Raw materials for manufacturing polyurea resin compositions, polyurea resin compositions, paints, coating films, and coating methods.

Abstract

To provide a polyurea resin composition that exhibits high tensile strength combined with high breaking elongation, superior wear resistance, and an appropriate curing time for hand application.SOLUTION: A raw material for producing a polyurea resin composition comprises a polyisocyanate compound (A) and a polyamine compound (B), wherein the polyisocyanate compound (A) comprises a carbodiimide-modified aromatic isocyanate compound or a derivative thereof (A') and an aliphatic polyisocyanate compound or a derivative thereof (A''), and the polyamine compound (B) comprises a compound (B') represented by the following general formula (I): [(NH2)m-C6H5-m-COA-]nR (I). (In formula (I), R represents an n-valent polyalkylene, polyalkylene ether, or polyalkylene polyester having an average molecular weight of 80 or more; A represents an oxygen atom or an imino group. The polyalkylene may contain an unsaturated bond. m represents an integer of 1 to 3, and n represents an integer of 2 to 4.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to raw materials for producing polyurea resin compositions, polyurea resin compositions, paints, coating films, and coating methods. [Background technology]

[0002] Two-component curable polyurea resin compositions, consisting of polyisocyanates and a curing agent containing polyamines, cure at room temperature, and the resulting polyurea resin exhibits excellent mechanical strength. In applications such as coating in enclosed spaces or on complex shapes, where spraying equipment cannot be used, polyurea resins with a long pot life (curing time) that can be applied manually (hereinafter referred to as manual coating) are being investigated.

[0003] Patent Document 1 reports a polyurea resin composition that has a good curing time and excellent water and chemical resistance by using an aliphatic polyisocyanate compound and an amine with a specific structure. Patent Document 2 reports a technology relating to an adhesive that exhibits high tensile strength and elongation at break, making it suitable for bonding structures. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2023 / 238855 [Patent Document 2] Patent No. 7377744 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In particular, paints, protective materials, and repair materials for items exposed to the outdoor environment, such as buildings and wind turbine components, require not only high mechanical strength but also resistance to the external environment (UV resistance, acid rain resistance, and maintenance of performance under temperature changes).

[0006] The polyurea resin composition disclosed in Patent Document 1 still has room for improvement in tensile strength and elongation at break for use as a protective coating (paint film) for buildings and the like.

[0007] The urethane composition disclosed in Patent Document 2 lacks any description regarding its resistance to external environments, and therefore has room for further improvement.

[0008] The present invention has been made in view of the above circumstances, and aims to provide a polyurea resin composition that, when used as a coating film, possesses both high tensile strength and high elongation at break, has excellent resistance to external environments, and has a good curing time. [Means for solving the problem]

[0009] As a result of diligent research, the inventors discovered that by using a combination of carbodiimide-modified aromatic polyisocyanate and aliphatic isocyanate, a coating film can be obtained that improves resistance to the external environment while maintaining high tensile strength and elongation at break, thereby solving the above-mentioned problems, and thus completed the present invention. In other words, the gist of the present invention is as follows:

[0010] (1) A raw material for producing a polyurea resin composition comprising a polyisocyanate compound (A) and a polyamine compound (B), wherein the polyisocyanate compound (A) comprises a carbodiimide-modified aromatic polyisocyanate compound or a derivative thereof (A') and an aliphatic polyisocyanate compound or a derivative thereof (A''), and the polyamine compound (B) comprises a polyamine compound (B') represented by the following general formula (I). [(NH2) m -C6H 5-m -COA-] n R (I) (In formula (I), R represents a polyalkylene, polyalkylene ether, or polyalkylene polyester with an average molecular weight of 80 or more and A represents an oxygen atom or an imino group. However, the polyalkylene may contain unsaturated bonds. Also, m represents an integer from 1 to 3, and n represents an integer from 2 to 4.) (2) A raw material for producing the polyurea resin composition of (1), wherein polyisocyanate compound (A) contains 30% by mass or more of carbodiimide-modified aromatic polyisocyanate compound (A'). (3) A raw material for producing the polyurea resin composition of (1) or (2), wherein the carbodiimide-modified aromatic polyisocyanate compound (A') is a carbodiimide-modified form of diphenylmethane diisocyanate. (4) A raw material for producing any of the polyurea resin compositions (1) to (3), wherein the isocyanate group content of polyisocyanate compound (A) is 15 to 30 NCO%. (5) A raw material for producing any of (1) to (4) polyurea resin compositions, wherein the content of polyamine compound (B') per 100 parts by mass of polyamine compound (B) is 30 parts by mass or more. (6) A raw material for producing any of (1) to (5) of a polyurea resin composition, wherein the content of amine compounds other than polyamine compound (B') is 50 parts by mass or less per 100 parts by mass of polyamine compound (B). (7) A raw material for producing any of (1) to (6) of a polyurea resin composition, wherein all components including the polyisocyanate compound (A) and the polyamine compound (B) are mixed under solvent-free conditions, and the time until touch-dry is 15 minutes or more. (8) A polyurea resin composition obtained from a polyurea resin composition manufacturing raw material described in any of (1) to (7). A paint containing the polyurea resin composition of (9)(8). (10) A paint film obtained from the paint in (9). (11) The coating of (10), which, according to JIS K7161-1:2014, has a tensile strength of 15 MPa or more and a fracture elongation of 150% or more when measured using a 1 mm thick test piece at a tensile speed of 200 mm / min, and according to JIS 7204:1999, has a wear loss of 10 mg or less after 1000 rotations in a Taber abrasion test measured using a CS17 abrasion wheel under a load of 1000 g. Articles comprising a coating of (12)(10) or (11). A painting method for applying the paint of (13)(9), wherein the method for applying the paint is brush painting, roller painting, or trowel painting.

