Polyurea resin composition production raw material, polyurea resin composition, and coating material

Abstract

To provide a polyurea resin composition production raw material which enables production of a coating material that has curing time suitable for hand coating and is excellent in sagging resistance and defoaming resistance of a coating film, and enables formation of a cured product that is excellent in adhesion to a base material, and a polyurea resin composition.SOLUTION: A polyurea resin composition production raw material contains a component (A) containing a polyisocyanate compound (a), and a component (B) containing a polyamine compound (b), and satisfies all the following conditions (1) to (4). (1) Residual viscosity after 30 seconds from mixing of all the components including the component (A) and the component (B) is 1,500 mPa s or more and 20,000 mPa s or less. (2) Residual viscosity after 30 seconds from mixing of all the components including the component (A) and the component (B) is 1,500 mPa s or more and 30,000 mPa s or less, and viscosity after 30 minutes from the mixture is 100,000 mPa s or less. (3) A coefficient of kinematic viscosity after 30 seconds from mixture of all the components including the component (A) and the component (B) is 1,200 m2 / s or more and 30,000 m2 / s or less. (4) Surface free energy of a cured product of a polyurea resin composition obtained from the polyurea resin composition production raw material is 30 mN / m or more and 63 mN / m or less.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 Art

[0002] Polyurea resin is used as a reinforcing material for aging buildings and structures, and as a material for imparting durability against natural disasters such as earthquakes, because it has excellent various physical properties.

[0003] Since the reaction between the polyisocyanate component and the polyamine component, which are raw materials of the polyurea resin, is extremely fast, in the coating of the polyurea resin composition, these two raw materials are generally mixed and spray-coated using a collision-type spraying device.

[0004] On the other hand, in coating in a closed space or on a complex shape, since a spraying device cannot be used, it can be applied manually (hereinafter also referred to as "hand painting"), and the development of a polyurea resin composition that is not affected by the state of the coated surface (such as a wall surface or a wet surface) and has excellent workability is desired.

[0005] As documents mentioning hand painting of a polyurea resin composition, for example, the following documents can be cited. Patent Document 1 describes that hand painting becomes possible by diluting a solid polyurea resin raw material with a specific plasticizer and an organic solvent. Patent Document 2 describes a urea resin composition containing an isocyanate prepolymer having a specific structure and an aromatic amine. Patent Document 3 describes that a polyaspartic paint composition having a low viscosity immediately after mixing of raw materials can be obtained by combining an aspartic acid ester compound having a specific structure and an isocyanate compound having a specific structure.

Prior Art Documents

Patent Documents

[0006] [Patent Document 1] Japanese Patent No. 5044879 [Patent Document 2] Japanese Unexamined Patent Application Publication No. 2009-91414 [Patent Document 3] Japanese Unexamined Patent Application Publication No. 2022-66853 [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] However, the polyurea resin compositions described in Patent Documents 1 to 3 do not have sufficient curing time when applied by hand over a large area such as in civil engineering and construction applications.

[0008] In addition, hand application allows for easier adjustment of the thickness and easier production of a uniform coating film compared to spraying. Therefore, a higher level of design quality for the coating film appearance is required compared to spraying. Against this background, there is a need for a polyurea resin composition that is difficult to sag (has sag resistance) when applied to a wall surface, has good bubble dissipation during application (excellent defoaming property of the coating film), and can form a coating film with good appearance. Also, a polyurea resin composition having a curing time suitable for hand application and capable of forming a coating film with excellent adhesion to a substrate (especially a concrete substrate) has not been developed.

[0009] An object of the present invention is to provide a raw material for producing a polyurea resin composition and a polyurea resin composition that can obtain a paint having a curing time suitable for hand application, excellent sag resistance and defoaming property of the coating film, and further can form a cured product with excellent adhesion to a substrate. [Means for Solving the Problems]

[0010] The inventor conducted intensive studies to solve the above problems. As a result, when applying by hand using a polyurea resin composition, it is not sufficient to only design the viscosity and pot life of the polyurea resin composition obtained by mixing the raw materials for producing the polyurea resin composition. Immediately after mixing all the components, the residual viscosity, viscosity, and kinematic viscosity coefficient are adjusted to specific ranges, and the surface free energy of the surface of the cured product of the polyurea resin composition is adjusted to a specific range, thereby finding that the above problems can be solved and reaching the present invention.

[0011] That is, the present invention provides inventions in 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), and satisfying all of the following conditions (1) to (4). (1) The residual viscosity after mixing all components including component (A) and component (B) for 30 seconds is 1,500 mPa·s or more and 20,000 mPa·s or less. (2) The viscosity after mixing all components including component (A) and component (B) for 30 seconds is 1,500 mPa·s or more and 30,000 mPa·s or less, and the viscosity after mixing for 30 minutes is 100,000 mPa·s or less. (3) The kinematic viscosity coefficient after mixing all components including component (A) and component (B) for 30 seconds is 1,200 m 2 / s or more and 30,000 m 2 / s or less. (4) The surface free energy of the cured product of the polyurea resin composition obtained from the raw material for producing the polyurea resin composition is 30 mN / m or more and 63 mN / m or less. <2> The raw material for producing a polyurea resin composition according to <1>, wherein the tensile product of the cured product is 150 N / mm or more. <3> The raw material for producing a polyurea resin composition according to <1> or <2>, wherein the weight loss rate of the cured product after immersion in a 10% sulfuric acid aqueous solution at 50°C for 30 days is 10% or less. <4> The raw material for producing the polyurea resin composition according to any one of <1> to <3>, wherein the cured product has a weight loss rate of 10% or less after being immersed in a saturated calcium hydroxide aqueous solution at 50°C for 30 days. <5> The raw material for producing the polyurea resin composition according to any one of <1> to <4>, wherein the adhesion strength when the cured product having a thickness of 0.7 mm is laminated on concrete is 1.5 N / mm 2 or more. <6> A polyurea resin composition obtained from the raw material for producing the polyurea resin composition according to any one of <1> to <5>. <7> A paint containing the polyurea resin composition according to <6>. <8> A coating film obtained from the paint according to <7>. <9> A painting method of applying the paint according to <7>, wherein the method of applying the paint is brush painting, roller coating, or trowel coating.

Advantages 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 curing time even when applied by hand to a large area such as in civil engineering and construction applications, and thus is extremely excellent in workability during hand application. Further, the polyurea resin composition of the present invention is excellent in sag resistance (difficult to sag), so it is easy to apply to a wall surface and can form a coating film excellent in thickness uniformity. Furthermore, the polyurea resin composition of the present invention is excellent in defoaming properties because bubbles disappear easily during coating, and thus can form a coating film excellent in appearance. Furthermore, the cured product obtained from the polyurea resin composition of the present invention is excellent in adhesion to a substrate, water resistance, chemical resistance, and physical strength, and thus can visually and physically maintain and protect the substrate for a long period of time.

Modes for Carrying Out the Invention

[0013] 1. Raw Material for Producing Polyurea Resin Composition The raw materials for producing the polyurea resin composition of the present invention include a component (A) containing a polyisocyanate compound (a) and a component (B) containing a polyamine compound (b), and satisfy all of the following conditions (1) to (4). (1) The residual viscosity after mixing all components including component (A) and component (B) for 30 seconds is 1,500 mPa·s or more and 20,000 mPa·s or less. (2) The viscosity after mixing all components including component (A) and component (B) for 30 seconds is 1,500 mPa·s or more and 30,000 mPa·s or less, and the viscosity after mixing for 30 minutes is 100,000 mPa·s or less. (3) The kinematic viscosity coefficient after mixing all components including component (A) and component (B) for 30 seconds is 1,200 m 2 / s or more and 30,000 m 2 / s or less. (4) The surface free energy of the cured product of the polyurea resin composition obtained from the raw materials for producing the polyurea resin composition is 30 mN / m or more and 63 mN / m or less.

