and the aromatic polyamine compound (b2).

[0044] [Other polyamine compounds] The polyamine compound (b) used in the present invention preferably contains only the aspartic acid ester compound (b1) and the aromatic polyamine compound (b2), but may contain other polyamine compounds as long as the effects of the present invention are not impaired.

[0045] The other polyamine compounds are not particularly limited, and examples thereof include aliphatic polyamines, alicyclic polyamines, heterocyclic polyamines, polyamide polyamines, polyether polyamines, cyanoethylated polyamines, and hydrazines. These may be used alone or in combination of two or more.

[0046] Examples of aliphatic polyamines include alkylenediamines (e.g., ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, and hexamethylenediamine), polyalkylenepolyamines (e.g., diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine), and alkyl or hydroxyalkyl substituted derivatives thereof (e.g., dialkylaminopropylamine ... amine, trimethylhexamethylenediamine, aminoethylethanolamine, methyliminobispropylamine, etc.), tetraethyl 2,2'-[(2-methylpentane-1,5-diyl)diimino]disuccinate, tetraethyl 2,2'-{[methylenebis(cyclohexane-4,1-diyl)]bis(azanediyl)}disuccinate, and tetraethyl 2,2'-{[methylenebis(2-methylcyclohexane-4,1-diyl)]bis(azanediyl)}disuccinate, etc. These may be used alone or in combination of two or more.

[0047] Examples of alicyclic polyamines include 1,3-diaminocyclohexane, isophoronediamine, menthanediamine, and 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc. These may be used alone or in combination of two or more.

[0048] Examples of heterocyclic polyamines include piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, etc. These may be used alone or in combination of two or more.

[0049] Examples of polyamide polyamines include low-molecular-weight polyamide polyamines obtained by condensation of dicarboxylic acids with polyamines, etc. These may be used alone or in combination of two or more.

[0050] Examples of polyether polyamines include hydrogenated cyanoethylated polyether polyols, etc. These may be used alone or in combination of two or more.

[0051] Examples of cyanoethylated polyamines include cyanoethylated polyamines (e.g., biscyanoethyldiethylenetriamine) obtained by addition reaction of acrylonitrile with polyamines (e.g., the above-mentioned alkylenediamines and polyalkylenepolyamines). These may be used alone or in combination of two or more.

[0052] Examples of hydrazines include hydrazine, monoalkylhydrazine, dihydrazides (e.g., succinic acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, etc.), guanidines (e.g., butylguanidine, 1-cyanoguanidine, etc.), and dicyandiamide. These may be used alone or in combination of two or more.

[0053] When the polyamine compound (b) used in the present invention contains other polyamine compounds, the content of the other polyamine compounds is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, per 100 parts by mass of the total of the aspartic acid ester compound (b1) and the aromatic polyamine compound (b2).

[0054] In the raw material for producing the polyurea resin composition of the present invention, the molar ratio of isocyanate groups in the polyisocyanate compound (a) to amino groups in the polyamine compound (b) (isocyanate groups / amino groups) is preferably 0.6 to 1.5, more preferably 0.8 to 1.2, even more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05. By keeping the molar ratio (isocyanate groups / amino groups) within this range, side reactions such as foaming can be suppressed, and a coating film that satisfies all of the practical requirements of transparency, elongation, water resistance, and chemical resistance can be more easily obtained.

[0055] <Other compounds> The raw materials for producing the polyurea resin composition of the present invention may contain other compounds to adjust the usable time and physical properties of the coating film. Examples of other compounds include polyol compounds, polythiol compounds, epoxy compounds, polyolefin compounds, polycarboxylic acid compounds, (meth)acrylic acid compounds, (meth)acrylic acid ester compounds, polyamide compounds, polyester compounds, and polyether compounds. These compounds may be used alone or in combination of two or more. The other compounds may be oligomers or polymers.

[0056] When the raw materials for producing the polyurea resin composition of the present invention contain other compounds, the content of the other compounds is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, per 100 parts by mass of the total of the aspartic acid ester compound (b1) and the aromatic polyamine compound (b2).