Advantages of the Invention

[0011] According to the raw materials for producing the polyurea resin composition of the present invention, it has a good curing time for manual application, has both high tensile strength and elongation at break, and provides a polyurea resin composition excellent in external environment resistance when formed into a paint film, and a paint composed of the same. In addition, according to the polyurea resin composition of the present invention, since it is also excellent in abrasion resistance, it can be suitably used, for example, as a paint for members where fine components collide at high speed, such as rotating blades in wind power generation.

Embodiments for Carrying Out the Invention

[0012] <Raw Materials for Producing Polyurea Resin Composition> The raw materials for producing the polyurea resin composition of the present invention contain a polyisocyanate compound (A) and a polyamine compound (B).

[0013] <Polyisocyanate Compound (A)> The polyisocyanate compound (A) is a compound having two or more isocyanate groups in one molecule, and its form may be any of monomer, oligomer, and polymer. Also, it may be modified with a chain extender such as a polyol component. Derivatives of the isocyanate compound in the present invention include isocyanate-terminated prepolymers obtained by reacting an isocyanate compound with a polyamine or polyol, allophanate-modified products, urea-modified products, carbodiimide-modified products, burette-modified products, uretdione-modified products, and isocyanurate-modified products, as well as those modified into a water-dispersed type.

[0014] The polyisocyanate compound (A) in the present invention needs to contain a carbodiimide-modified aromatic polyisocyanate compound or its derivative (A´). The content of the carbodiimide-modified aromatic polyisocyanate compound or its derivative (A´) can be arbitrarily adjusted according to the target physical properties, but it is more preferably contained at 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more based on the polyisocyanate compound (A). Since the polyisocyanate compound (A) contains a carbodiimide-modified aromatic polyisocyanate compound or its derivative (A´), the resulting polyurea resin composition has a touch-dry time (curing time) suitable for manual painting, and further, it can achieve both high tensile strength and elongation at break when formed into a coating film, as well as high acid rain resistance and temperature change resistance.

[0015] The isocyanate group content of the carbodiimide-modified aromatic polyisocyanate compound or its derivative (A´) is preferably 15 - 40 NCO% (mass%), more preferably 17 - 38 NCO% (mass%), and particularly preferably 20 - 35 NCO% (mass%). If the isocyanate group content exceeds 40 NCO%, the elongation at break of the resulting coating film may deteriorate, and if the isocyanate group content is less than 15 NCO%, the tensile strength of the resulting coating film may decrease.

[0016] As the carbodiimide-modified aromatic polyisocyanate compound, known ones can be used, and examples thereof include carbodiimide-modified products such as 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate.

[0017] Among these, carbodiimide-modified diphenylmethane diisocyanate (MDI) is preferred. By using carbodiimide-modified diphenylmethane diisocyanate as the carbodiimide-modified aromatic polyisocyanate compound (A'), even higher tensile strength and higher elongation at break can be achieved.

[0018] The polyisocyanate compound (A) in this invention must contain an aliphatic polyisocyanate or a derivative thereof (A''). By containing an aliphatic polyisocyanate or a derivative thereof (A'') in the polyisocyanate compound (A), the UV resistance and temperature change resistance when applied as a coating film are improved, and a better touch-dry time (curing time) can be achieved.

[0019] The content of the aliphatic polyisocyanate or its derivative (A'') can be arbitrarily adjusted according to the desired physical properties, but is preferably 1 to 70% by mass, preferably 3 to 50% by mass, and particularly preferably 5 to 40% by mass relative to the polyisocyanate compound (A). If the content is less than 1%, the effect of adding the aliphatic polyisocyanate or its derivative (A'') may not be achieved, and if the content exceeds 70% by mass, the tensile strength and elongation at break may decrease.

[0020] Examples of aliphatic polyisocyanate compounds 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-diisocyanate methyl caproate, lysine diisocyanate, trioxyethylene diisocyanate, isophorone diisocyanate. Examples include annetes, 1,4-bis(isocyanatomethyl)cyclohexane, 4,4'-methylenebis(cyclohexyl isocyanate), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatoethyl)cyclohexane, 1,4-bis(isocyanatoethyl)cyclohexane, and 2,5- or 2,6-bis(isocyanatomethyl)norbornane (NBDI).

[0021] Among these, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and 4,4'-methylenebis(cyclohexyl isocyanate) are preferred, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are more preferred, and hexamethylene diisocyanate is particularly preferred. When the polyisocyanate compound (A) contains these aliphatic isocyanates or their derivatives, the resulting coating film exhibits improved properties such as resistance to the external environment. Furthermore, derivatives of aliphatic isocyanates can be obtained by known methods.

[0022] The isocyanate group content of the aliphatic polyisocyanate or its derivative (A'') is preferably 15 to 30 NCO% (mass%), more preferably 7 to 28 NCO% (mass%), and particularly preferably 10 to 25 NCO% (mass%). If the isocyanate group content exceeds 30 NCO%, the elongation at break of the resulting coating film may deteriorate, and if the isocyanate group content is less than 5 NCO%, the tensile strength of the resulting coating film may decrease or the UV resistance may deteriorate.