[0014] (Polyisocyanate compound) The polyisocyanate compound (a) used in the present invention is a compound having two or more isocyanate groups in one molecule, and its form may be any of a monomer, an oligomer, and a polymer. The polyisocyanate compound (a) is not particularly limited. For example, aliphatic polyisocyanates, alicyclic polyisocyanates, polycyclic aliphatic polyisocyanates, aromatic ring-containing aliphatic polyisocyanates, aromatic polyisocyanates, and their derivatives (for example, isocyanate-terminated prepolymers, allophanate-modified products, urea-modified products, carbodiimide-modified products, burette-modified products, uretdione-modified products, and isocyanurate-modified products obtained by reacting the above polyisocyanates with polyamines or polyols, etc.) can be mentioned. These may be used alone or in combination of two or more.

[0015] Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl octane, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate and the like. These may be used alone or in combination of two or more.

[0016] Examples of the alicyclic polyisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated methylene bisphenyl diisocyanate, and isocyanurate compounds thereof. These may be used alone or in combination of two or more.

[0017] Examples of the polycyclic aliphatic polyisocyanate include 2,5(6)-diisocyanatomethylbicyclo[2,2,1]heptane, 2-isocyanatomethyl-5(6)-isocyanatoethylbicyclo[2,2,1]heptane, 2-isocyanatomethyl-5(6)-isocyanatopropylbicyclo[2,2,1]heptane, 2-isocyanatomethyl-5(6)-isocyanatobutylbicyclo[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)-isocyanatopentylbicyclo[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 2,6Decane, 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)-diisocyanatopropyltricyclo[5,2,1,0 2,6 Decane, 3(4),8(9)-diisocyanatobutyltricyclo[5,2,1,0 2,6 Decane, 3(4),8(9)-diisocyanatopentyltricyclo[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 Examples include nonane, etc. These may be used individually or in combination of two or more.

[0018] Examples of the aromatic ring-containing aliphatic polyisocyanate include xylylene diisocyanate, tetramethylxylylene diisocyanate, etc. These may be used individually or in combination of two or more.

[0019] Examples of the aromatic polyisocyanate 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-naphthalene diisocyanate, 4,4'-diphenylpropane diisocyanate, and the like. These may be used alone or in combination of two or more.

[0020] The polyisocyanate compound (a) preferably has an isocyanate group content of 3 to 45 NCO%, more preferably 5 to 40 NCO%. By setting the isocyanate group content of the polyisocyanate compound (a) within the above range, a curing time suitable for manual coating can be obtained, and a cured product (coating film) excellent in adhesion to the substrate, water resistance, chemical resistance, and physical strength can be obtained.

[0021] (Polyamine compound) The polyamine compound (b) used in the present invention is a compound having two or more amino groups in one molecule, and its form may be any of a monomer, an oligomer, and a polymer. The polyamine compound (b) is not particularly limited. For example, it includes aliphatic polyamines, aromatic ring-containing aliphatic amines, alicyclic polyamines, heterocyclic polyamines, aromatic polyamines, aromatic polyamines having a nucleus-substituted alkyl group, aromatic polyamines having a nucleus-substituted electron-withdrawing group, aromatic polyamines having a secondary amino group, polyamide polyamines, polyether polyamines, cyanoethylated polyamines, and hydrazines. These may be used alone or in combination of two or more.

[0022] Examples of the aliphatic polyamine include alkylene diamines [such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, and hexamethylenediamine, etc.], polyalkylene polyamines [such as diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine, etc.], their alkyl or hydroxyalkyl substituted products [such as dialkylaminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, and 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.

[0023] Examples of the aromatic ring-containing aliphatic amine include xylylenediamine, and tetrachloro-p-xylylenediamine, etc. These may be used alone or in combination of two or more.

[0024] Examples of the alicyclic polyamine 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.

[0025] Examples of the heterocyclic polyamine 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.

[0026] Examples of the aromatic polyamine include 1,2-, 1,3- and 1,4-phenylenediamine, 2,4'- and 4,4'-diphenylmethanediamine, crude diphenylmethanediamine [polyphenylpolymethylene polyamine], 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-aminobenzoate). These may be used alone or in combination of two or more kinds.

[0027] Aromatic polyamines having a nuclear substitution alkyl group (for example, alkyl groups such as methyl, ethyl, n- and i-propyl, butyl, etc.) include, for example, 2,4- and 2,6-tolylene diamine, crude tolylene diamine, diethyl tolylene diamine, 4,4'-diamino-3,3'-dimethyl diphenylmethane, 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-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'-dimethyl diphenylmethane, 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,Examples include 4'-diaminodiphenyl sulfone and mixtures of various ratios of these isomers. These may be used individually or in combination of two or more kinds.

[0028] Examples of the aromatic polyamine having a nuclear-substituted electron-withdrawing group (e.g., halogen such as Cl, Br, I, and F; alkoxy groups such as methoxy and ethoxy; nitro group, etc.) include methylene bis-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 individually or in combination of two or more kinds.

[0029] Examples of the aromatic polyamine having a secondary amino group [a compound in which part or all of -NH2 of the above aromatic polyamine is replaced by -NH-R' (R' is an alkyl group, e.g., a lower alkyl group such as methyl and ethyl)] include 4,4'-di(methylamino)diphenylmethane and 1-methyl-2-methylamino-4-aminobenzene. These may be used individually or in combination of two or more kinds.

[0030] Examples of the polyamide polyamine include, for example, low molecular weight polyamide polyamines obtained by condensation of dicarboxylic acids and polyamines. These may be used alone or in combination of two or more.

[0031] Examples of the polyether polyamine include, for example, hydrogenated products of cyanoethylated polyether polyols. These may be used alone or in combination of two or more.

[0032] Examples of the cyanoethylated polyamine include, for example, cyanoethylated polyamines obtained by an addition reaction of acrylonitrile and polyamines (such as the above-mentioned alkylene diamines and polyalkylene polyamines) (for example, biscyanoethyldiethylenetriamine). These may be used alone or in combination of two or more.

[0033] Examples of the hydrazines include, for example, hydrazine, monoalkyl hydrazine, dihydrazide (such as succinic acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, etc.), guanidine (such as butyl guanidine, 1-cyanoguanidine, etc.), and dicyandiamide. These may be used alone or in combination of two or more.

[0034] In the raw materials for producing the polyurea resin composition of the present invention, the molar ratio (isocyanate group / amino group) of the isocyanate group of the polyisocyanate compound (a) to the amino group of the polyamine compound (b) is preferably 0.6 to 1.5, and more preferably 0.8 to 1.2. By setting the molar ratio (isocyanate group / amino group) within the above range, a curing time suitable for manual coating can be obtained, and a cured product (coating film) excellent in adhesion to the substrate, water resistance, chemical resistance, and physical strength can be obtained.

[0035] (Polyol compound) The raw materials for producing the polyurea resin composition of the present invention may further contain a polyol compound (c).

[0036] Examples of the polyol compound (c) include divalent alkyl alcohols such as ethylene glycol, propylene glycol, and 1,6 - hexanediol; trivalent alkyl alcohols such as glycerin; tetravalent or higher alkyl alcohols such as diglycerin, erythritol, and sorbitol; oligomers and polymers such as polyester polyol, polyether polyol, acrylic polyol, polyolefin polyol, polyurethane polyol, and alkylene oxide adducts of amines (where the terminal monomer component is an aliphatic alcohol). These may be used alone or in combination of two or more.

