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

Abstract

To provide a polyurea resin composition that exhibits high tensile strength combined with high breaking elongation, excels in long-term outdoor durability, and ensures suppressed thickening and improved resin dispersibility upon mixing a polyisocyanate compound and a polyamine compound.SOLUTION: A raw material for producing a polyurea resin composition comprises a polyisocyanate compound (A) and a polyamine compound (B), wherein (A) comprises a carbodiimide-modified aromatic polyisocyanate compound or a derivative thereof, and (B) is a compound represented by the following formula. (R1 is a polyalkylene ether group having alkylene ether groups having 1 to 20 carbon atoms as constitutional units and having an average molecular weight of 100 to 3000.)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, a paint, and a coating film. [Background technology]

[0002] Two-component curing polyurea resin compositions, which consist of two components: a polyisocyanate and a curing agent containing a polyamine, are known to cure at room temperature, and the cured polyurea resins produced thereby have excellent mechanical strength. Among these, polyalkylene ether polyamines are used as raw materials for polyurethane resins or polyurethane urea resins and structural adhesives because they exhibit good physical properties while maintaining low-temperature mixability and room-temperature curability in reactions with isocyanate compounds (e.g., Patent Document 1 and Patent Document 2). Furthermore, Patent Document 3 discloses a coating material made of a polyurea resin using a polyalkylene ether polyamine, which contains an aliphatic isocyanate as a main component. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-138811 [Patent Document 2] Japanese Patent Application Publication No. 06-271640 [Patent Document 3] Patent No. 7445354 Summary of the Invention [Problem to be solved by the invention]

[0004] The above Patent Documents 1 and 2 do not mention use as a paint or describe specific paint design, and the properties required for use as a coating, such as tensile strength and elongation at break, are insufficient. In addition, Patent Document 1 states that further improvement in durability is required for paints that are exposed to sunlight, wind, and rain outdoors for long periods of time. Furthermore, Patent Document 2 may cause problems with coating properties, such as significant thickening and heat generation. In Patent Document 3, depending on the environment (for example, outdoor use) and application when used as a paint, further improvement in mechanical strength is required.

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a manufacturing raw material for obtaining a polyurea resin composition that, when formed into a coating film, has both high tensile strength and high elongation at break, is excellent in long-term durability in outdoor use, and is improved in terms of thickening and heat generation when a polyisocyanate compound and a polyamine compound are mixed. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by using a carbodiimide-modified aromatic polyisocyanate and a polyalkylene ether polyamine having a specific structure, and have completed the present invention. That is, the gist of the present invention is as follows.

[0007] (1) A raw material for producing a polyurea resin composition containing a polyisocyanate compound (A) and a polyamine compound (B), A raw material for producing a polyurea resin composition, wherein the polyisocyanate compound (A) contains a carbodiimide-modified aromatic polyisocyanate compound or a derivative thereof, but does not contain a prepolymer consisting of a polyisocyanate component and a diol component, and the polyamine compound (B) is a compound represented by the following general formula: [ka] (wherein R1 is a polyalkylene ether group having an alkylene ether group of 1 to 20 carbon atoms as a constituent unit, the polyalkylene ether group has an average molecular weight of 100 to 3000, and two identical atomic groups are bonded to one carbon atom in all carbon atoms in the alkylene ether group). (2) A raw material for producing a polyurea resin composition according to (2), comprising: a polyamine compound (B1) in which the average molecular weight of the polyalkylene ether group is 100 to 500; and a polyamine compound (B2) in which the average molecular weight of the polyalkylene ether group is more than 500 and not more than 3,000. (3) A raw material for producing a polyurea resin composition according to (1) or (2), further comprising a polyol compound (C). (4) A polyurea resin composition obtained from the raw material for producing the polyurea resin composition according to any one of (1) to (3). (5) A paint containing the polyurea resin composition of (4). (6) A coating film made from the paint of (5). [Effects of the Invention]

[0008] According to the raw material for producing a polyurea resin composition of the present invention, it is possible to provide a polyurea resin composition that has both high tensile strength and high elongation at break, is excellent in outdoor durability, and is improved in terms of thickening and heat generation that occurs when a polyisocyanate compound and a polyamine compound are mixed. DETAILED DESCRIPTION OF THE INVENTION

[0009] <Raw materials for producing polyurea resin compositions> The raw material for producing the polyurea resin composition of the present invention contains a polyisocyanate compound (A) and a polyamine compound (B).