[0023] In addition to carbodiimide-modified aromatic polyisocyanate compounds (A') and aliphatic polyisocyanate compounds and their derivatives (A''), polyisocyanate compound (A'') may also contain other polyisocyanate compounds (A'''') depending on the desired properties such as physical properties and curing time. Examples of other polyisocyanate compounds (A'''') include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and 1,5-naphthylene diisocyanate.

[0024] The content of other polyisocyanate compounds (A'') is not particularly limited and can be added according to the desired performance, but it is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less relative to polyisocyanate compound (A). If it exceeds 30% by mass, the resulting coating film may have poor elongation at break and abrasion resistance.

[0025] The isocyanate group content in polyisocyanate compound (A) is preferably 15 to 30 NCO% (mass%), more preferably 18 to 30 NCO% (mass%), even more preferably 20 to 30 NCO% (mass%), and particularly preferably 22 to 30 NCO% (mass%). A polyurea resin composition containing polyisocyanate compound (A) with an isocyanate group content higher than the above range may not yield a good touch-dry time, and if the isocyanate group content in polyisocyanate compound (A) is lower than the above range, the resulting coating film may have inferior tensile strength.

[0026] <Polyamine compound (B)> The polyamine compound (B) in this invention contains a polyamine compound (B') represented by the following general formula (I) (hereinafter sometimes referred to as a benzoate-type polyamine compound (B'). [(NH2) m -C6H 5-m -COA-] n R (I) (In formula (I), R represents a polyalkylene, polyalkylene ether, or polyalkylene polyester with an average molecular weight of 80 or more and A represents an oxygen atom or an imino group. However, the polyalkylene may contain unsaturated bonds. Also, m represents an integer from 1 to 3, and n represents an integer from 2 to 4.)

[0027] By containing polyamine compound (B') in polyamine compound (B), the compound (B) has a touch-dry time (curing time) suitable for hand application, and furthermore, when formed into a coating film, it can achieve high tensile strength and elongation at break, as well as resistance to external environments and abrasion resistance.

[0028] The content of polyamine compound (B') is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, relative to the total amount of polyamine compound (B). If it is less than 30% by mass, the resulting coating film may have poor elongation at break and abrasion resistance, or a good curing time may not be obtained.

[0029] Among the above benzoate polyamine compounds (B'), commercially available products with m=1, n=2, and R being a polyether include, for example, "Elasmer 1000P" (manufactured by Kumiai Chemical Industry Co., Ltd., amine value 84 gKOH / g), "Elasmer 650P" (manufactured by Kumiai Chemical Industry Co., Ltd., amine value 126 gKOH / g), "Elasmer 250P" (manufactured by Kumiai Chemical Industry Co., Ltd., amine value 221 gKOH / g), "VERSALINK P-1000" (manufactured by Air Products Japan Co., Ltd., amine value 80-90), and "Porea SL-100A" (manufactured by Kumiai Chemical Industry Co., Ltd.).

[0030] The polyamine compound (B) of the present invention may contain other polyamine compounds (B'') other than the benzoate-based polyamine compound (B'') for the purpose of adjusting the properties of the coating film and the curing time. Other amine compounds (B'') include, for example, aromatic amine compounds such as 4,4′-diamino-3,3′-dichlorodiphenylmethane, 4,4'-methylenebis(N-sec-butylaniline), N,N'-di-sec-butyl-p-phenylenediamine, and diethyltoluenediamine; polyetheramine compounds such as O,O′-bis(2-aminopropyl)propylene glycol; and aliphatic amine compounds such as hexamethylenediamine, nonanediamine, 4,4'-methylenebis(N-sec-butylcyclohexaneamine), and reaction products of epoxy compounds and primary amines. Both primary and secondary amines can be used for the other amine compounds (B'').

[0031] The content of the other amine compound (B'') is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, and particularly preferably 0 to 30 parts by mass, based on 100 parts by mass of the total amount of the benzoate-based polyamine compound (B''). If the content of the other amine compound (B'') exceeds 50 parts by mass, the polyurea resin composition may have poor elongation at break.

[0032] <Other ingredients (C)> The raw materials for producing the polyurea resin composition of the present invention may contain compounds or resins having functional groups that react with isocyanate groups other than amino groups, to the extent that they do not impair the effects of the invention. The type of liquid resin is not particularly limited, but examples include polyol compounds, epoxy compounds, polyester compounds, polyolefin compounds, polyamide compounds, polycarboxylic acid compounds, methanoacrylic compounds, vinyl ester compounds, polyurethane compounds, and resins thereof. Among these, polyol resins are preferred in order to achieve high elongation at break.

[0033] The molecular weight of the other component (C) is not particularly limited, and monomers, oligomers, or polymers can all be used.

[0034] The content of other component (C) in the raw materials for producing the polyurea resin composition of the present invention is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less, relative to the total of the polyisocyanate compound (A), polyamine compound (B), and other component (C). If the content of other component (C) exceeds 20% by mass, the polyurea resin composition may have inferior tensile strength.

[0035] In the raw materials for producing the polyurea resin composition of the present invention, the equivalent ratio (NCO / NH2) of the isocyanate group of the polyisocyanate compound (A) and the amino group of the polyamine compound (B) is preferably 0.6 to 1.5, more preferably 0.8 to 1.2, even more preferably 0.9 to 1.1, and particularly preferably 0.95 to 1.05. Furthermore, if other components (C) are included, the total amount of the amino groups of the polyamine compound (B) and the active hydrogen groups of the other component (C) is used instead of the amount of amino groups of the polyamine compound (B). If the equivalent ratio is less than 0.6 or greater than 1.5, a cured product such as a coating film may not be obtained, or the coating film properties such as tensile strength may be inferior.