[0037] In the raw materials for producing the polyurea resin composition of the present invention, the amount of the polyol compound (c) used may be appropriately adjusted within the range that satisfies all of the conditions (1) to (4) described later. Preferably, it is an amount that is 50 mol% or less, more preferably 20 mol% or less, based on the total of the amino group and the hydroxy group.

[0038] (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 cured product (coating film) or to adjust the pot life and curing temperature.

[0039] Examples of the catalyst 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, butyltin trichloride, bismuth trichloride, bismuth octenoate, tetrakis(2 - ethylhexyl) titanate, tetrabutoxy titanium, 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. The amount of the catalyst used may be appropriately adjusted within the range that satisfies all of the conditions (1) to (4) described later.

[0040] (Additive) The raw materials for producing the polyurea resin composition of the present invention may contain additives as required.

[0041] Examples of the additives include basic inorganic compounds, pH adjusters, metal oxide fine particles, tackifiers, waxes, ultraviolet absorbers, surface modifiers, defoamers, thixotropy imparting agents, colorants, dispersants, fillers, diluents, and the like. These may be used alone or in combination of two or more. The amount of the additive used may be appropriately adjusted according to the purpose.

[0042] (Physical properties of the raw materials for producing the polyurea resin composition) (Residual viscosity) The raw materials for producing the polyurea resin composition of the present invention satisfy the following condition (1). (1) All components including component (A) and component (B) are mixed, and the residual viscosity after 30 seconds is 1,500 mPa·s or more and 20,000 mPa·s or less. When the residual viscosity is less than 1,500 mPa·s, the polyurea resin composition obtained by mixing the raw materials for producing the polyurea resin composition is inferior in defoaming property and sag resistance during coating. On the other hand, when the residual viscosity exceeds 20,000 mPa·s, the polyurea resin composition obtained by mixing the raw materials for producing the polyurea resin composition does not have a sufficient curing time or requires too much force for coating, and thus is unsuitable for manual coating. From the viewpoints of obtaining a polyurea resin composition having a curing time suitable for manual coating and obtaining a polyurea resin composition excellent in defoaming property and sag resistance during coating, the residual viscosity is preferably 1,750 mPa·s or more and 17,500 mPa·s or less, more preferably 2,000 mPa·s or more and 15,000 mPa·s or less. In the present invention, the residual viscosity is a value obtained by the following measurement method. In a 50 mL glass beaker, all components including component (A) and component (B) are added so that the total amount becomes 15 mL, and mixed with a medicine spoon for 15 seconds. Then, using a B-type viscometer, the viscosity at a temperature of 25°C 30 seconds after mixing is measured at three points while changing the rotation speed. When the viscosity exceeds 1,000 mPa·s, the spindle of the B-type viscometer is LV-4, and when it is 1,000 mPa·s or less, SC4-18 is used. Also, as the rotation speed, three points are adopted in order from the one closest to the measurement upper limit of the B-type viscometer among 0.3 rpm, 0.6 rpm, 1.5 rpm, 3 rpm, 6 rpm, 12 rpm, 30 rpm, and 60 rpm. From the rotation speed and the spindle shape, the shear rate D and the shear stress σ are obtained, plotted with the x-axis being the shear rate D and the y-axis being the shear stress σ, and the value obtained by squaring the slope of the straight line obtained by performing linear regression by the least squares method is taken as the residual viscosity η∞ (mPa·s).

[0043] Examples of the method for setting the residual viscosity within the above range include adjusting the molecular weights of the polyisocyanate compound (a), polyamine compound (b), and polyol compound (c), introducing substituents into the compounds to adjust symmetry, and adding an appropriate amount of additives such as fillers, diluents, and viscosity modifiers. When introducing substituents into the compounds to adjust symmetry, generally, the larger and more bulky the substituents are, the more the symmetry is disrupted and the lower the residual viscosity becomes, while the smaller and more symmetric the substituents are, the higher the residual viscosity tends to be.

[0044] (Viscosity) The raw materials for producing the polyurethane resin composition of the present invention satisfy the following condition (2). (2) The viscosity after mixing all the components containing component (A) and component (B) for 30 seconds is 1,500 mPa·s or more and 30,000 mPa·s or less, and the viscosity after mixing for 30 minutes is 100,000 mPa·s or less. When the viscosity after mixing for 30 seconds is less than 1,500 mPa·s, the polyurea resin composition obtained by mixing the raw materials for producing the polyurea resin composition is inferior in sag resistance during coating. On the other hand, when the viscosity after mixing for 30 seconds exceeds 30,000 mPa·s and when the viscosity after mixing for 30 minutes exceeds 100,000 mPa·s, the polyurea resin composition obtained by mixing the raw materials for producing the polyurea resin composition does not have a sufficient curing time and is thus unsuitable for manual coating. From the viewpoints of obtaining a polyurea resin composition having a curing time suitable for manual coating and obtaining a polyurea resin composition excellent in sag resistance during coating, the viscosity after mixing for 30 seconds is preferably 1,750 mPa·s or more and 27,500 mPa·s or less, more preferably 2,000 mPa·s or more and 25,000 mPa·s or less. Also, from the viewpoint of obtaining a polyurea resin composition having a curing time suitable for manual coating, the viscosity after mixing for 30 minutes is preferably 90,000 mPa·s or less, more preferably 80,000 mPa·s or less. In the present invention, the viscosities after mixing for 30 seconds and 30 minutes are values obtained by the following measurement method. In a 50 mL glass beaker, add all the components containing component (A) and component (B) so that the total amount becomes 15 mL, and mix for 15 seconds with a medicine spoon. Then, using a B-type viscometer, measure the viscosities at a temperature of 25°C after mixing for 30 seconds and 30 minutes. Note that for the spindle of the B-type viscometer, LV-4 is used when the viscosity exceeds 1,000 mPa·s, and SC4-18 is used when the viscosity is 1,000 mPa·s or less.

[0045] As a method for making the viscosities after mixing for 30 seconds and 30 minutes within the above ranges, for example, adjusting the molecular weights of the polyisocyanate compound (a), polyamine compound (b), and polyol compound (c), or adding an appropriate amount of additives such as fillers, diluents, and viscosity-imparting agents can be mentioned.

[0046] (Kinematic viscosity coefficient) The raw materials for producing the polyurea resin composition of the present invention satisfy the following condition (3). (3) The kinematic viscosity coefficient 30 seconds after mixing all the components including component (A) and component (B) is 1,200 m 2 / s or more and 30,000 m 2 / s or less. When the kinematic viscosity coefficient 30 seconds after mixing is less than 1,200 m 2 / s, the polyurea resin composition obtained by mixing the raw materials for producing the polyurea resin composition is inferior in defoaming property during coating, or the cured product (coating film) obtained from the polyurea resin composition is inferior in adhesion to the substrate. On the other hand, when the kinematic viscosity coefficient 30 seconds after mixing exceeds 30,000 m 2 / s, the cured product (coating film) obtained from the polyurea resin composition is inferior in adhesion to the substrate or inferior in uniformity. The kinematic viscosity coefficient 30 seconds after mixing is preferably 1,500 m 2 / s or more and 27,000 m 2 / s or less. In the present invention, the kinematic viscosity coefficient 30 seconds after mixing is a value obtained by the following measurement method. In a 50 mL glass beaker, add all the components including component (A) and component (B) so that the total amount becomes 15 mL, and mix for 15 seconds with a medicine spoon. Then, using a B-type viscometer, measure the viscosity η (Pa·s) at a temperature of 25°C 30 seconds after mixing. Note that for the spindle of the B-type viscometer, use LV-4 when the viscosity exceeds 1,000 mPa·s, and use SC4-18 when the viscosity is 1,000 mPa·s or less. Also, using a pycnometer, in an environment of 25°C, determine the density ρ (kg / m 3 ) of the mixture obtained by mixing all the components including component (A) and component (B). Then, calculate the kinematic viscosity coefficient using the following formula. Kinematic viscosity coefficient ν (m 2 / s) = η (Pa·s) / ρ (kg / m 3 )

[0047] As a method for making the kinematic viscosity coefficient after mixing reach the above range within 30 seconds, for example, introducing a halogen group or the like into the polyisocyanate compound (a), polyamine compound (b), and polyol compound (c) to increase the density, or adding an appropriate amount of additives such as fillers, diluents, and viscosity - imparting agents, etc. can be mentioned.