[0057] <Catalyst> The raw materials for producing the polyurea resin composition of the present invention may contain a catalyst in order to improve the physical properties of the resulting coating film or to adjust the usable time or curing temperature.

[0058] Examples of catalysts include tertiary amines such as triethylamine, tributylamine, triethylenediamine, 2-dimethylaminoethyl ether, diazabicycloundecene, and N-methylmorpholine; metal-based catalysts such as dibutyltin diacetate, dibutyltin laurate, 3-diacetoxytetrabutylstannoxane, tin octenoate, tin chloride, butyl tin trichloride, bismuth trichloride, bismuth octenoate, tetrakis(2-ethylhexyl)titanate, tetrabutoxytitanium, and metal salts of acetoacetic acid; quaternary ammonium salts such as tetramethylammonium chloride; and acidic compounds such as hydrochloric acid, sulfuric acid, acetic acid, succinic acid, and trifluoromethanesulfonic acid. These may be used alone or in combination of two or more.

[0059] <Additives> The raw materials for producing the polyurea resin composition of the present invention may contain additives as needed.

[0060] Examples of additives include basic inorganic compounds, pH adjusters, metal oxide fine particles, tackifiers, waxes, UV absorbers, surface conditioners, antifoaming agents, thixotropy-imparting agents, colorants, dispersants, fillers, and diluents. These may be used alone or in combination of two or more. The amount of additive used may be adjusted appropriately depending on the purpose.

[0061] Examples of basic inorganic compounds include hydroxides, oxides, and (hydrogen)carbonates of alkali metals or alkaline earth metals, such as calcium hydroxide, sodium hydroxide, magnesium hydroxide, calcium oxide, calcium carbonate, sodium carbonate, and sodium hydrogencarbonate. These may be used alone or in combination of two or more. Among these, hydroxides of alkali metals or alkaline earth metals are preferred from the viewpoint of their influence on stability and viscosity.

[0062] Examples of pH adjusters include organic acid salts of alkali metals or alkaline earth metals such as calcium acetate, sodium acetate, potassium acetate, calcium formate, sodium formate, potassium formate, calcium propionate, sodium propionate, potassium propionate, etc. These may be used alone or in combination of two or more.

[0063] Examples of metal oxide fine particles include titanium oxide, magnesium oxide, ferrous oxide, ferric oxide, triiron tetroxide, aluminum oxide, vanadium oxide, copper oxide, etc. These may be used alone or in combination of two or more.

[0064] Examples of tackifiers include polysaccharides such as xanthan gum and guar gum, rosin resins and derivatives thereof, terpene resins and derivatives thereof, aliphatic resins and derivatives thereof, aromatic resins and derivatives thereof, etc. These may be used alone or in combination of two or more.

[0065] Examples of waxes include paraffin wax, amide wax, olefin wax, olefin oxide wax, montan wax, copolymer wax, etc. These may be used alone or in combination of two or more.

[0066] Examples of ultraviolet absorbents include hindered amine-based, cinnamic acid-based, benzophenone-based, triazine-based, triazole-based, etc. These may be used alone or in combination of two or more.

[0067] Examples of surface conditioners include silicone-based, acrylic polymer-based, vinyl-based, acetylene-based, fluorine-based, alkylene oxide-based, etc. These may be used alone or in combination of two or more.

[0068] Examples of antifoaming agents include mineral oil-based, amide-based, metal soap-based, silicone-based, higher alcohols and their derivatives, fatty acid derivatives, and polyolefin-based agents. These may be used alone or in combination of two or more. Among these, polyolefin-based agents are preferred from the viewpoints of antifoaming properties and chemical resistance.

[0069] Examples of thixotropy-imparting agents include acrylic polymers, organic urea compounds and modified compounds thereof, fumed silica, bentonite, organic clay, layered silicates, phyllosilicates, and wollastonite. Among these, inorganic materials may be organically modified. These may be used alone or in combination of two or more. Among these, organic urea compounds and modified compounds thereof, or phyllosilicates are preferred from the viewpoint of the effect relative to the amount added.