[0036] The raw materials for producing the polyurea resin composition of the present invention may contain a catalyst to improve the properties of the resulting coating film or to adjust the curing time and curing temperature. Specific examples of catalysts include tertiary amines such as triethylamine, tributylamine, triethylenediamine, 2-dimethylaminoethyl ether, diazabicycloundecene, and N-methylmorpholine; metal catalysts such as dibutyltin diacetate, dibutyltin laurate, 3-diacetoxytetrabutylstanoxane, tin octenoate, tin chloride, butyl 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.

[0037] The raw materials for producing the polyurea resin composition of the present invention may contain additives as needed. Examples of additives include basic inorganic compounds, pH adjusters, metal oxide microparticles, tackifiers, waxes, UV absorbers, surface modifiers, defoamers, thixotropy agents, colorants, dispersants, fillers, and diluents. These may be used individually or in combination of two or more. They can also be pre-mixed with polyisocyanate compounds (A) or polyamine compounds (B). The amount of additive added can be determined appropriately depending on the purpose.

[0038] Examples of basic inorganic compounds include hydroxides, oxides, and carbonates (hydrogen salts) of alkali metals or alkaline earth metals, such as calcium hydroxide, sodium hydroxide, magnesium hydroxide, calcium oxide, calcium carbonate, sodium carbonate, and sodium bicarbonate. Among these, hydroxides of alkali metals or alkaline earth metals are more preferred from the viewpoint of stability and viscosity.

[0039] Examples of pH adjusters include calcium acetate, sodium acetate, potassium acetate, calcium formate, sodium formate, potassium formate, calcium propionate, sodium propionate, potassium propionate, and organic salts of alkali metals or alkaline earth metals.

[0040] Examples of metal oxide nanoparticles include titanium oxide, magnesium oxide, ferrous oxide, ferric oxide, triiron tetroxide, aluminum oxide, vanadium oxide, and copper oxide.

[0041] Examples of tackifiers include polysaccharides such as xanthan gum and guar gum, rosin resins and their derivatives, terpene resins and their derivatives, aliphatic resins and their derivatives, and aromatic resins and their derivatives.

[0042] Examples of waxes include paraffinic waxes, amide waxes, olefinic waxes, oxidized olefinic waxes, montan waxes, and copolymer waxes.

[0043] Examples of UV absorbers include hindered amines, cinnamic acid, benzophenones, triazines, and triazoles.

[0044] Examples of surface modifiers include silicone-based, acrylic polymer-based, vinyl-based, acetylene-based, fluorine-based, and alkylene oxide-based agents.

[0045] Examples of defoaming agents include mineral oil-based, amide-based, metal soap-based, silicone-based, higher alcohols and their derivatives, fatty acid derivatives, and polyolefin-based agents. Among these, polyolefin-based agents are more preferred from the viewpoint of defoaming properties and chemical resistance.

[0046] Examples of thixotropy-imparting agents include acrylic polymers, organic urea compounds and their modified forms, fumed silica, bentonite, organic clay, and layered silicates. Among these, organic urea compounds and their modified forms are more preferred from the viewpoint of their effectiveness relative to the amount added.

[0047] 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, sappanwood, and indigo.

[0048] Examples of dispersants include acrylic polymers, polycarboxylic acid compounds, phosphonic acid compounds, sulfonic acid compounds and their neutralized compounds, quaternary ammonium salt compounds, amide compounds, and polyether compounds.

[0049] 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 fibers, and silica. Among these, talc, glass beads, and silica are preferred from the viewpoint of addition amount and viscosity.

[0050] Any common organic solvent can be used as a diluent, as long as it does not react with the polyisocyanate compound (A). 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 individually or in combination of two or more.

[0051] The organic solvent content in the raw materials for manufacturing polyurea resin compositions is preferably 10% by mass or less. If the organic solvent content exceeds 10% by mass, not only may the physical properties of the resulting coating film deteriorate, but the inherent advantage of polyurea resin, which can be manufactured without solvents, may also be lost.

[0052] The raw material for producing the polyurea resin composition of the present invention is obtained by mixing all components, including a polyisocyanate compound (A) and a polyamine compound (B), under solvent-free conditions. Preferably, the viscosity at 25°C immediately after mixing (for example, after 30 seconds) is 100 to 500,000 mPa·s, more preferably 500 to 300,000 mPa·s, and particularly preferably 1,000 to 200,000 mPa·s. If the viscosity is less than 100 mPa·s, it may be difficult to obtain a coating film with sufficient thickness. If it exceeds 500,000 mPa·s, it may be difficult to remove air bubbles from the resulting resin composition, or the coating process may become difficult.

[0053] The raw materials for producing the polyurea resin composition of the present invention preferably have a touch-dry time of 15 minutes or more, more preferably 30 minutes or more, even more preferably 45 minutes or more, and particularly preferably 60 minutes or more, after mixing all components, including the polyisocyanate compound (A) and the polyamine compound (B), under solvent-free conditions. If the touch-dry time is less than 15 minutes, the coating workability may be poor.

[0054] 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 method for obtaining the polyurea resin composition of the present invention is not particularly limited as long as all components, including the polyisocyanate compound (A) and the polyamine compound (B), are mixed, and any mixing method can be used. Furthermore, the mixing conditions (mixing temperature and mixing time) are not particularly limited and can be appropriately selected depending on the physical properties of the resulting resin composition.