[0048] 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 adopted. Also, if necessary, other optional components such as polyol compound (c), catalyst, and additives may be mixed. Other optional components such as polyol compound (c), catalyst, and additives may be blended in component (A) and / or component (B) in advance, or may be mixed simultaneously with component (A) and component (B).

[0049] 3. Paint The paint of the present invention contains the polyurea resin composition of the present invention. Since it has sufficient curing time even when hand - painting a large area such as for civil engineering and construction applications, it is extremely excellent in workability during hand - painting. Also, the paint of the present invention is excellent in sag resistance (difficult to sag), so it is easy to apply to the wall surface and can form a coating film with excellent thickness uniformity. Furthermore, since the paint of the present invention has excellent defoaming properties and the bubbles disappear easily during painting, it can form a coating film with excellent appearance.

[0050] 4. Cured product The cured product (coating film) of the present invention is obtained by curing the polyurea resin composition of the present invention and has the following physical properties.

[0051] (Surface free energy) The cured product of the present invention has a surface free energy of 30 mN / m or more and 63 mN / m or less, preferably 32 mN / m or more and 60 mN / m or less. When the residual viscosity, viscosity, and kinematic viscosity coefficient of the raw material for producing the polyurea resin composition are within a specific range and the surface free energy of the cured product is within the above range, the foam-breaking property when the cured product is formed is improved, and a cured product excellent in adhesion to a substrate, physical strength, water resistance, and chemical resistance can be obtained. In the present invention, the surface free energy of the cured product is a value obtained by the following measurement method. A mixture obtained by mixing all components including component (A) and component (B) is poured into a gold frame having a thickness of 1 mm, a length of 15 cm, and a width of 10 cm, and allowed to stand at 25 °C for 48 hours to prepare a cured plate of polyurea resin. Then, based on JIS K 6768:1999 (Plastics - Films and Sheets - Method of Test for Wettability Tension), the surface free energy of the cured plate is measured in a standard test chamber atmosphere at a temperature of 23 °C and a relative humidity of 50% using a test mixture for wettability tension measurement.

[0052] As a method for making the surface free energy of the cured product within the above range, for example, the amount of polar monomers of the polyisocyanate compound (a) or the polyamine compound (b) can be adjusted, the molecular weight of the monomer or prepolymer of the raw material can be adjusted, additives such as a filler, a diluent, a surfactant, and a viscosity-imparting agent can be added, or it can be adjusted by containing other components such as an alcohol and a carboxylic acid. It should be noted that the more polar components there are in the monomer or other components, and the smaller the molecular weight of the monomer or prepolymer, the higher the surface free energy tends to be.

[0053] (Tensile product) From the viewpoint of excellent adhesion to the substrate, the tensile product of the cured product of the present invention is preferably 150 N / mm or more, more preferably 200 N / mm or more. In the present invention, the tensile product of the cured product is a value obtained by the following measurement method. 60 g of a mixture obtained by mixing all the components including component (A) and component (B) is poured into a metal frame having a thickness of 1 mm, a length of 15 cm, and a width of 10 cm, and allowed to stand at 25 °C for 48 hours to produce a cured plate of polyurea resin. The produced cured plate is punched into a dumbbell shape No. 2 to obtain a test piece. Using a testing machine, the tensile strength (N / mm 2 ) and the elongation at break (mm) of the test piece are determined, and the tensile product (N / mm) is determined by the following formula. The number of measurements is 5, the gripping distance of the test piece is 70 mm, and the tensile speed is 5 mm / min for the measurement. The average value of the tensile products obtained by 5 measurements is adopted. Tensile product (N / mm) = Tensile strength (N / mm 2 ) × Elongation at break (mm)

[0054] As a method for making the tensile product of the cured product within the above range, for example, adjusting the amount of polar monomers of the polyisocyanate compound (a) or the polyamine compound (b), adjusting the molecular weight, the amount of flexible components, and the presence or absence of side chain functional groups of the monomer or prepolymer of the raw materials, adjusting the amount of additives such as fillers, diluents, surfactants, and viscosity imparting agents, and containing other components such as alcohols and carboxylic acids for adjustment, etc. can be mentioned.

[0055] (Weight loss rate) From the perspective of excellent water resistance, the weight loss rate of the cured product of the present invention after immersion in water at 50°C for 30 days is preferably 10% or less, more preferably 8% or less. Further, from the perspective of excellent chemical resistance, the weight loss rate of the cured product of the present invention after immersion in a 10% sulfuric acid aqueous solution at 50°C for 30 days is preferably 10% or less, more preferably 8% or less. Also, from the perspective of excellent chemical resistance, the weight loss rate of the cured product of the present invention after immersion in a saturated calcium hydroxide aqueous solution at 50°C for 30 days is preferably 10% or less, more preferably 8% or less. In the present invention, the weight loss rate of the cured product is a value obtained by the following measurement method. 10 g of a mixture obtained by mixing all the components including component (A) and component (B) is poured into a metal frame having a thickness of 1 mm, a length of 5 cm, and a width of 5 cm, and allowed to stand at 25°C for 48 hours to produce a cured plate of a polyurethane resin having a thickness of 1 mm. The produced cured plate is immersed in water (50°C), a 10% sulfuric acid aqueous solution (50°C), or a saturated calcium hydroxide aqueous solution (50°C) for 30 days. After immersion, the cured plate is washed with water and then dried at 150°C for 2 hours. Then, the weight loss rate is determined by the following formula. Weight loss rate (%) = (weight of the cured plate after immersion / weight of the cured plate before immersion) × 100

[0056] As a method for making the weight loss rate of the cured product within the above range, for example, adjusting the amount of polar monomers of the polyisocyanate compound (a) or the polyamine compound (b), adjusting the molecular weight of the monomer or prepolymer of the raw material, the amount of flexible components, the presence or absence of side chain functional groups, and the balance of hydrophilicity and hydrophobicity, adjusting the amount of additives such as fillers, diluents, surfactants, and viscosity imparting agents, etc. can be mentioned.