[0070] As colorants, inorganic pigments, organic pigments, and dyes can all be used. Examples of inorganic pigments include red clay, yellow clay, green clay, graphite, Prussian blue, zinc oxide, cobalt blue, viridian, and titanium white. Examples of organic pigments include alkali blue, lysol red, disazo yellow, phthalocyanine blue, quinacridone red, and isoindoline yellow. Examples of dyes include madder, sappan, and indigo. These may be used alone or in combination of two or more.

[0071] Examples of dispersants include acrylic polymers, polycarboxylic acid compounds, phosphonic acid compounds, sulfonic acid compounds and neutralized compounds thereof, quaternary ammonium salt compounds, amide compounds, polyether compounds, etc. These may be used alone or in combination of two or more.

[0072] Examples of fillers include inorganic compounds such as calcium carbonate and calcium hydroxide, inorganic minerals such as talc, kaolin, apatite, and layered silicates, glass beads, glass fiber, and silica. These may be used alone or in combination of two or more. Among these, talc, glass beads, and silica are preferred from the viewpoint of viscosity relative to the amount added.

[0073] As the diluent, any common organic solvent can be used as long as it is not reactive with the polyisocyanate compound (A). Examples of organic solvents that can be used as diluents include hydrocarbon compounds such as toluene, xylene, and cyclohexane; carbonyl compounds such as acetone, 2-butanone, and isophorone; and ester compounds such as ethyl acetate and butyl acetate. These may be used alone or in combination. The content of the organic solvent in the raw materials for producing the polyurea resin composition is preferably 10% by mass or less. If the content of the organic solvent exceeds 10% by mass, not only may the physical properties of the resulting coating film be reduced, but the inherent advantage of the polyurea resin composition, which can be produced without a solvent, will be lost.

[0074] 2. Polyurea resin composition The polyurea resin composition of the present invention is obtained from the raw materials for producing the polyurea resin composition of the present invention. The polyurea resin composition of the present invention can be obtained by mixing at least component (A) and component (B). A known mixing method can be used. If necessary, other optional components such as other compounds, catalysts, and additives may be mixed. Other optional components such as other compounds, catalysts, and additives may be blended in advance with component (A) and / or component (B), or may be mixed simultaneously with component (A) and component (B).

[0075] (Viscosity of Polyurea Resin Composition) The viscosity of the polyurea resin composition of the present invention, 30 seconds after mixing all components including component (A) and component (B), is preferably 100 to 500,000 mPa·s, more preferably 500 to 300,000 mPa·s, and even more preferably 1,000 to 200,000 mPa·s. If the viscosity 30 seconds after mixing is less than 100 mPa·s, the polyurea resin composition tends to exhibit poor sagging resistance during application and to be difficult to obtain a coating film with sufficient thickness. On the other hand, if the viscosity 30 seconds after mixing is greater than 500,000 mPa·s, the polyurea resin composition tends to be unsuitable for hand application due to its difficulty in removing air bubbles and its insufficient pot life.

[0076] Examples of methods for adjusting the viscosity 30 seconds after mixing to fall within the above range include adjusting the steric hindrance near the amino group of the polyamine compound (b), adjusting the functional group concentration or number of functional groups of the polyisocyanate compound (a) and the polyamine compound (b), adjusting the compounding ratio of the polyisocyanate compound (a) and the polyamine compound (b), and adding appropriate amounts of additives such as a filler, a diluent, and a viscosity imparting agent.

[0077] (Pot life of polyurea resin composition) To ensure that the polyurea resin composition of the present invention is suitable for hand application, its pot life is 2 minutes or more, preferably 3 to 180 minutes, more preferably 4 to 180 minutes, even more preferably 10 to 180 minutes, even more preferably 15 to 180 minutes, even more preferably 15 to 150 minutes, and particularly preferably 20 to 120 minutes. A pot life of less than 2 minutes results in poor workability when applying a large area by hand to civil engineering and construction applications, while a pot life of more than 180 minutes reduces application efficiency due to the long curing time required. In the present invention, the pot life is a value obtained by the following measurement method. All components, including components (A) and (B), are added to a 100 mL glass beaker to a total volume of 20 mL, and mixed at 25°C using a metal stirrer until the mixture appears uniform. The viscosity after mixing is then measured using a Brookfield viscometer. Measurements are then continued, and the time required for the viscosity to double from the value after mixing is determined as the pot life. For the B-type viscometer, use the LV-4 spindle when the viscosity exceeds 1,000 mPa·s, and the SC4-18 when the viscosity is 1,000 mPa·s or less.