[0010] <Polyisocyanate compound (A)> The polyisocyanate compound (A) refers to a compound having two or more isocyanate groups in one molecule, and the polyisocyanate compound (A) in the present invention must contain a carbodiimide-modified aromatic polyisocyanate compound or its derivative (A').

[0011] The derivative is a general term for compounds obtained by modifying the terminal isocyanate group, and examples thereof include allophanate-modified compounds, urea-modified compounds, biuret-modified compounds, uretdione-modified compounds, adduct compounds, and isocyanurate-modified compounds. In the present invention, isocyanate-terminated prepolymers obtained by reaction with diols (including oligomers and polymers) are not included, since resistance to outdoor use is reduced.

[0012] The content of the carbodiimide-modified aromatic polyisocyanate compound or its derivative (A') can be adjusted as desired depending on the desired physical properties, but is preferably 51 mass % or more, even more preferably 80 mass % or more, and particularly preferably 90 mass % or more, relative to the polyisocyanate compound (A). By using the carbodiimide-modified aromatic polyisocyanate compound or its derivative (A') as the main component, the polyisocyanate compound (A) can achieve high elongation at break and tensile strength when formed into a coating film.

[0013] The isocyanate group content of the carbodiimide-modified aromatic polyisocyanate compound or its derivative (A') is preferably 10 to 40 NCO% (mass%), more preferably 15 to 37 NCO%, and particularly preferably 20 to 35 NCO%. If the isocyanate group content exceeds 40 NCO%, the breaking elongation of the resulting coating film may deteriorate, or significant viscosity increase or self-heating may occur when mixing raw materials during production of the polyurea resin composition. If the isocyanate group content is less than 15 NCO%, the tensile strength of the resulting coating film may decrease.

[0014] Known carbodiimide-modified aromatic polyisocyanate compounds can be used, and examples thereof include carbodiimide-modified compounds such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, and 1,4-phenylene diisocyanate.

[0015] Among these, a carbodiimide-modified product of diphenylmethane diisocyanate is preferred. By using a carbodiimide-modified product of diphenylmethane diisocyanate as the carbodiimide-modified aromatic polyisocyanate compound (A'), it is possible to realize even higher tensile strength and higher elongation at break.

[0016] The polyisocyanate compound (A) in the present invention may contain other polyisocyanate compounds. The content can be adjusted as desired depending on the desired physical properties, but is preferably 49% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass, relative to the polyisocyanate compound (A). If the content exceeds 49%, the tensile strength and elongation at break may decrease.

[0017] Other polyisocyanate compounds include, for example, 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, 1,4-bis(isocyanatomethyl)cyclohexane, 4,4' Examples of suitable isocyanates include methylenebis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatoethyl)cyclohexane, 1,4-bis(isocyanatoethyl)cyclohexane, and 2,5- or 2,6-bis(isocyanatomethyl)norbornane (NBDI). Derivatives of these can also be used, but isocyanate-terminated prepolymers obtained by reaction with diols (including oligomers and polymers) are not used.

[0018] The isocyanate group content of the other polyisocyanate compound is preferably 10 to 40 NCO%, more preferably 12.5 to 37.5 NCO%, and particularly preferably 15 to 235 NCO%. If the isocyanate group content exceeds 40 NCO%, the breaking elongation of the resulting coating film may deteriorate, or significant viscosity increase or self-heating may occur when mixing raw materials during production of the polyurea resin composition, while if the isocyanate group content is below 10 NCO%, the tensile strength of the resulting coating film may decrease, or outdoor resistance may deteriorate.

[0019] <Polyamine compound (B)> The polyamine compound (B) in the present invention contains a polyamine compound represented by the following general formula (1). [ka] (wherein R1 is a polyalkylene ether group having an alkylene ether group of 1 to 20 carbon atoms as a constituent unit, the average molecular weight is 100 to 3000, and among all the carbon atoms in the alkylene ether group, one carbon atom has two identical atomic groups bonded thereto.) This polyamine compound is sometimes called a polyalkylene ether polyamine or a benzoate amine, and will hereinafter be referred to as a "polyalkylene ether polyamine."

[0020] In the present invention, R1 is an alkylene ether group having 1 to 20 carbon atoms, preferably 1 to 17 carbon atoms, even more preferably 2 to 15 carbon atoms, and particularly preferably 3 to 10 carbon atoms from the viewpoint of mechanical strength. If the number of carbon atoms exceeds 20, the tensile strength of the resulting coating film may decrease.

[0021] In the present invention, among all the carbon atoms in the alkylene ether group, one carbon atom is bonded to two identical atomic groups, which prevents significant thickening or self-heating when the raw materials are mixed, improving the coatability of the resulting coating material.