[0057] (Adhesion strength) From the perspective of excellent adhesion to the substrate, the adhesion strength when a cured product with a thickness of 0.7 mm is laminated on concrete is 1.5 N / mm 2 or more, preferably 2.0 N / mm 2The above is the case. In the present invention, the adhesion strength is a value obtained by the following measurement method. It is measured in accordance with "7.4 Adhesion Strength Test" described in JIS A 1171:2016 (Test Methods for Polymer Cement Mortar). Specifically, a concrete block of 7 cm × 7 cm × 2 cm is prepared. A mixture obtained by mixing all components including component (A) and component (B) is applied to the surface with an area of 49 cm 2 of the concrete block, and left standing at 25°C for 48 hours to prepare a test piece (thickness of the cured film: 0.7 mm). An epoxy adhesive is applied to a 4 cm square tensile jig, attached to the polyurethane-coated surface of the test piece, and left standing at 25°C for 24 hours. Then, a cut is made around the tensile jig with a cutter knife so as to form a 4 cm square polyurethane coating film, and a lower tensile jig is attached to the test piece via a steel backing plate. Then, a load is applied in the vertical direction of the test piece at a load rate of 2,000 N per minute to obtain the maximum load. The adhesion strength of the test piece is determined by the following formula. The adhesion strength is the value obtained by rounding the average value of the adhesion strengths of 5 test pieces to one decimal place. Adhesion strength (N / mm 2 ) = Maximum load (N) / 1600 (mm 2 )

[0058] Examples of the method for making the adhesion strength fall within the above range include adjusting the amount of the polar monomer of the polyisocyanate compound (a) or the polyamine compound (b), adjusting the molecular weight, amount of flexible component, and presence or absence of side chain functional groups of the monomer or prepolymer of the raw material, and adjusting the amounts of additives such as fillers, diluents, surfactants, and viscosity modifiers.

[0059] 5. Coating method Since the paint of the present invention has a sufficient curing time, known methods can be used without particular limitation as the method for applying the paint. The method for applying the paint may be appropriately selected according to the thickness of the paint film, the shape of the object to be coated, etc. For example, dipping painting (immersion painting, dipping), wire bar, baker applicator, gravure roll, potting, brush painting, roller painting, and trowel painting can be mentioned. In addition, it is also possible to form a cured product (paint film) three-dimensionally by a 3D printer or the like. Since the paint of the present invention has a sufficient curing time even when hand-painted on a large area such as for civil engineering and construction applications, it is preferably applied by brush painting, roller painting, or trowel painting.

[0060] Since the paint of the present invention has reactivity at room temperature, heating is usually not necessary, but heating may be performed to accelerate curing. The curing temperature can be appropriately determined from the construction method and the curing time, but from the viewpoint of safety, it is preferably 40 to 80°C.

[0061] As the heating device for the paint of the present invention, known ones can be used in view of 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, an air high-temperature heater, a heat gun, a dryer, a drying furnace, a baking furnace, a constant-temperature dryer, and a constant-temperature furnace.

[0062] The curing time may be appropriately selected in view of the characteristics of the paint, the heating device, and the curing process, but from the viewpoint of productivity, it is preferably less than 24 hours, more preferably less than 12 hours, and even more preferably less than 8 hours. The catalyst may be used to adjust the curing time.

[0063] The thickness of the paint film can be appropriately selected according to the intended physical properties, the material of the base material, etc. Usually, from the viewpoints of economy and physical properties, 10 to 10,000 μm is preferable, 50 to 8,000 μm is more preferable, and 100 to 5,000 μm is even more preferable. Also, as a method for obtaining the above thickness, it may be applied at once, or overcoated in multiple times.

[0064] 6. Use The polyurea resin composition of the present invention has a viscosity, pot life, and curing time that enable manual painting work, and furthermore, it is excellent in sag resistance, defoaming property of the coating film, workability, adhesion to the substrate, and physical strength. Examples of the uses of the polyurea resin composition of the present invention include, for example, coated floors, linings, roof waterproofing, exterior wall painting, waterproofing of bridge deck slabs, waterproof paints, anticorrosive paints, protective paints for the inside and outside of steel pipes, metal pipes, and tanks, reinforcement and repair of buildings, protection of resin parts and metal parts, and storage ponds.

[0065] The polyurea resin composition of the present invention can also be compounded with planar bodies such as fibers (including both long fibers and short fibers), non-woven fabrics (including both long fibers and short fibers), cloth, wire mesh, mesh, and punched metal. Known methods can be adopted for the compounding method. The coating amount when compounding with the planar body may be appropriately adjusted according to the target physical properties and the material of the substrate, etc., but from the viewpoints of economy and physical properties, 0.01~5 kg / m 2 is preferable, 0.03~4 kg / m 2 is more preferable, and 0.05~3 kg / m 2 is even more preferable.

[0066] Also, the polyurea resin composition of the present invention can be poured into a metal frame to manufacture a molded body.

Examples

[0067] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The evaluation methods for various physical properties in the examples and comparative examples are as follows.

[0068] (1) Viscosity Using a B-type viscometer (manufactured by BROOKFIELD ENGINEERING LABORATORIES, INC., BROOKFIELD DIAL VISCOMETER Model LVT), the rotational viscosity (mPa·s) at a temperature of 25°C was measured. All components containing the polyisocyanate compound (a) and the polyamine compound (b) were added to a 50 mL glass beaker so that the total volume became 15 mL. Then, using a metal spatula, it was quickly mixed for 15 seconds. And the viscosities at 25°C after 30 seconds and 30 minutes of mixing were measured. In addition, for the spindle of the B-type viscometer, LV-4 was used when the viscosity exceeded 1,000 mPa·s, and SC4-18 was used when the viscosity was 1,000 mPa·s or less.

[0069] (2) Foam-breaking property of the coating film All components containing the polyisocyanate compound (a) and the polyamine compound (b) were put into a 1 L metal can so that the total amount became 500 g, and they were mixed with a paint mixer at 400 rpm for 30 seconds. The obtained mixture was applied to a concrete plate using a trowel with a length of 210 mm, a tip width of 75 mm, and a butt width of 80 mm so that the coating thickness became 1 mm. The coating film was visually confirmed, and those that foamed during coating and a uniform coating film was obtained were evaluated as ○, and those that did not foam and bubbles remained in the coating film were evaluated as ×. In addition, the temperature of the mixture, the concrete plate, and at the time of confirmation was all 25°C.

[0070] (3) Residual viscosity The same operation as in the viscosity in (1) above was performed, and the viscosities at 25°C after 30 seconds of mixing were measured at 3 points by changing the rotation speed. In addition, for the spindle of the B-type viscometer, LV-4 was used when the viscosity exceeded 1,000 mPa·s, and SC4-18 was used when the viscosity was 1,000 mPa·s or less. Also, for the rotation speed, 3 points were adopted in order from the one close to the measurement upper limit of the B-type viscometer. From the rotation speed and the spindle shape, the shear rate D and the shear stress σ were obtained, plotted with the x-axis as the shear rate D and the y-axis as the shear stress, and the value obtained by squaring the slope of the straight line obtained by performing linear regression by the least squares method was determined, and the obtained value was taken as the residual viscosity η∞ (mPa·s).

[0071] (4) Kinematic viscosity The same operation as in the viscosity (1) was performed, and the mixture was mixed, and the viscosity η (Pa·s) at a temperature of 25°C after 30 seconds was measured. Also, using a pycnometer, in an environment of 25°C, the density ρ (kg / m 3 ) of the mixture obtained by mixing all the components including the polyisocyanate compound (a) and the polyamine compound (b) was measured. Then, the kinematic viscosity was determined by the following formula. Kinematic viscosity ν (m 2 / s) = η (Pa·s) / ρ (kg / m 3 )

[0072] (5) Surface free energy The mixture containing all the components of the polyisocyanate compound (a) and the polyamine compound (b) was poured into a gold frame with a thickness of 1 mm, a length of 15 cm, and a width of 10 cm, and left standing at 25°C for 48 hours to prepare a cured plate of the polyurethane resin. Then, based on JIS K 6768:1999 (Plastics - Films and Sheets - Method of Test for Wettability Tension), using a test mixture for wettability tension measurement, the surface free energy of the cured plate was measured in a standard test chamber atmosphere at a temperature of 23°C and a relative humidity of 50%.