[0078] Examples of methods for setting the pot life within the above range include adjusting the steric hindrance near the amino group of the polyamine compound (b), adjusting the functional group concentration or number of functional groups of the polyisocyanate compound (a) and the polyamine compound (b), adjusting the compounding ratio of the polyisocyanate compound (a) and the polyamine compound (b), and adding appropriate amounts of additives such as a filler, a diluent, and a viscosity imparting agent.

[0079] 3.Paint The coating material of the present invention contains the polyurea resin composition of the present invention, and has a sufficient pot life even when applied by hand to large areas for civil engineering and construction applications, making it extremely easy to work with by hand. Furthermore, the coating material of the present invention has excellent sagging resistance (less likely to drip), making it easy to apply to wall surfaces and capable of forming a coating film with excellent thickness uniformity. Furthermore, the coating material of the present invention has excellent bubble-breaking properties and easily eliminates bubbles during application, making it possible to form a coating film with excellent appearance.

[0080] 4. Coating The coating film of the present invention is obtained by curing the polyurea resin composition of the present invention.

[0081] (Haze value) The coating film of the present invention preferably has a haze value of less than 40%, more preferably 30% or less, even more preferably 20% or less, and even more preferably 10% or less at a thickness of 1 mm. If the haze value exceeds 40%, it may be difficult to visually confirm any abnormalities (e.g., cracks) in the substrate. In the present invention, the haze value is determined in accordance with the method described in JIS K 7136:2000 (Method for determining the haze of plastics - transparent materials). Specifically, the haze value of a square coating film sample (test piece) with a thickness of 1 mm and a side length of 50 mm is measured using a haze meter at 23°C and 50% RH. The average haze value of three test pieces is used as the haze value.

[0082] As a method for adjusting the haze value within the above range, known methods can be employed, such as using a combination of a polyisocyanate compound (a) and a polyamine compound (b) which are highly compatible, using a combination of an aspartic acid ester compound (b1) and an aromatic polyamine compound (b2) which are highly compatible, or using the above compound having an organic group that does not contain a double bond.

[0083] 5.Painting method The coating material of the present invention has a sufficient pot life, and therefore, known methods can be used for coating the coating material without any particular limitations. The method for applying the coating material may be appropriately selected depending on the thickness of the coating film and the shape of the substrate, and examples thereof include immersion coating (dipping, dipping coating), wire bar coating, Baker-type applicator coating, gravure roll coating, potting, brush coating, roller coating, and trowel coating. It is also possible to form a three-dimensional cured product (coating film) using a 3D printer or the like. The coating material of the present invention has a sufficient pot life even when applied by hand to large areas such as in civil engineering and construction applications, and therefore is preferably applied by brush coating, roller coating, or trowel coating.

[0084] The coating material of the present invention is reactive at room temperature and therefore does not usually require heating, but may be heated to accelerate curing after application. The curing temperature can be determined appropriately based on the application method and curing time, but from the viewpoint of safety, it is preferably 40 to 80°C.

[0085] As the heating device for the paint of the present invention, any known device can be used, taking into consideration the viscosity of the paint, the shape of the object to be coated, etc. Examples of the heating device include a heating roller, a roller heater, a polyimide heater, an infrared radiation heater, a high-temperature air heater, a heat gun, a dryer, a drying oven, a baking oven, a constant-temperature dryer, and a constant-temperature oven.

[0086] The curing time may be appropriately selected in consideration of the characteristics of the coating material, the heating device, and the curing process, but from the viewpoint of productivity, it is preferably less than 3 hours, more preferably less than 2 hours, and even more preferably less than 1 hour. The above-mentioned catalyst may be used to adjust the curing time.