[0022] Furthermore, an atomic group other than hydrogen may be bonded to the side chain of the alkylene ether group. Examples of atomic groups other than hydrogen include halogens such as fluorine, chlorine, bromine and iodine, and silicon-containing substituents such as trimethylsilyl and trimethoxysilyl groups. In this case, too, two identical atomic groups must be bonded to one carbon atom of the alkylene ether group.

[0023] The content of polyalkylene ether polyamine in the polyamine compound (B) is more preferably 50% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. If it is less than 50% by mass, the resulting coating film may have poor elongation at break or may not have a satisfactory curing time.

[0024] The polyamine compound (B) in the present invention may contain two or more polyalkylene ether polyamines having different molecular weights. By containing two or more polyalkylene ether polyamines having different molecular weights, the resulting coating film tends to have improved elongation at break and a better curing time as a coating material. In this case, it is preferable to contain, for example, a polyamine compound (B1) in which the average molecular weight of the polyalkylene ether group is 100 to 500, and a polyamine compound (B2) in which the average molecular weight of the polyalkylene ether group is more than 500 and 3000 or less.

[0025] The polyalkylene ether polyamine of the present invention can be produced by a known method, for example, a method for producing a polyalkylene ether aminobenzoate by reducing a nitrobenzoate compound of a polyalkylene ether glycol obtained by a reaction in the presence of an acid scavenger.

[0026] Among polyalkylene ether polyamines, examples of commercially available products in which R is butyl ether include "Elasmer 1000P" (manufactured by Kumiai Chemical Industry Co., Ltd., amine value 80 to 90 mgKOH / g).

[0027] The polyamine compound (B) of the present invention may contain polyamine compounds other than polyalkylene ether polyamines for the purpose of adjusting the coating film properties and curing time. Examples include 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; aliphatic amine compounds such as hexamethylenediamine, nonanediamine, 4,4'-methylenebis(N-sec-butylcyclohexanamine), and reaction products of epoxy compounds and primary amines; and aspartic acid ester compounds. Both primary and secondary amines can be used.

[0028] The content of the other amine compound is preferably 50% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass, relative to the polyamine compound (B). If the content of the other amine compound exceeds 50% by mass, the polyurea resin composition may produce a coating film with poor elongation at break, or may undergo significant viscosity increase or self-heating when mixed with a polyisocyanate compound.

[0029] <Polyol compound (C)> The raw material for producing the polyurea resin composition of the present invention may contain a polyol compound. The type of polyol is not particularly limited, and various polyols can be used depending on the desired physical properties. Examples of polyol compounds include polyether polyols, polyester polyols, carbonate diols, hydroxyl-terminated polyolefins, and acrylic polyols.

[0030] The molecular weight of the polyol compound (C) is not particularly limited, and any of a monomer, oligomer, and polymer can be used.

[0031] The content of the polyol compound (C) in the raw material for producing the polyurea resin composition of the present invention is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less, based on the total of the polyisocyanate compound (A), the polyamine compound (B), and the polyol compound (C). If the content of the polyol compound (C) exceeds 50% by mass, the polyurea resin composition may be inferior in tensile strength and outdoor durability.

[0032] In the raw materials for producing the polyurea resin composition of the present invention, the equivalent ratio (NCO / NH2) of the isocyanate groups of the polyisocyanate compound (A) to the amino groups 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, when a polyol compound (C) is contained, the total amount of the amino groups of the polyamine compound (B) and the active hydrogen groups of the polyamine compound (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 more than 1.5, a cured product may not be obtained or the coating film may have poor physical properties, such as tensile strength.

[0033] The raw materials for producing the polyurea resin composition of the present invention may contain a catalyst in order to improve the physical properties of the resulting coating film or to adjust the curing time or temperature. Specific 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, tin 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.

[0034] 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 fine particles, tackifiers, waxes, UV absorbers, surface conditioners, antifoaming agents, thixotropy-imparting agents, colorants, dispersants, fillers, and diluents. These may be used alone or in combination of two or more. They may also be mixed in advance with the polyisocyanate compound (A) and the polyamine compound (B). The amount of the additive to be added can be determined appropriately depending on the purpose.

[0035] Examples of basic inorganic compounds include hydroxides, oxides, and (hydrogen)carbonates of alkali metals or alkaline earth metals, such as calcium hydroxide, sodium hydroxide, magnesium hydroxide, calcium oxide, calcium carbonate, sodium carbonate, and sodium hydrogencarbonate. Among these, hydroxides of alkali metals or alkaline earth metals are more preferred from the viewpoint of their influence on stability and viscosity.