[0073] (6) Tensile strength, elongation at break, tensile product All the components including the polyisocyanate compound (a) and the polyamine compound (b) were quickly mixed using a metal spatula so that the total amount was 60 g, and the obtained mixture was poured into a gold frame with a thickness of 1 mm, a length of 15 cm, and a width of 10 cm, and left standing at 25°C for 48 hours to prepare a cured plate of the polyurethane resin with a thickness of 1 mm. The prepared cured plate was punched into a dumbbell shape No. 2 to obtain a test piece. Using a desktop precision universal testing machine (manufactured by Shimadzu Corporation, Autograph AGS-X) in an environment of 25°C, the tensile strength (N / mm 2 ) and elongation at break (mm) of the test piece were determined, and the tensile product (N / mm) was determined by the following formula. The number of measurements was 5, the gripping distance of the test piece was 70 mm, and the tensile speed was 5 mm / min for the measurement. The average value of the tensile products obtained from 5 measurements was adopted. Tensile product (N / mm) = Tensile strength (N / mm 2 ) × Elongation at break (mm)

[0074] (7) Immersion test (water resistance, chemical resistance) All components including the polyisocyanate compound (a) and the polyamine compound (b) were quickly mixed using a metal medicine spoon so that the total amount became 10 g, and the obtained mixture was poured into a metal frame with a thickness of 1 mm, a length of 5 cm, and a width of 5 cm, and left standing at 25 °C for 48 hours to prepare a cured plate of the polyurethane resin with a thickness of 1 mm. The prepared cured plate was immersed in water (50 °C), 10% sulfuric acid aqueous solution (50 °C), or saturated calcium hydroxide aqueous solution (50 °C) for 30 days. After immersion, the cured plate was washed with water and then dried at 150 °C for 2 hours. Then, the weight loss rate was determined by the following formula. Weight loss rate (%) = (weight of the cured plate after immersion / weight of the cured plate before immersion) × 100

[0075] (8) Adhesion It was measured according to the "7.4 Adhesion Strength Test" described in JIS A 1171:2016 (Test Method for Polymer Cement Mortar). A concrete block of 7 cm × 7 cm × 2 cm was prepared. A mixture of all components including the polyisocyanate compound (a) and the polyamine compound (b) was applied to the surface of the concrete block with an area of 49 cm 2 , and left standing at 25 °C for 48 hours to prepare a test piece (thickness of the cured film: 0.7 mm). Epoxy adhesive was applied to a 4 cm square tensile jig, pasted on the polyurethane-coated surface of the test piece, and left standing at 25 °C for 24 hours. Then, a cut was made around the tensile jig with a cutter knife so as to form a 4 cm square polyurethane coating film, and a lower tensile jig was attached to the test piece via a steel backing plate. Then, a load was applied in the vertical direction of the test piece at a load rate of 2,000 N per minute to obtain the maximum load. The adhesion strength of the test piece was determined by the following formula. The value obtained by rounding the average value of the adhesion strengths of 5 test pieces to one decimal place was taken as the adhesion strength. Adhesion strength (N / mm 2 ) = maximum load (N) / 1600 (mm 2 ) In practice, an adhesion strength of 1.0 N / mm 2 or more is required, and an adhesion strength of 1.5 N / mm 2 or more is preferable.

[0076] (9) Sag resistance A sag tester (manufactured by BEVS) was placed parallel to one side of a 20 cm × 20 cm × 1 cm glass plate, and a polyurethane resin composition quickly mixed using a metal medicine spoon to a total amount of 15 g was poured from above the sag tester. While gently pressing down on the sag tester, it was linearly moved at a uniform speed, and a coating film was formed with a thickness in 100-μm increments from 100 μm to 500 μm. Then, immediately with the thicker side of the coating film facing down, the glass plate was set vertically, and sag resistance was judged based on whether or not paint flow (sagging) occurred. When sagging did not occur in a coating film of 400 μm or more, it was marked as ○, and when sagging occurred, it was marked as ×.

[0077] <Polyisocyanate compound (a)> The following were used as the polyisocyanate compound (a). A1: Coronate 2785 (manufactured by Tosoh Corporation, HDI (hexamethylene diisocyanate)-based isocyanate, 19.2% NCO, kinematic viscosity 1,800 mm 2 / s) A2: Isophorone diisocyanate (IPDI, manufactured by Tokyo Chemical Industry Co., Ltd., alicyclic isocyanate, 37.8% NCO, kinematic viscosity 9 mm 2 / s) A3: A prepolymer having an NCO group content of 5.2% by mass obtained by reacting 1.2 parts by mass of polyoxypropylene triol having a molecular weight of 3,000 and 72 parts by mass of polyoxypropylene diol having a molecular weight of 1,000 with 37 parts by mass of 4,4'-diphenylmethane diisocyanate (MDI) (NCO / OH ratio = 2.03) A4: A prepolymer having an NCO group content of 6.1% obtained by reacting 284 parts by mass of polytetramethylene glycol having a molecular weight of 2,000 and 15 parts by mass of diethylene glycol with 100 parts by mass of toluene diisocyanate (TDI, isomer mixture) (NCO / OH ratio = 2.03)

[0078] <Polyamine compound (b)> The following were used as the polyamine compound (b). B1: Elastmer 250P (manufactured by Kumiai Chemical Industry Co., Ltd., aromatic polyamine, amine value 221 mg KOH / g) B2: Elastmer 650P (manufactured by Kumiai Chemical Industry Co., Ltd., aromatic polyamine, amine value 126 mg KOH / g) B3: Feispartic F420 (manufactured by Feiyang, aliphatic polyamine, amine value 203 mg KOH / g) B4: Unilink 4200 (manufactured by Dorf Ketal, aromatic polyamine, amine value 361 mg KOH / g) B5: A prepolymer with an amine value of 70 mg KOH / g obtained by reacting 39 parts by mass of trimethylene-bis(4-aminobenzoate) (NH2 / NCO ratio = 2.0) with 100 parts by mass of the above A3 B6: A prepolymer with an amine value of 106 mg KOH / g obtained by reacting 6 parts by mass of ethylenediamine (NH2 / acrylate ratio = 2.0) with 100 parts by mass of acrylate-terminated hydrogenated polybutadiene with a number average molecular weight of 2,000 (manufactured by Nippon Soda Co., Ltd., TEAI-1000) B7: Diethyltoluenediamine (manufactured by Tokyo Chemical Industry Co., Ltd., aromatic polyamine, amine value 629.5 mg KOH / g) B8: Primacure P-25i (manufactured by Arxada, chlorinated diethyltoluenediamine, amine value 527 mg KOH / g)

[0079] As other components (polyol compounds and additives), the following were used. G700: Glycerin-propylene oxide adduct (manufactured by ADEKA, hydroxyl value 224 mg KOH / g) 231: Organic viscosity modifier (manufactured by Enomoto Kasei Co., Ltd., Disparon PFA-231) P-3: Filler (manufactured by Nippon Talc Co., Ltd., Talc P-3) TiO2: Filler (manufactured by Tokyo Chemical Industry Co., Ltd., titanium dioxide) cHex: Diluent (manufactured by Tokyo Chemical Industry Co., Ltd., cyclohexane) MS4A: Dehydrating agent (manufactured by Resonac Universal Co., Ltd., Molecular Sieves 4A powder)

[0080] Example 1 28 parts by mass of A1 as a polyisocyanate compound, 32 parts by mass of B1 as a polyamine compound, and 1.2 parts by mass of cHex as an additive were added to a 100 g glass beaker, and stirred quickly with a medicine spoon until it became uniformly visible, to obtain a polyurethane resin composition (also in the following examples, the addition amount of the polyamine compound was adjusted so that the isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). Thereafter, the evaluations of (1) to (9) above were carried out. The raw materials used and the evaluation results are shown in Tables 1 to 3.