[0087] The thickness of the coating film can be appropriately selected depending on the desired physical properties, the material of the substrate, etc., but is usually preferably 10 to 10,000 μm, more preferably 50 to 8,000 μm, and even more preferably 100 to 5,000 μm, from the viewpoints of economy and physical properties. The thickness can be achieved by coating in one go or by multiple separate coatings.

[0088] 6.Applications The polyurea resin composition of the present invention has a viscosity, usable life, and curing time that allow hand application. Furthermore, the coating film obtained from the polyurea resin composition of the present invention satisfies all of the practical requirements of transparency, elongation, water resistance, and chemical resistance. Therefore, the polyurea resin composition and coating film of the present invention can be suitably used as a material for protecting substrates against water and chemicals, or as a material for protecting substrates against deformation and cracking. Applications of the polyurea resin composition of the present invention include, for example, coated floors, linings, roof waterproofing, exterior wall coatings, bridge deck waterproofing, waterproof paints, anticorrosion paints, protective paints for the inside and outside of steel pipes, metal pipes, and tanks, reinforcement and repair of buildings, protection of plastic and metal parts, and reservoirs.

[0089] The polyurea resin composition of the present invention can also be compounded with flat bodies such as fibers (including both long and short fibers), nonwoven fabrics (including both long and short fibers), cloth, wire netting, mesh, and punched metal. A known method can be used for compounding. The amount of coating when compounding with the flat body can be adjusted appropriately depending on the desired physical properties and the material of the substrate. From the viewpoints of economy and physical properties, the amount of coating is preferably 0.01 to 5 kg / m. 2 is preferable, and 0.03 to 4 kg / m 2 More preferably, 0.05 to 3 kg / m 2 is more preferable.

[0090] The polyurea resin composition of the present invention can also be poured into a metal frame to produce a molded article. A release agent can also be used to improve the releasability of the polyurea resin composition from the metal frame. Known release agents can be used, and they can be applied to the metal frame before pouring the polyurea resin composition into it, or they can be mixed when preparing the polyurea resin composition. In addition, if the release agent does not have reactivity with the polyurea resin composition, it can be blended in component (A) and / or component (B) in advance.

[0091] 7.Laminate The laminate of the present invention is not particularly limited as long as it has at least the coating film of the present invention, and examples thereof include a laminate having a coating film on a substrate. The material forming the substrate is not particularly limited, and examples thereof include metals, resins, glass, ceramics, and composites thereof. The laminate of the present invention can be obtained, for example, by forming a coating film on a substrate by the above-mentioned coating method. [Example]

[0092] The present invention will be described in more detail below with reference to examples, but is not limited to these examples. The raw materials used in the examples and comparative examples are listed below. The raw materials were used as they were without purification or distillation.

[0093] <Polyisocyanate compound (a)> HDI: 1,6-hexamethylene diisocyanate (Tokyo Chemical Industry Co., Ltd., 49.9 NCO%, viscosity 3 mPa·s) WL72-100: Water-dispersible modified hexamethylene diisocyanate (Asahi Chemical Industry Co., Ltd. "Duranate WL72-100", 21.3 NCO%, viscosity 1,000 mPa s) HXR: Nurate-modified hexamethylene diisocyanate (Tosoh Corporation's "Coronate HXR," 21.9 NCO%, viscosity 1,500 mPa·s) D201: Bifunctional HDI-based prepolymer (Asahi Chemical Industry Co., Ltd. "Duranate D201", 15.8 NCO%, viscosity 1,800 mPa s) IPDI: Isophorone diisocyanate (mixture of isomers) (Tokyo Chemical Industry Co., Ltd., 37.8 NCO%, viscosity 14 mPa s) MR-200: Polymeric MDI (Tosoh Corporation's "Millionate MR-200", 30.9 NCO%, viscosity 200 mPa·s) T100: 2,4-toluene diisocyanate (Mitsui Fine Chemicals, 48.2 NCO%, viscosity 3 mPa·s)