[0055] The paint of the present invention contains the polyurea resin composition of the present invention. Furthermore, the coating film of the present invention is formed by applying the paint of the present invention.

[0056] Since the raw materials for producing the polyurea resin composition of the present invention have a sufficient touch-dry time, known methods can be used for applying the coating. The method can be appropriately selected depending on the desired thickness and the shape of the object to be coated, but examples include dipping, wire bar, baker-type applicator, gravure roll, potting, brush coating, roller coating, or trowel coating. It is also possible to form a cured product in three dimensions using a 3D printer or the like.

[0057] The thickness of the coating film can be appropriately selected depending on the desired physical properties, the material of the article or substrate to be coated, etc. However, from the viewpoint of economy and physical properties, 10 to 10,000 μm is generally preferred, 50 to 8,000 μm is more preferred, and 100 to 5,000 μm is even more preferred. Furthermore, the above thickness can be achieved by applying the coating in a single coat or by applying multiple coats in separate layers.

[0058] The coating film of the present invention has good tensile strength, elongation at break, abrasion resistance, and resistance to external environments, and can therefore be suitably used as a protective layer for substrates or as a layer to prevent the penetration of specific substances. Specific examples include floor coatings, linings, roof waterproofing, exterior wall coatings, bridge deck waterproofing, waterproof paints, anticorrosion paints, protective coatings for steel pipes, metal pipes, the inside and outside of tanks, and wind power generation components, reinforcement and repair of buildings, protection of resin and metal parts, and reservoirs. In particular, because it also has excellent abrasion resistance, it can be suitably used as a coating for substrates and articles where fine components collide at high speed, such as the rotating blades of wind power generators.

[0059] The coating film of the present invention can also be composited with flat surfaces such as fibers (including both long and short fibers), nonwoven fabrics (including both long and short fibers), cloth, wire mesh, mesh, and perforated metal. Publicly known methods for composite formation can be used. The amount of coating applied when compounding with the above-mentioned planar body can be appropriately selected depending on the desired physical properties and the material of the base material, but usually, from the standpoint of economy and physical properties, it is 0.01 to 5 kg / m 2is preferred, 0.03 to 4 kg / m 2 is more preferred, 0.05 to 3 kg / m 2 is even more preferred.

[0060] The coating film of the present invention preferably has a tensile strength of 15 MPa or more, more preferably 20 MPa or more, and even more preferably 25 MPa or more, when measured at a tensile speed of 200 mm / min using a test piece with a thickness of 1 mm based on JIS K7161-1:2014. Further, the elongation at break is preferably 150% or more, more preferably 200% or more, even more preferably 250% or more, and particularly preferably 300% or more. If the tensile strength is less than 20 MPa or the elongation at break is less than 150%, the protective ability for the base material or article to be protected may be inferior.

[0061] The coating film of the present invention preferably has a wear loss of 10 mg or less after 1000 rotations in a Taber abrasion test measured under the condition of a load of 1000 g using a CS17 abrasion wheel based on JIS 7204:1999, more preferably 7.5 mg or less, and even more preferably 5 mg or less. If the wear loss is 10 mg or more, the protective ability for the base material or article to be protected may be inferior.

Examples

[0062] The present invention will be described more specifically by way of Examples and Comparative Examples, but the present invention is not limited to the following Examples at all. The raw materials used in the Examples and Comparative Examples are shown below. The raw materials were used as they were without purification or distillation.

[0063] <Polyisocyanate compound (A)> <Carbodiimide-modified aromatic polyisocyanate (A´)> A´1: Carbodiimide-modified MDI (manufactured by Tosoh Corporation, "Millionate MTL", 28.9% NCO, viscosity 42 mPa·s) A´2: Carbodiimide-modified TDI synthesized by the following method, 28.0% NCO, viscosity 30 mPa·s) In a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 3000 parts by mass of TDI (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate = 80 / 20 (weight ratio)) and 0.012 parts by mass of 1-phenyl-3-methyl-3-phosphorene-1-oxide were charged, and the temperature was raised to 90°C while stirring, and the carbodiimide was prepared. The carbodiimide reaction was carried out. When the isocyanate group content reached 28 NCO%, 0.36 parts by mass of β-naphthalene sulfonic acid was added, and the reactor was rapidly cooled to 45°C in ice water to stop the carbodiimide reaction.

[0064] <Aliphatic polyisocyanate compound (A'')> A''1: Nurate-modified hexamethylene diisocyanate (Tosoh Corporation's "Coronate HXR", 21.9 NCO%, viscosity 3,000 mPa·s) A''2:1,6-Hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd., 49.9 NCO%, viscosity 3 mPa·s) A''3: Water-dispersible modified hexamethylene diisocyanate (Asahi Kasei Corporation "Duranate WL72-100", 21.3 NCO%, viscosity 540 mPa·s)

[0065] A''4: Isocyanate-terminated HDI prepolymer synthesized by the following method (isocyanate group content 20.5% by mass, viscosity 2,000 mPa·s) A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was placed under a nitrogen atmosphere. 100 parts by mass of hexamethylene diisocyanate (HDI) and 21.5 parts by mass of polypropylene glycol (number average molecular weight 750) were charged into the flask, and the reactor temperature was maintained at 95°C for 90 minutes under stirring to carry out the urethane reaction. After filtering the cooled reaction solution, unreacted HDI was removed using a thin-film evaporator. An isocyanate-terminated HDI prepolymer was obtained with an isocyanate group content of 20.5% by mass, a viscosity of 3,000 mPa·s at 25°C, and a number-average molecular weight of 1520.