[0081] Example 2 In Example 1, the same operation was carried out except that the polyamine compound was changed to B2 and the additive was changed to 231 of 1.2 parts by mass, to obtain a polyurethane resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0082] Example 3 In Example 1, the same operation was carried out except that the polyamine compound was changed to B3 and the additive was changed to P-3 of 9 parts by mass, to obtain a polyurethane resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0083] Example 4 In Example 1, the same operation was carried out except that the polyisocyanate compound was changed to A2, the polyamine compound was changed to B4, and the additive was changed to MS4A of 6 parts by mass, to obtain a polyurethane resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0084] Example 5 In Example 4, the same operation was carried out except that the polyamine compound was changed to B5, the additive was changed to cHex of 1.2 parts by mass, and 12.5 parts by mass of G700 was added as a polyol compound, to obtain a polyurethane resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0, hydroxy group amount / amino group amount = 0.25). The evaluation results are shown in Tables 1 to 3.

[0085] Example 6 In Example 4, the same operations were performed except that the polyamine compound was changed to B6 and the additives were changed to 1.2 parts by mass of 231 and 6 parts by mass of TiO2 to obtain a polyurethane resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0086] Example 7 In Example 1, the same operations were performed except that the polyisocyanate compound was changed to A3 and the polyamine compound was changed to B7 to obtain a polyurethane resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0087] Example 8 In Example 7, the same operations were performed except that the polyamine compound was changed to B8, 1.7 parts by mass of G700 was added as the polyol compound, and no additive was added to obtain a polyurethane resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0, hydroxy group amount / amino group amount = 0.25). The evaluation results are shown in Tables 1 to 3.

[0088] Example 9 In Example 7, the same operations were performed except that the polyamine compound was changed to B2 and the additives were changed to 9 parts by mass of P-3 and 6 parts by mass of MS4A to obtain a polyurethane resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0089] Example 10 In Example 1, the same operations were performed except that the polyisocyanate compound was changed to A4, the polyamine compound was changed to B2, and the additive was changed to 1.2 parts by mass of 231 to obtain a polyurethane resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0090] Example 11 In Example 10, the same operations were performed except that the polyamine compound was changed to B3 and the additives were changed to 231 at 1.2 parts by mass and P-3 at 9 parts by mass to obtain a polyurea resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0091] Example 12 In Example 10, the same operations were performed except that the polyamine compound was changed to B6 and the additive was changed to cHex at 1.2 parts by mass to obtain a polyurea resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0092] Example 13 In Example 1, the same operations were performed except that cHex was not added to obtain a polyurea resin composition. A polyurea resin composition was obtained (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0093] Example 14 In Example 1, the same operations were performed except that 10 parts by mass of G700 was added instead of cHex to obtain a polyurea resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0094] Example 15 In Example 1, the same operations were performed except that 1.2 parts by mass of 231 was added instead of cHex to obtain a polyurea resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0095] Example 16 In Example 1, the same operations were performed except that 9 parts by mass of P-3 was added instead of cHex to obtain a polyurea resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0096] Example 17 In Example 1, the same operations were carried out except that 6 parts by mass of MS4A was added instead of cHex to obtain a polyurea resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0097] Comparative Example 1 As the polyisocyanate compound, 17 parts by mass of polyoxypropylene triol with a molecular weight of 3,000 and 68 parts by mass of polyoxypropylene diol with a molecular weight of 2,000 were reacted with 15 parts by mass of tolylene diisocyanate (80% by mass of 2,4-isomer) (NCO / OH ratio = 2.03) to use a prepolymer with an NCO group content of 3.6% by mass. Hereinafter, this prepolymer may be referred to as PP1. As the polyamine compound, a molten mixture obtained by melting 7.30 parts by mass of 4,4'-methylenebis(2-chloroaniline) was used, which was dissolved in 21.04 parts by mass of polyoxypropylene diol with a molecular weight of 2,000. As the additive, a mixture of 12.7 parts by mass of a monocarboxylic acid methyl ester mixture obtained by transesterifying soybean oil with methanol (viscosity at 20 °C: 7.9 mPa·s), 55 parts by mass of calcium carbonate, 3 parts by mass of a pigment paste, and 1 part by mass of lead 2-ethylhexanoate (lead content: 24% by mass) was used. These were quickly stirred with a spatula until they had a uniform appearance to obtain a polyurea resin composition (isocyanate group amount / amino group amount = 1 / 1, isocyanate group / (hydroxy group + amino group) = 1.1). The evaluation results are shown in Tables 1 to 3.

[0098] Comparative Example 2 As the polyisocyanate compound, 50 parts by mass of Excenol 2020 (Asahi Glass Co., Ltd., trade name, polypropylene glycol, molecular weight 2000, bifunctional, hydroxyl value 56) and 10 parts by mass of Excenol 903 (Asahi Glass Co., Ltd., trade name, glycerin-based polyol, molecular weight 1500, trifunctional, hydroxyl value 109) were mixed, and 40 parts by mass of Millionate MT (Nippon Polyurethane Industry Co., Ltd., trade name, 4,4′-MDI, NCO group content: 33.6% by mass) was added. The mixture was stirred at 60 °C for 3 hours to obtain a prepolymer, which was used (NCO group content: 10.5% by mass). Hereinafter, this prepolymer may be referred to as PP2. As the polyamine compound, 155 parts by mass of Elastmer 1000P (Ihara Chemical Co., Ltd., trade name, amine value 90.6) was used. These were stirred quickly with a medicine spoon until they had a uniform appearance to obtain a polyurethane resin composition. The evaluation results are shown in Tables 1 to 3.

[0099] Comparative Example 3 As the polyisocyanate compound, the inside of a four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was made into a nitrogen atmosphere, 100 parts by mass of HDI and 0.12 parts by mass of isobutanol were charged, and the temperature inside the reactor was maintained at 80 °C for 2 hours with stirring. Then, 0.08 parts by mass of a solution in which the isocyanurate-forming reaction catalyst trimethyl-2-methyl-2-hydroxyethylammonium hydroxide was diluted to 5% by mass with isobutanol was added to carry out the isocyanurate-forming reaction. Phosphoric acid was added to stop the reaction when the conversion rate reached 20% by mass. Thereafter, the reaction solution was maintained at 160 °C for 1 hour. After the cooled reaction solution was filtered, unreacted HDI was removed using a thin-film evaporator. A polyisocyanate composition having an NCO content of 23.2% by mass, a viscosity of 470 mPa·s at 25 °C, a number-average molecular weight of 540, an average number of isocyanate groups of 3.0, and an HDI monomer mass concentration of 0.1% by mass was used. Hereinafter, this prepolymer may be referred to as PP3. As the polyamine compound, 50 parts by mass of the aspartic acid ester compound with the trade name "Amicure IC-221" (manufactured by Evonik, amine value 188 mg KOH / resin g, viscosity 450 mPa·s (representative value measured at 25°C)), and 50 parts by mass of the trade name "Amicure IC-321" (manufactured by Evonik, amine value 190 mg KOH / resin g, viscosity 450 mPa·s (representative value measured at 25°C)). As additives, 0.17 part by mass of a silicone-based surface conditioner (trade name "Tegowet 250", manufactured by Evonik), 0.84 part by mass of an acrylic-based surface conditioner (trade name "BYK-361N", manufactured by BYK), 0.84 part by mass of a polymer-based antifoaming agent (trade name "Tego Airex 944", manufactured by Evonik), and 1.67 parts by mass of a dehydrating agent (trade name "Molecular sieves 4A-Powder", manufactured by Union Showa) were pre-blended to obtain a mixture. The obtained mixture and 67 parts by mass of the polyisocyanate composition PP3 were blended so that the molar ratio of the amino group of the aspartic acid ester compound (A) to the isocyanate group of the polyisocyanate composition (B) was 10 / 11, and stirred quickly with a spatula until it became uniformly visually appealing to obtain a polyurea resin composition. The evaluation results are described in Tables 1 to 3.