[0094] <Aspartic acid ester compound (b1)> F220: Aspartic acid ester compound (Feiyang Co., Ltd. "Feispartic F220", amine value 241 mg KOH / g, viscosity 80 mPa s) F420: Aspartic acid ester compound (Feiyang "Feispartic F420", amine value 203 mg KOH / g, viscosity 1,450 mPa s) F520: Aspartic acid ester compound (Feiyang "Feispartic F520", amine value 190 mg KOH / g, viscosity 1,400 mPa s)

[0095] <Aromatic polyamine compound (b2)> 250P: Polytetramethylene oxide-di-p-aminobenzoate (Kumiai Chemical Co., Ltd. "Elasmer 250P", average number of moles of tetramethylene oxide added: approximately 3, amine value: 221 mg KOH / g, molecular weight: 488, viscosity: 205,000 mPa s) 650P: Polytetramethylene oxide-di-p-aminobenzoate (Kumiai Chemical Co., Ltd. "Elasmer 650P", average number of moles of tetramethylene oxide added: approximately 8.5, amine value 126 mg KOH / g, molecular weight 888, viscosity 8,000 mPa s) 1000P: Polytetramethylene oxide-di-p-aminobenzoate (Kumiai Chemical Co., Ltd. "Elasmer 1000P", average number of moles of tetramethylene oxide added: approximately 13, amine value: 84 mg KOH / g, molecular weight: 1238, viscosity: 6,000 mPa s) DETDA: Diethyltoluenediamine (Mitsui Chemicals Fine Co., Ltd. "Ethacure 100 Plus", amine value 629 mg KOH / g, molecular weight 178, viscosity 290 mPa s) 4200: 4,4'-bis(sec-butylamino)diphenylmethane (Dorfketal "Unilink 4200", amine value 158 mg KOH / g, molecular weight 310, viscosity 118 mPa·s (38°C))

[0096] <Other compounds> G1500: Glycerin / propylene oxide adduct (ADEKA "G-1500", hydroxyl value 110 mg KOH / g, viscosity 350 mPa s)

[0097] The methods for measuring and evaluating various physical properties in the examples and comparative examples are as follows. (1) Isocyanate group content (NCO%) The isocyanate group content (NCO%) was determined in accordance with the hydrochloric acid back titration method of di-n-butylamine described in "6.3 Isocyanate group content" of JIS K 7301-1995 (Testing methods for tolylene diisocyanate prepolymers for thermosetting urethane elastomers).

[0098] (2) Amine value The amine value was determined in accordance with the description of "4.2 Indicator titration method" in JIS K 7237-1995 (Test method for total amine value of amine-based curing agents for epoxy resins).

[0099] (3) Hydroxyl value The hydroxyl value was determined in accordance with the description of "7.3 Pyridine-acetyl chloride method" in JIS K 0070-1992 (Test methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products).

[0100] (4) Equivalent ratio of NCO / (NH2 or active hydrogen group) It was calculated using the isocyanate group content obtained in (1) to (3) above and the amine value or hydroxyl value.

[0101] (5) Viscosity of raw materials Rotational viscosity (mPa·s) at 25°C was measured using a Brookfield Dial Viscometer (Brookfield Engineering Laboratories, Inc., Brookfield Dial Viscometer Model LVT). The Brookfield viscometer spindle was LV-4 when the viscosity exceeded 1,000 mPa·s, and SC4-18 when the viscosity was 1,000 mPa·s or less.

[0102] (6) Pot life All components, including the polyisocyanate compound (a) and polyamine compound (b), were added to a 100 mL glass beaker until the total volume reached 20 mL. The mixture was quickly mixed at 25°C using a metal stirrer until uniform. The viscosity was then measured using the Brookfield viscometer. The measurement was continued, and the time required for the viscosity to double from the initial value was determined as the pot life. The Brookfield viscometer spindle was LV-4 for viscosities above 1,000 mPa·s and SC4-18 for viscosities below 1,000 mPa·s. A pot life of 2 minutes or longer is considered suitable for hand application.