[0036] Examples of pH adjusters include organic acid salts of alkali metals or alkaline earth metals, such as calcium acetate, sodium acetate, potassium acetate, calcium formate, sodium formate, potassium formate, calcium propionate, sodium propionate, and potassium propionate.

[0037] Examples of metal oxide fine particles include titanium oxide, magnesium oxide, ferrous oxide, ferric oxide, triiron tetroxide, aluminum oxide, vanadium oxide, and copper oxide.

[0038] Examples of tackifiers include polysaccharides such as xanthan gum and guar gum, rosin resins and derivatives thereof, terpene resins and derivatives thereof, aliphatic resins and derivatives thereof, and aromatic resins and derivatives thereof.

[0039] Examples of waxes include paraffin wax, amide wax, olefin wax, olefin oxide wax, montan wax, and copolymer wax.

[0040] Examples of ultraviolet absorbers include hindered amine-based, cinnamic acid-based, benzophenone-based, triazine-based, and triazole-based ones.

[0041] Examples of the surface conditioner include silicone-based, acrylic polymer-based, vinyl-based, acetylene-based, fluorine-based, and alkylene oxide-based agents.

[0042] Examples of antifoaming agents include mineral oil-based, amide-based, metal soap-based, silicone-based, higher alcohols and derivatives thereof, fatty acid derivatives, polyolefin-based, etc. Among these, polyolefin-based agents are more preferred from the viewpoints of antifoaming properties and chemical resistance.

[0043] Examples of the thixotropy-imparting agent include acrylic polymers, organic urea compounds and modified compounds thereof, fumed silica, bentonite, organic clay, layered silicates, etc. Among these, from the viewpoint of the effect relative to the amount added, organic urea compounds and modified compounds thereof are more preferred.

[0044] Any of inorganic pigments, organic pigments, and dyes can be used as colorants. Examples of inorganic pigments include red clay, yellow clay, green clay, graphite, Prussian blue, zinc oxide, cobalt blue, viridian, and titanium white. Examples of organic pigments include alkali blue, lysol red, disazo yellow, phthalocyanine blue, quinacridone red, and isoindoline yellow. Examples of dyes include madder, sappan, and indigo.

[0045] Examples of dispersants include acrylic polymers, polycarboxylic acid compounds, phosphonic acid compounds, sulfonic acid compounds and neutralized compounds thereof, quaternary ammonium salt compounds, amide compounds, and polyether compounds.

[0046] Examples of fillers include inorganic compounds such as calcium carbonate and calcium hydroxide, inorganic minerals such as talc, kaolin, apatite and layered silicates, glass beads, glass fiber, silica, etc. Among these, talc, glass beads and silica are preferred from the viewpoints of the amount added and viscosity.

[0047] As the diluent, any common organic solvent can be used as long as it is not reactive with the polyisocyanate compound (A). Examples of organic solvents that can be used as the diluent include hydrocarbon compounds such as toluene, xylene, and cyclohexane, carbonyl compounds such as acetone, 2-butanone, and isophorone, and ester compounds such as ethyl acetate and butyl acetate. These may be used alone or in combination of two or more.

[0048] The content of the organic solvent in the raw materials for producing the polyurea resin composition is preferably 10% by mass or less. If the content of the organic solvent exceeds 10% by mass, not only may the physical properties of the resulting coating film be reduced, but also the inherent advantage of the polyurea resin, that is, the ability to be produced without a solvent, may be lost.

[0049] The raw material for producing the polyurea resin composition of the present invention is preferably tack-dry in 5 to 240 minutes, more preferably 10 to 180 minutes, even more preferably 15 to 120 minutes, and particularly preferably 20 to 90 minutes, after mixing all components including the polyisocyanate compound (A) and the polyamine compound (B) under solvent-free conditions. If the tack-dry time is shorter than 5 minutes, coating workability may be poor, and if it exceeds 240 minutes, the paint may sag or be less economical.

[0050] 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, and any mixing method can be used, as long as it involves mixing all components including the polyisocyanate compound (A) and the polyamine compound (B). 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.

[0051] The coating material of the present invention contains the polyurea resin composition of the present invention. The coating film of the present invention is formed by applying the coating material of the present invention.