[0066] A'5: Biuret-modified hexamethylene diisocyanate (Asahi Kasei Corporation's "Duranate 24A-100", 23.5 NCO%, viscosity 1,800 mPa·s)

[0067] <Other polyisocyanate compounds (A'´´)> A'´´1: Polymeric MDI (Tosoh Corporation's "Millionate MR-200", 30.9 NCO%, viscosity 150 mPa·s)

[0068] <Polyamine compound (B)> <Benzoate-based polyamine compounds (B')> B'1: Polytetramethylene oxide-di-p-aminobenzoate (Elasmer 1000P, manufactured by Kumiai Chemical Co., Ltd., amine value 84 mgKOH / g, molecular weight 1238, viscosity 5,300 mPa·s) B'2: Polytetramethylene oxide-di-p-aminobenzoate (Elasmer 650P, manufactured by Kumiai Chemical Co., Ltd., amine value 126 mgKOH / g, molecular weight 888, viscosity 6,000 mPa·s) B'3: Polytetramethylene oxide-di-p-aminobenzoate (Elasmer 250P, manufactured by Kumiai Chemical Co., Ltd., amine value 221 mgKOH / g, molecular weight 488, viscosity 175,000 mPa·s)

[0069] <Other polyamine compounds (B'´)> B''1:4.4''-Methylenebis(N-sec-butylaniline) (Dorfketal "Unilink 4200", amine value 362 mgKOH / g, viscosity 324 mPa·s)

[0070] <Other ingredients (C)> C1: Glycerin propylene oxide adduct (ADEKA "G-700", hydroxyl value 224 mgKOH / g, viscosity 250 mPa·s)

[0071] The various physical properties were measured using the following evaluation method. (1) Isocyanate group content (NCO%) The result was obtained according to the back titration method of dinormalbutylamine with hydrochloride, as specified in JIS K 7301.

[0072] (2) Amine value The result was obtained according to the indicator titration method specified in JIS K 7237.

[0073] (3) Equivalent ratio of NCO / NH2 The amine value was calculated from the isocyanate group content and amine value obtained in (1) and (2) above.

[0074] (4) Viscosity Using a B-type viscometer (BROOKFIELD DIAL VISCOMETER Model LVT, manufactured by BROOKFIELD ENGINEERING LABORATORIES, INC.), all components, including the polyisocyanate compound (A) and the polyamine compound (B), were mixed, and the rotational viscosity (mPa·s) at 25°C was measured after 30 seconds.

[0075] (5) Dry to touch time (curing time) All components, including the polyisocyanate compound (A) and the polyamine compound (B), were placed in a glass container (100 mL capacity) and quickly mixed using a metal stirring rod at 25°C until uniform. The mixture was then poured into a mold, and the touch-dry time was measured. The touch-dry time was determined by lightly pressing a polyethylene film against the resin composition and stopping the transfer of resin components to the film, according to the following criteria. 5. Touch-dry time is between 2 hours and 4 hours. 4. Touch-dry time is between 90 minutes and 2 hours, or between 4 hours and 6 hours. 3. Touch-dry time is between 60 minutes and 90 minutes, or between 6 hours and 12 hours. 2: Touch-dry time is between 30 minutes and 60 minutes, or between 12 hours and 24 hours. 1: Touch-dry time is between 5 minutes and 30 minutes, or between 24 hours and 36 hours. 0: Touch-dry time is 5 minutes or less or exceeds 36 hours. In practical terms, a touch-dry time rating of "2" or higher is preferable, and "3" or higher is more preferable.

[0076] (6) Tensile strength and elongation at break All components, including the polyisocyanate compound (A) and the polyamine compound (B), were placed in a glass container (100 mL capacity) and quickly mixed using a metal stirring rod at 25°C until uniform. The mixture was then poured into a 30 cm x 30 cm metal frame and cured at 40°C for 48 hours to obtain a 1 mm thick cured material. This was punched out to form a dumbbell-shaped tensile test specimen (Type A1) as specified in JIS K7139. The tensile strength and elongation at break of this specimen were determined using a Shimadzu constant-temperature chamber tensile testing apparatus at 23°C, a test speed of 200 mm / min, and a chuck distance of 70 mm. The evaluation was performed according to the following criteria. (Tensile strength) 5:25MPa or more 4: 20 MPa or higher, less than 25 MPa 3: 15 MPa or higher, less than 20 MPa 2: 10 MPa or higher, less than 15 MPa 1: Less than 10 MPa (Elongation at break) 5: 250% or more 4: 200% or more, less than 250% 3: 150% or more, less than 200% 2: 100% or more, less than 150% 1: Less than 100% In practical terms, a rating of "2" or higher is preferable for tensile strength and elongation at break, and "3" or higher is more preferable.