[0100] Comparative Example 4 17.9 parts by mass of B1 and 11.1 parts by mass of CUA-4 (trimethylene-bis(4-aminobenzoate), manufactured by Kumiai Chemical Industry Co., Ltd.) were added to a 100 g glass beaker as polyamine compounds, heated to 60°C, stirred, and a uniform solution was obtained. 30.9 parts by mass of A1 (active hydrogen equivalent = 1.0) was added thereto as a polyisocyanate compound, stirred quickly with a spatula until it became uniformly visually appealing, and a polyurea resin composition was obtained. The results are described in Tables 1 to 3.

[0101] Comparative Example 5 A polyurea resin composition was obtained by performing the same operations as in Example 2 except that the addition amount of 231 as an additive was 6 parts by mass (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are described in Tables 1 to 3.

[0102] Comparative Example 6 As 44.7 parts by mass of A3 was used as the polyisocyanate compound and 15.3 parts by mass of B3 was used as the polyamine compound, they were stirred quickly with a medicine spoon until they became uniformly visually appealing to obtain a polyurethane resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0103] Comparative Example 7 In Example 15, the same operations were carried out except that the addition amount of 231 as an additive was changed to 6 parts by mass to obtain a polyurethane resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0104] Comparative Example 8 In Example 16, the same operations were carried out except that the addition amount of P-3 as an additive was changed to 30 parts by mass to obtain a polyurethane resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0105] Comparative Example 9 In Example 17, the same operations were carried out except that the addition amount of MS4A as an additive was changed to 30 parts by mass to obtain a polyurethane resin composition (isocyanate group amount / (hydroxy group amount + amino group amount) = 1.0). The evaluation results are shown in Tables 1 to 3.

[0106] [Table 1]

[0107] [Table 2]

[0108] [Table 3]

[0109] (Discussion) The raw materials for manufacturing the polyurea resin compositions of Examples 1 to 17 have a residual viscosity immediately after mixing (30 seconds after mixing), viscosities immediately after mixing and 30 minutes after mixing, and a kinematic viscosity coefficient immediately after mixing within the scope of the present invention, and the surface free energy when formed into a cured product (coating film) is also within the scope of the present invention. Therefore, a polyurea resin composition having a curing time suitable for manual coating, excellent sag resistance and defoaming properties of the coating film can be obtained, and furthermore, a cured product excellent in adhesion to a substrate can be formed.

[0110] The raw materials for manufacturing the polyurea resin composition of Comparative Example 1 satisfy the viscosity characteristics within the scope of the present invention and have a curing time suitable for manual coating. However, since the surface free energy when formed into a cured product (coating film) is outside the scope of the present invention, it is inferior in water resistance, chemical resistance, and adhesion to a substrate.

[0111] Since the viscosity of the raw materials for manufacturing the polyurea resin composition of Comparative Example 2 is high after 30 minutes have elapsed, its manual coating characteristics are inferior and its adhesion to a substrate is poor.

[0112] The raw materials for manufacturing the polyurea resin composition of Comparative Example 3 have a low residual viscosity and viscosity immediately after mixing, a high viscosity after 30 minutes have elapsed, and a low kinematic viscosity coefficient. Therefore, it is inferior in sag resistance, manual coating characteristics, defoaming properties, and adhesion to a substrate.

[0113] Since the residual viscosity immediately after mixing and the viscosities immediately after mixing and 30 minutes after mixing of the raw materials for manufacturing the polyurea resin composition of Comparative Example 4 are high, it is not suitable for manual coating and is inferior in sag resistance and adhesion to a substrate.

[0114] Since the viscosities immediately after mixing and 30 minutes after mixing and the kinematic viscosity coefficient immediately after mixing of the raw materials for manufacturing the polyurea resin composition of Comparative Example 5 are high, it is not suitable for manual coating and is inferior in adhesion to a substrate.

[0115] The raw materials for producing the polyurea resin composition of Comparative Example 6 hardened after 30 minutes of mixing, and the viscosity could not be measured. Further, when it was made into a cured product (coating film), the surface free energy was outside the scope of the present invention, and it was inferior in adhesion to the substrate and foam-breaking property.

[0116] The raw materials for producing the polyurea resin composition of Comparative Example 7 were unsuitable for manual coating and inferior in adhesion to the substrate because the viscosity immediately after mixing and after 30 minutes of mixing and the kinematic viscosity coefficient immediately after mixing were high.

[0117] The raw materials for producing the polyurea resin composition of Comparative Example 8 were unsuitable for manual coating because the residual viscosity immediately after mixing, the viscosity immediately after mixing and after 30 minutes of mixing, and the kinematic viscosity coefficient immediately after mixing were high. After 30 minutes of mixing, the viscosity exceeded the measurement upper limit and the viscosity could not be measured. Further, it was also inferior in adhesion to the substrate, and the coating film after the immersion test eluted unevenly and was inferior in chemical resistance.

[0118] The raw materials for producing the polyurea resin composition of Comparative Example 9 were unsuitable for manual coating because the residual viscosity immediately after mixing, the viscosity immediately after mixing and after 30 minutes of mixing, and the kinematic viscosity coefficient immediately after mixing were high. After 30 minutes of mixing, the viscosity exceeded the measurement upper limit and the viscosity could not be measured. Further, it was also inferior in adhesion to the substrate, and the coating film after the immersion test eluted unevenly and was inferior in chemical resistance.

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), and satisfying all of the following conditions (1) to (4): (1) The residual viscosity 30 seconds after mixing all of the components including component (A) and component (B) is 1,500 mPa·s or more and 20,000 mPa·s or less. (2) The viscosity 30 seconds after mixing all of the components, including component (A) and component (B), is 1,500 mPa·s or more and 30,000 mPa·s or less, and the viscosity 30 minutes after mixing is 100,000 mPa·s or less. (3) The dynamic viscosity coefficient after 30 seconds of mixing all the components including component (A) and component (B) is 1,200 m 2 / s or more 30,000m 2 / s or less. (4) The surface free energy of a cured product of the polyurea resin composition obtained from the raw materials for producing the polyurea resin composition is 30 mN / m or more and 63 mN / m or less.

2. The raw material for producing a polyurea resin composition according to claim 1, wherein the cured product has a tensile product of 150 N / mm or more.

3. The raw material for producing a polyurea resin composition according to claim 1, wherein the cured product has a weight loss rate of 10% or less after immersion in a 10% aqueous sulfuric acid solution at 50°C for 30 days.

4. The raw material for producing a polyurea resin composition according to claim 1, wherein the cured product has a weight loss rate of 10% or less after immersion in a saturated aqueous calcium hydroxide solution at 50°C for 30 days.

5. When the cured product having a thickness of 0.7 mm was laminated on concrete, the adhesion strength was 1.5 N / mm 2 The raw material for producing the polyurea resin composition according to claim 1 .

6. A polyurea resin composition obtained from the raw material for producing a polyurea resin composition according to any one of claims 1 to 5.

7. A paint comprising the polyurea resin composition according to claim 6.

8. A coating film obtained from the coating material according to claim 7.

9. A coating method for applying the paint according to claim 7, wherein the coating method is brush coating, roller coating, or trowel coating.

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