[0052] Because the raw materials for producing the polyurea resin composition of the present invention have a sufficient dry-to-touch time, known methods can be used to apply the coating. The coating method can be selected appropriately depending on the desired thickness and the shape of the substrate, but examples include immersion coating (dipping, dipping coating), wire bar coating, Baker-type applicator coating, gravure roll coating, potting, brush coating, roller coating, and trowel coating. It is also possible to form a three-dimensional cured product using a 3D printer or the like.

[0053] The thickness of the coating film can be appropriately selected depending on the desired physical properties and the material of the substrate, but from the viewpoints of economy and physical properties, it is usually preferably 10 to 10,000 μm, more preferably 50 to 8,000 μm, and even more preferably 100 to 5,000 μm. The thickness can be obtained by applying the coating in one go or by applying the coating in multiple steps.

[0054] The coating film of the present invention has good tensile strength, elongation at break, and outdoor durability, and therefore can be suitably used as a layer for protecting substrates or preventing the penetration of specific substances, etc. Specific examples include coated floors, linings, rooftop waterproofing, exterior wall painting, bridge deck waterproofing, waterproof paints, anticorrosion paints, protective paints for steel pipes, metal pipes, the inside and outside of tanks, and wind power generation components, reinforcement and repair of buildings, protection of plastic and metal parts, and reservoirs.

[0055] The coating film of the present invention can also be combined with flat bodies such as fibers (including both long and short fibers), nonwoven fabrics (including both long and short fibers), cloth, wire netting, mesh, punched metal, etc. Known methods for combining can be used.

[0056] The amount of coating when compounding with the above-mentioned planar body can be appropriately selected depending on the desired physical properties and the material of the substrate, but is usually 0.01 to 5 kg / m from the viewpoints of economy and physical properties. 2 is preferable, and 0.03 to 4 kg / m 2 More preferably, 0.05 to 3 kg / m 2 is more preferable. [Example]

[0057] The present invention will be explained in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples in any way. The raw materials used in the examples and comparative examples are listed below. The raw materials were used as they were without purification or distillation.

[0058] <Polyisocyanate compound (A)> A-1: Carbodiimide-modified MDI (Tosoh Corporation's "Millionate MTL", 28.9 NCO%, viscosity 42 mPa·s)

[0059] A-2: Carbodiimide-modified TDI synthesized by the following method, 28.0 NCO%, viscosity 30 mPa s) A four-neck flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube was charged with 3,000 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-phospholene-1-oxide, and the temperature was raised to 90°C with stirring to carry out a carbodiimidization reaction. When the isocyanate group content reached 28 NCO%, 0.36 parts by mass of β-naphthalenesulfonic acid was added, and the reactor was rapidly cooled to 45°C with ice water to terminate the carbodiimidization reaction.

[0060] A-3: Prepolymer of carbodiimide-modified MDI and diol, synthesized by the following method, 7.5% NCO, viscosity 2500 mPa·s 34 g of P-2000 (manufactured by ADEKA Corporation, polyether polyol, bifunctional, hydroxyl value 56) was weighed into a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, and dehydrated at 100°C and 6.7 kPa. After confirming that the moisture content was 500 ppm or less, 66 g of Millionate MLT was added, the system was replaced with a nitrogen atmosphere, and the reaction was carried out at 80°C for 2 hours.

[0061] A-4: Nurate-modified hexamethylene diisocyanate (Tosoh Corporation's "Coronate HXR," 21.9 NCO%, viscosity 3,000 mPa·s)

[0062] <Polyamine compound (B)> Synthesis Example 1 A 5-liter four-neck flask equipped with a thermometer, dropping funnel, condenser, and stirrer was charged with 422.3 g (0.430 mol) of polytetramethylene glycol having a molecular weight of 982, 175.6 g (0.946 mol) of p-nitrobenzoyl chloride, and 2 L of toluene. 100.6 g (0.994 mol) of triethylamine was added dropwise to the solution while stirring at room temperature, and the reaction was carried out under toluene reflux for 5 hours. After the reaction was completed, the reaction solution was cooled to near room temperature, and the triethylamine hydrochloride in the reaction solution was filtered. The resulting filtrate was washed with aqueous sodium hydroxide and aqueous hydrochloric acid to remove by-products, and the toluene layer was distilled under reduced pressure to obtain 490 g (93% yield) of a dinitro polytetramethylene glycol compound as a pale yellow liquid. Next, 470 g of this dinitro compound was placed in a 2-liter four-neck flask equipped with a thermometer, dropping funnel, condenser, and stirrer. 1.2 liters of ethanol and 3.5 g of Pt / Pd / C (Platinum, Palladium, Carbon Catalyst, 50% wet product, manufactured by Nippon Engelhard Co., Ltd.) were then added. With stirring at room temperature, 57.7 g (1.15 mol) of hydrazine hydrate was added dropwise from the dropping funnel over 40 minutes. This condition was maintained and the reaction was carried out under reflux with ethanol for 5 hours. After the reaction was completed, the reaction solution was filtered, and the ethanol in the filtrate was completely removed under atmospheric and reduced pressure distillation to obtain polytetramethylene oxide-di-p-aminobenzoate, a pale yellow, transparent, low-viscosity liquid. Hereafter, this product will be referred to as B-1.