[0077] (7) Abrasion resistance All components, including the polyisocyanate compound (A) and the polyamine compound (B), were placed in a glass container (100 mL capacity) and quickly mixed using a metal stirring rod at 25°C until uniform. The mixture was then poured into a 30 cm x 30 cm metal frame and cured at 40°C for 48 hours to obtain a 1 mm thick cured material. This was cut into 10 cm x 10 cm pieces to form test specimens (mass of test specimen: 10 g). These test specimens were subjected to a Taber abrasion test using a Taber abrasion tester manufactured by Toyo Seiki Co., Ltd., in accordance with JIS 72040:1999. A CS17 abrasion wheel was used, with a load of 1000 g and 1000 rotations. The mass was measured before and after the test, and the difference in mass before and after the test was defined as wear loss. The evaluation was performed according to the following criteria. 5: Wear loss of 2.5 mg or less 4: Wear loss exceeds 2.5 mg and is 5.0 mg or less. 3: Weight loss due to wear exceeds 5.0 mg and is 7.5 mg or less. 2: Weight loss due to wear exceeds 7.5 mg and is 10.0 mg or less. 1: Weight loss due to wear exceeds 10.0 mg and is 12.5 mg or less. 0: Wear loss exceeds 12.5 mg In practical terms, a wear resistance rating of "2" or higher is preferable, and "3" or higher is more preferable.

[0078] (8) Acid rain resistance All components, including the polyisocyanate compound (A) and the polyamine compound (B), were placed in a glass container (100 mL capacity) and quickly mixed using a metal stirring rod at 25°C until uniform. The mixture was then poured into a 30 cm x 30 cm metal frame and cured at 40°C for 48 hours to obtain a 1 mm thick cured material. This was punched out to form a dumbbell-shaped tensile test specimen (Type A1) as specified in JIS K7139. This specimen was immersed in a 5% sulfuric acid aqueous solution at 60°C for 120 days. After immersion, the specimen was washed with water and dried at 25°C for 24 hours. Tensile strength and elongation at break were determined under the same conditions as in (6). Ten test points were used, and the average value was adopted. Based on the results, acid rain resistance was evaluated according to the following criteria. 5. The larger of the absolute values ​​of the rate of change between tensile strength and elongation at break must be 1% or less. 4. Of the absolute values ​​of the rate of change between tensile strength and elongation at break, the larger one must be greater than 1% and less than or equal to 5%. 3. Of the absolute values ​​of the rate of change between tensile strength and elongation at break, the larger one must be greater than 5% and less than or equal to 15%. 2: Of the absolute values ​​of the rate of change between tensile strength and elongation at break, the larger one must be greater than 15% and less than or equal to 30%. 1: Of the absolute values ​​of the rate of change between tensile strength and elongation at break, the larger one is greater than 30% and less than or equal to 50%. 0: The larger of the absolute values ​​of the rate of change between tensile strength and elongation at break exceeds 50%, or the test specimen has dissolved. In practical terms, a rating of "2" or higher is preferable, and a rating of "3" or higher is even preferable.

[0079] (9) UV resistance All components, including the polyisocyanate compound (A) and the polyamine compound (B), were placed in a glass container (100 mL capacity) and quickly mixed using a metal stirring rod at 25°C until uniform. The mixture was then poured into a 30 cm x 30 cm metal frame and cured at 40°C for 48 hours to obtain a 1 mm thick cured material. This was cut into 75 mm x 150 mm sections and subjected to an accelerated weathering test as described in JIS K 5600-7-8 using a QUV accelerated weathering tester manufactured by Q-Lab Corporation. A UVA (340) lamp was used, with an illuminance of 0.89 W / m². 2 The black panel temperature was maintained at 60°C (during irradiation) for 4 hours, then at 50°C (during water spraying) for 4 hours. This was considered one cycle and repeated 125 times. The test specimens were washed with water and dried at 25°C for 24 hours. Then, the tensile strength and elongation at break were measured, the percentage change before and after the test was determined, and evaluated according to the following criteria. 5. The larger of the absolute values ​​of the rate of change between tensile strength and elongation at break must be 10% or less. 4. Of the absolute values ​​of the rate of change between tensile strength and elongation at break, the larger one must be greater than 10% and less than or equal to 20%. 3. Of the absolute values ​​of the rate of change between tensile strength and elongation at break, the larger one must be greater than 20% and less than or equal to 30%. 2: Of the absolute values ​​of the rate of change between tensile strength and elongation at break, the larger one is greater than 30% and less than or equal to 50%. 1: Of the absolute values ​​of the rate of change between tensile strength and elongation at break, the larger one is greater than 50% and less than or equal to 100%. 0: The larger of the absolute values ​​of the rate of change between tensile strength and elongation at break exceeds 100%, or a crack occurred in the test specimen and evaluation was not possible. In practical terms, a rating of "2" or higher is necessary, and a rating of "3" or higher is even more preferable.

[0080] (10) Temperature change tolerance The same procedure as in (6) was followed, except that the measurement temperatures were set to -10°C and 40°C, and the tensile strength and elongation at break were measured. The results were then evaluated according to the following criteria. 5: Using 25°C as the baseline, the larger of the absolute values ​​of the percentage change in tensile strength and elongation at break at -10°C and 40°C must be 20% or less. 4. Using 25°C as the baseline, the greater of the absolute values ​​of the percentage change in tensile strength and elongation at break at -10°C and 40°C must be greater than 20% and less than or equal to 40%. 3. Using 25°C as the baseline, the greater of the absolute values ​​of the percentage change in tensile strength and elongation at break at -10°C and 40°C must be greater than 40% and less than or equal to 80%. 2. Using 25°C as the baseline, the greater of the absolute values ​​of the percentage change in tensile strength and elongation at break at -10°C and 40°C must be greater than 80% and less than or equal to 140%. 1: Using 25°C as a baseline, the greater of the absolute values ​​of the percentage change in tensile strength and elongation at break at -10°C and 40°C must be greater than or equal to 140% and less than or equal to 200%. Using 0:25℃ as a baseline, if the larger of the absolute values ​​of the rate of change between tensile strength and elongation at break at -10℃ and 40℃ exceeds 200%, or if the test specimen melts or cracks, In practical terms, a rating of "2" or higher is preferable, and a rating of "3" or higher is even preferable.