[0103] (7) Haze value (transparency) All components, including the polyisocyanate compound (a) and the polyamine compound (b), were added to a 100 mL glass beaker and rapidly mixed at 25°C using a metal stirrer until uniform. The mixture was then poured onto a flat, enclosed polytetrafluoroethylene plate to a thickness of 1 mm and cured at 25°C for 48 hours. Three 50 mm square test pieces were cut from the resulting 1 mm-thick cured plate. The haze value was measured according to the method described in JIS K 7136:2000 (Determination of haze for plastics and transparent materials). Specifically, the haze value was measured at 23°C and 50% RH using a haze meter (NDH4000, manufactured by Nippon Denshoku Industries Co., Ltd.). The average haze value of the three test pieces was used as the haze value. A haze value of less than 40% is considered to have the transparency required for practical use.

[0104] (8) Growth rate All components, including the polyisocyanate compound (a) and the polyamine compound (b), were added to a 100 mL glass beaker and rapidly mixed at 25°C using a metal stirrer until uniform. The mixture was then poured onto a flat, enclosed polytetrafluoroethylene plate to a thickness of 1 mm and cured at 25°C for 48 hours. Three dumbbell-shaped No. 1 test pieces were punched out from the resulting 1 mm-thick cured plate, as described in JIS K 6251:2017 (Vulcanized and Thermoplastic Rubbers - Determination of Tensile Properties). The elongation of the resulting dumbbell-shaped No. 1 test pieces was measured according to "3.5 Elongation at Break" in JIS K 6251:2017. Specifically, the elongation was measured using a tensile tester (Shimadzu Corporation, Autograph AGS-X) at 25°C, a tensile speed of 500 mm / min, and a gauge length of 40 mm. The average value of the elongation percentages of three dumbbell-shaped No. 1 test pieces was used as the elongation percentage. The elongation percentage was evaluated according to the following criteria. If the elongation percentage is 10% or more, it can be said that the elongation percentage is sufficient for practical use. [Evaluation criteria] 5: Elongation rate is 30% or more 4: Elongation rate is 20% or more but less than 30% 3: Elongation rate is 15% or more but less than 20% 2: Elongation rate is 10% or more but less than 15% 1: Elongation rate is less than 10%

[0105] (9) Water resistance and chemical resistance All components, including the polyisocyanate compound (a) and the polyamine compound (b), were added to a 100 mL glass beaker and rapidly mixed at 25°C using a metal stirrer until uniform. The mixture was then poured onto a flat, enclosed polytetrafluoroethylene plate to a thickness of 1 mm and cured at 25°C for 48 hours. Rectangular test pieces measuring 2 cm wide and 5 cm long were then cut from the resulting 1 mm-thick cured plate. The test pieces were immersed in distilled water (40°C), a 5% aqueous sulfuric acid solution (40°C), or a 5% aqueous sodium hydroxide solution (40°C) for 60 days. After immersion, the test pieces were dried in a thermostatic oven at 150°C for 2 hours. The weight loss rate was calculated using the following formula, and the water resistance and chemical resistance were evaluated according to the following criteria. A weight loss rate of 15% or less was considered to have the water resistance and chemical resistance required for practical use. Weight loss rate (%) = (weight of test piece after immersion / weight of test piece before immersion) x 100 [Evaluation criteria] 5: Weight loss rate is within 2% 4: Weight loss rate is over 2% and within 5% 3: Weight loss rate is over 5% and within 10% 2: Weight loss rate is over 10% and within 15% 1: Weight loss rate exceeds 15%, or dissolution or swelling is visible

[0106] Example 1 To a 100 mL glass beaker, 12.6 parts by mass of HDI as the polyisocyanate compound (a), 29.4 parts by mass of F220 as the aspartic acid ester compound (b1), and 7.5 parts by mass of 250P as the aromatic polyamine compound (b2) were added, and the mixture was quickly stirred with a metal stirring rod until it appeared homogeneous, yielding a polyurea resin composition (isocyanate group amount / amino group amount = 1.0). The measurements and evaluations (6) to (9) above were then carried out. The raw materials used and the measurement and evaluation results are shown in Tables 1 and 2.