[0063] Synthesis Example 2 Polyneopentyloxide-di-p-aminobenzoate was obtained by the same procedure as in Synthesis Example 1, except that 68.8 g (0.430 mol) of polytetramethylene glycol having a molecular weight of 160 was used. Hereinafter, this product will be referred to as B-2.

[0064] Synthesis Example 3 Polyneopentyl oxide-di-p-aminobenzoate was obtained by the same procedure as in Synthesis Example 1, except that 451.5 g (0.430 mol) of polyneopentyl glycol having a molecular weight of 1050 was used. Hereinafter, this product will be abbreviated as B-3.

[0065] Synthesis Example 4 Poly(3-methyl-1,3-butaneoxide)-di-p-aminobenzoate was obtained by the same procedure as in Synthesis Example 1, except that 451.5 g (0.430 mol) of poly(3-methyl-1,3-butanediol) having a molecular weight of 1050 was used. Hereinafter, this product is abbreviated as B-4.

[0066] Synthesis Example 5 Polyhexamethylene oxide-di-p-aminobenzoate was obtained by the same procedure as in Synthesis Example 1, except that 93.7 g (0.430 mol) of di-(1-hexanol) ether having a molecular weight of 218 was used. Hereinafter, this product is abbreviated as B-5.

[0067] Synthesis Example 6 Poly(tetrahydrofuran / 3-methyltetrahydrofuran ether)-di-p-aminobenzoate was obtained by the same procedure as in Synthesis Example 1, except that 400.0 g (0.430 mol) of poly(tetramethylene / 3-methyltetramethylene ether) glycol (containing 15% by weight of 3-methyltetramethylene ether groups) having a molecular weight of 929 was used. Hereinafter, this product is abbreviated as B-6.

[0068] Details of (B-1) to (B-6) obtained as above are described below. B-1: Polytetramethylene oxide-di-p-aminobenzoate (Amine value: 84 mg KOH / g, molecular weight: 1238, viscosity: 5,300 mPa·s, all carbon atoms in the alkylene ether group have two identical atomic groups bonded to one carbon atom)

[0069] B-2: Polytetramethylene oxide-di-p-aminobenzoate (Amine value 221 mg KOH / g, molecular weight 488, viscosity 250,000 mPa·s, all carbon atoms in the alkylene ether group have two identical atomic groups bonded to one carbon atom)

[0070] B-3: Polyneopentyl oxide-di-p-aminobenzoate (Amine value 80 mgKOH / g, molecular weight 1306, viscosity 4,700 mPa·s, all carbon atoms in the alkylene ether group have two identical atomic groups bonded to one carbon atom)

[0071] B-4: Poly(3-methyl-1,3-butane oxide)-di-p-aminobenzoate (Amine value 81 mgKOH / g, molecular weight 1306, viscosity 4,500 mPa·s, all carbon atoms in the alkylene ether group have two identical atomic groups bonded to one carbon atom)

[0072] B-5: Polyhexamethylene oxide-di-p-aminobenzoate (Amine value 81 mgKOH / g, molecular weight 516, viscosity 113,000 mPa·s, all carbon atoms in the alkylene ether group have two identical atomic groups bonded to one carbon atom)

[0073] B-6: Poly(tetrahydrofuran / 3-methyltetrahydrofuran ether)-di-p-aminobenzoate (Amine value 84 mg KOH / g, molecular weight 1183, viscosity 3,200 mPa·s, some of the carbon atoms in the alkylene ether group are not identical.)

[0074] B-7: Polytetramethylene oxide-di-p-aminobenzoate (Kumiai Chemical Co., Ltd. "Elasmer 650P", amine value 126 mg KOH / g, molecular weight 888, viscosity 6,000 mPa·s) (All carbon atoms in the alkylene ether group have two identical atomic groups bonded to one carbon atom)

[0075] <Other ingredients, alcohol compounds (C)> C-1: Glycerin-propylene oxide adduct (ADEKA "G-700", hydroxyl value 224 mg KOH / g, viscosity 250 mPa·s)

[0076] The various physical properties were measured by the following evaluation methods. (1) Isocyanate group content (NCO%) It was determined according to the hydrochloric acid back titration method for di-n-butylamine specified in JIS K 7301.