[0081] Example 1 14.8 g of polyisocyanate compound (A'1) (0.102 mol of isocyanate groups), 3.7 g of polyisocyanate compound (A''1) (0.019 mol of isocyanate groups), and 81.5 g of polyamine compound (B'1) (0.121 mol of amino groups) were mixed at 25°C using a metal stirring rod until a uniform appearance was obtained to obtain a polyurea resin composition (mol ratio (isocyanate groups / amino groups) = 1.0 / 1.0). Subsequently, the composition was evaluated using the evaluation methods described in (1) to (10) above.

[0082] Examples 2-15 (Example 4 、12~14 (These are for reference only), Comparative Examples 1-8 A polyurea resin composition was obtained in the same manner as in Example 1, except that (A'), (A''), (A'''')(B'), (B''''), and (C) listed in Table 1 were used. Subsequently, it was evaluated using the evaluation methods described in (1) to (10) above.

[0083] Table 1 shows the composition of the polyurea resin compositions in the examples and comparative examples, and Table 2 shows the properties of the obtained polyurea resin compositions.

[0084] [Table 1]

[0085] [Table 2]

[0086] As shown in Tables 1 and 2, the polyurea resin compositions of the present invention obtained in the examples exhibited high tensile strength and elongation at break when formed into a coating film, had a curing time suitable for manual application, and also demonstrated excellent resistance to external environments and abrasion resistance.

[0087] Comparative Examples 1 and 2, which did not contain aliphatic polyisocyanate (A'') in the polyisocyanate compound, had a fast curing time and were unsuitable for manual application. Furthermore, they exhibited poor UV resistance when applied as a coating film.

[0088] In Comparative Example 3, where the polyisocyanate compound did not contain the carbodiimide-modified aromatic polyisocyanate compound (A'), the curing time was slow, and the resulting coating film exhibited inferior tensile strength and elongation at break. Furthermore, it also showed inferior resistance to acid rain and temperature changes.

[0089] In Comparative Example 4, where the polyisocyanate compound did not contain the carbodiimide-modified aromatic polyisocyanate compound (A'), curing was extremely rapid, making it impossible to prepare test specimens necessary for performance evaluation.

[0090] Comparative Example 5, which did not contain polyamine compound (B'), exhibited a faster curing time and inferior tensile strength and elongation at break. Furthermore, it also had inferior abrasion resistance.

[0091] Comparative Example 6, which did not contain a polyamine compound, and Comparative Example 7, which did not contain a polyisocyanate compound, did not undergo curing and therefore could not be evaluated.

[0092] In Comparative Example 8, where a polyol compound was used instead of a polyamine compound, the curing time was slower and the tensile strength was inferior. Furthermore, it also exhibited inferior resistance to acid rain and temperature changes.

Claims

1. A raw material for producing a polyurea resin composition containing a polyisocyanate compound (A) and a polyamine compound (B), The polyisocyanate compound (A) contains a carbodiimide-modified aromatic polyisocyanate compound or a derivative thereof (A') and an aliphatic polyisocyanate compound or a derivative thereof (A''), wherein the content of (A') is 60 to 80% by mass of the total amount of the polyisocyanate compound (A), and the content of (A'') is 20% by mass or more of the total amount of the polyisocyanate compound (A). A raw material for producing a polyurea resin composition, wherein the polyamine compound (B) contains only the polyamine compound (B') represented by the following general formula (I). [(NH ２ ) ｍ -C ６ H ５－ｍ -COA-] ｎ R (I) (In formula (I), R represents a polyalkylene, polyalkylene ether, or polyalkylene polyester with an average molecular weight of 80 or more and A represents an oxygen atom or an imino group. However, the polyalkylene may contain unsaturated bonds. Also, m represents an integer from 1 to 3, and n represents an integer from 2 to 4.)

2. The raw material for producing a polyurea resin composition according to Claim 1, wherein the polyamine compound (B') is polytetramethylene oxide-di-p-aminobenzoate.

3. The raw material for producing a polyurea resin composition according to claim 1, wherein the carbodiimide-modified aromatic polyisocyanate compound (A') is a carbodiimide-modified form of diphenylmethane diisocyanate.

4. The raw material for producing a polyurea resin composition according to claim 1, wherein the isocyanate group content of the polyisocyanate compound (A) is 15 to 30 NCO%.

5. The raw material for producing a polyurea resin composition according to claim 1, wherein all components, including a polyisocyanate compound (A) and a polyamine compound (B), are mixed under solvent-free conditions, and the time until touch-dry is 15 minutes or more.

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

7. A paint containing the polyurea resin composition described in claim 6.

8. A coating film obtained from the paint described in claim 7.

9. The coating according to claim 8, wherein, based on JIS K7161-1:2014, the tensile strength measured at a tensile speed of 200 mm / min using a 1 mm thick test piece is 15 MPa or more, and the elongation at break is 150% or more, and based on JIS 7204:1999, the wear loss after 1000 rotations in a Taber abrasion test measured under a load of 1000 g using a CS17 abrasion wheel is 10 mg or less.

10. An article comprising the coating film described in claim 8.

11. A painting method for applying the paint described in claim 7, wherein the method of applying the paint is by brush application, roller application, or trowel application.

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