[0107] Examples 2 to 18, Comparative Examples 1 to 3 A polyurea resin composition was obtained by the same procedure as in Example 1, except that the raw materials and compounding ratios were changed to those shown in Table 1 (isocyanate group amount / (amino group amount or hydroxy group amount)=1.0). Thereafter, the measurements and evaluations (6) to (9) above were carried out. The raw materials used and the measurement and evaluation results are shown in Tables 1 and 2.

[0108] [Table 1]

[0109] [Table 2]

[0110] (Consideration) The polyurea resin compositions of Examples 1 to 18 each had a content of the aspartic acid ester compound (b1) of more than 50 mass % relative to the total mass of the aspartic acid ester compound (b1) and the aromatic polyamine compound (b2). Therefore, the compositions had a usable life suitable for hand application, and were able to provide coating films that satisfied all of the transparency, elongation, water resistance, and chemical resistance required for practical use.

[0111] On the other hand, the polyurea resin composition of Comparative Example 1 did not contain the aromatic polyamine compound (b2), and therefore was unable to provide a coating film having an elongation percentage required for practical use.

[0112] In the polyurea resin composition of Comparative Example 2, the content of the aspartic acid ester compound (b1) was 45 mass % relative to the total mass of the aspartic acid ester compound (b1) and the aromatic polyamine compound (b2), and therefore a coating film having the transparency required for practical use could not be obtained.

[0113] The polyurethane resin composition of Comparative Example 3, in which a polyol compound was used instead of the polyamine compound (b), had an excessively long pot life and was therefore poor in application efficiency, and was unable to obtain a coating film having the chemical resistance required for practical use.

Claims

1. A raw material for producing a polyurea resin composition, comprising a component (A) containing a polyisocyanate compound (a) and a component (B) containing a polyamine compound (b), The polyamine compound (b) contains an aspartic acid ester compound (b1) and an aromatic polyamine compound (b2), A raw material for producing a polyurea resin composition, characterized in that the content of the aspartic acid ester compound (b1) is more than 50 mass% based on the total mass of the aspartic acid ester compound (b1) and the aromatic polyamine compound (b2).

2. 2. The raw material for producing a polyurea resin composition according to claim 1, wherein the aspartic acid ester compound (b1) is a compound represented by the following general formula (1): X(-NH-CH(CH) 2 COOR 2 )COOOR 1 ) n (1) (wherein X is an organic group, R 1 and R 2 are the same or different organic groups, and n is an integer of 2 or more.

3. The raw material for producing a polyurea resin composition according to claim 1, wherein the aromatic polyamine compound (b2) is a compound represented by the following general formula (2): 【Chemistry 1】 (In the formula, R 1 is a polyoxyalkylene group having alkylene oxide having 2 to 20 carbon atoms as a constituent unit.

4. The raw material for producing a polyurea resin composition according to claim 1, wherein the polyisocyanate compound (a) comprises an aliphatic polyisocyanate and / or a derivative thereof.

5. The raw material for producing a polyurea resin composition according to claim 4, wherein the aliphatic polyisocyanate is 1,6-hexamethylene diisocyanate.

6. 5. The raw material for producing a polyurea resin composition according to claim 4, wherein the total content of isocyanate groups possessed by the aliphatic polyisocyanate and / or its derivative is more than 50 mol% relative to the total content of isocyanate groups possessed by all polyisocyanates in the polyisocyanate compound (a).

7. A polyurea resin composition obtained from the raw material for producing a polyurea resin composition according to any one of claims 1 to 6.

8. The polyurea resin composition according to claim 7, which has a pot life of 10 minutes or more.

9. A paint containing the polyurea resin composition according to claim 7.

10. A coating film obtained from the coating material according to claim 9.

11. 11. The coating of claim 10, having a haze value of less than 40% at a thickness of 1 mm.

12. A laminate having the coating film according to claim 10.

13. 10. A coating method for applying the paint according to claim 9, wherein the method for applying the paint is brush coating, roller coating, or trowel coating.

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