[0077] (2) Amine value, hydroxyl value It was determined according to the indicator titration method of JIS K 7237 and K0070.

[0078] (3) Equivalent ratio of NCO / NH2 or NCO / (NH2 + OH) It was calculated from the isocyanate group content, amine value, and hydroxyl value obtained in (1) and (2) above.

[0079] (4) Viscosity All components, including the polyisocyanate compound (A) and the polyamine compound (B), were mixed and the rotational viscosity (mPa s) was measured after 30 seconds using a Brookfield Dial Viscometer (Brookfield Engineering Laboratories, Inc., Brookfield Dial Viscometer Model LVT). Unless otherwise specified, the measurement temperature was 25°C.

[0080] (5) Tensile strength and elongation at break All components, including the polyisocyanate compound (A) and polyamine compound (B), were placed in a glass container (100 mL) and rapidly mixed at 25°C using a metal stirrer 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 product. This was then punched into dumbbell-shaped tensile test specimens (Type A1) as specified in JIS K7139. Tensile strength and elongation at break were measured using a Shimadzu thermostatic chamber tensile tester at 23°C, a test speed of 200 mm / min, and a chuck distance of 70 mm. Evaluation was based on the following criteria. (tensile strength) 5: 40 MPa or more 4: 35 MPa or more, less than 40 MPa 3: 30MPa or more, less than 35MPa 2: 25 MPa or more, less than 30 MPa 1: Less than 25 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: 50% or more and less than 100% In practice, the tensile strength and elongation at break are preferably rated "2" or higher, and more preferably "3" or higher.

[0081] (6) Moisture and heat resistance Dumbbell-shaped tensile test specimens (Type A1) were prepared using the same procedure as in (5), and then stored at 85°C and 85% RH for 1,000 hours using a thermo-hygrostat IG400 manufactured by Yamato Chemical Co., Ltd. After that, they were dried in an environment of 25°C and 50% RH for 24 hours, and the tensile strength and elongation at break were determined using the same procedure. The test score was 10, and the average value was used. Evaluation was based on the following criteria. 5: The larger of the absolute values ​​of the rate of change in tensile strength and elongation at break is 10% or less 4: The larger of the absolute values ​​of the rate of change in tensile strength and elongation at break is more than 10% and less than 20% 3: The larger of the absolute values ​​of the rate of change in tensile strength and elongation at break is more than 20% and less than 30% 2: The absolute value of the rate of change between tensile strength and elongation at break, whichever is larger, is greater than 30% and less than 50% 1: The larger of the absolute values ​​of the rate of change of tensile strength and elongation at break is greater than 50% and less than 100% 0: The larger of the absolute values ​​of the rate of change in tensile strength and breaking elongation exceeded 100%, or the test piece was dissolved. In practice, a rating of "2" or higher is preferable, and a rating of "3" or higher is even more preferable.

[0082] (7) Acid rain resistance All components, including the polyisocyanate compound (A) and polyamine compound (B), were placed in a glass container (100 mL) and rapidly mixed at 25°C using a metal stirrer 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 product. This was then punched out to obtain dumbbell-shaped tensile test specimens (Type A1) as specified in JIS K7139. These specimens were immersed in a 5% aqueous sulfuric acid solution at 60°C for 120 days. After immersion, the specimens were rinsed with water and dried at 25°C for 24 hours. The tensile strength and elongation at break were measured under the same conditions as in (6). The test score was 10, and the average was used. Acid rain resistance was evaluated based on the results using the following criteria. 5: The larger of the absolute values ​​of the rate of change in tensile strength and elongation at break is 1% or less 4: The larger of the absolute values ​​of the rate of change of tensile strength and elongation at break is more than 1% and less than 5% 3: The larger of the absolute values ​​of the rate of change of tensile strength and elongation at break is more than 5% and less than 15% 2: The larger of the absolute values ​​of the rate of change in tensile strength and elongation at break is greater than 15% and less than 30% 1: The larger of the absolute values ​​of the rate of change in tensile strength and elongation at break is greater than 30% and less than 50% 0: The larger of the absolute values ​​of the rate of change in tensile strength and breaking elongation exceeded 50%, or the test piece was dissolved. In practice, a rating of "2" or higher is preferable, and a rating of "3" or higher is even more preferable.

[0083] (8) 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) and rapidly mixed at 25°C using a metal stirring rod until the mixture appeared uniform. The mixture was then poured into a mold, and the tack-free time was measured. The tack-free time was defined as the time it took for no transfer of the resin component to the film when a polyethylene film was lightly pressed against the resin composition, and was evaluated according to the following criteria. 5: Dry to the touch time is over 45 minutes and up to 1 hour 4: Dry to the touch time is more than 30 minutes but less than 45 minutes, or more than 1 hour but less than 3 hours 3: Dry to the touch time is more than 15 minutes but less than 30 minutes, or more than 3 hours but less than 4 hours 2: Dry to the touch time is more than 5 minutes but less than 15 minutes, or more than 4 hours but less than 6 hours 1: Dry to the touch time is more than 6 hours and less than 12 hours 0: Dry to the touch in 5 minutes or less or over 12 hours In practice, a rating of "2" or higher is preferable for the dry-to-touch time, and a rating of "3" or higher is even more preferable.

[0084] (9) Thickening during mixing A 50 mL glass beaker and a metal spoon were prepared, and all components, including the polyisocyanate compound (A) and the polyamine compound (B), were added to the glass beaker so that the total amount of the resin composition of the present invention obtained was 20 g. The components were quickly mixed using the spoon for 30 seconds, and the viscosity was measured 10 minutes after mixing using the same procedure as in (4). If the viscosity 10 minutes after mixing exceeded 50,000 mPa·s, it was rated as ×, and if it did not exceed this value, it was rated as ○.

[0085] (10) Heat generation during mixing A stirrer, a thermometer, and a 2000 mL glass beaker were prepared, and all components including the polyisocyanate compound (A) and the polyamine compound (B) were added so that the total amount of the resin composition of the present invention to be obtained would be 1 kg. Stirring was continued at 200 rpm, and the maximum temperature of the resin composition was measured. Those exceeding 60°C were rated as x, and those not exceeding 60°C were rated as ◯. The test was carried out in a laboratory maintained at 25°C, and all materials before mixing were at 25°C.

[0086] Example 1 17.8 g of A-1 as the polyisocyanate compound (A) and 82.2 g of B-1 as the polyamine compound (B) were mixed using a metal stirring rod until a uniform appearance was achieved, to obtain a polyurea resin composition (isocyanate group / (amino group+hydroxy group)=1.0 / 1.0). Thereafter, evaluation was performed using the evaluation methods described above in (1) to (10).

[0087] Examples 2 to 7, Comparative Examples 1 to 3 The same operation as in Example 1 was carried out, except that the polyisocyanate compound (A) and the polyamine compound (B) were changed to those shown in Table 1, to obtain a polyurea resin composition (isocyanate group / (amino group+hydroxy group)=1.0 / 1.0). In Example 7, 19.8 g of A-1 was used as the polyisocyanate compound (A), and 73.3 g of B-1 and 6.9 g of B-2 were used as the polyamine compounds (B).

[0088] Example 8 A polyurea resin composition (isocyanate group / (amino group+hydroxy group)=1.0 / 1.0) was obtained by the same procedure as in Example 1, except that 19.9 g of A-1 was used as the polyisocyanate compound (A), 73.3 g of B-1 was used as the polyamine compound (B), and 6.8 g of C-1 was used as the alcohol compound (C).

[0089] [Table 1]

[0090] In the examples and comparative examples, evaluations were carried out using the evaluation methods described in (1) to (10) above. The evaluation results are shown in Table 2. [Table 2]

[0091] In Examples 1 to 8, the polyisocyanate compound used contained a carbodiimide-modified aromatic isocyanate, and further, the polyamine compound (B) used had two identical atomic groups bonded to one carbon atom in all carbon atoms of the alkylene ether. Therefore, the mechanical strength (tensile strength, elongation at break) and outdoor resistance were good, thickening and heat generation during mixing could be suppressed, and the coating properties when made into a paint were excellent.

[0092] In Comparative Example 1, since a prepolymer made of a carbodiimide-modified isocyanate and a diol compound was contained, the mechanical strength was good but the outdoor resistance was poor.

[0093] In Comparative Example 2, among the carbon atoms in the alkylene ether group, some of the atomic groups bonded to one carbon atom were not the same, and therefore, when the polyisocyanate compound (A) and the polyamine compound (B) were mixed, significant thickening and heat generation occurred, and the coating properties when made into a paint were poor.

[0094] Comparative Example 3, which did not contain a carbodiimide-modified aromatic isocyanate, was inferior in mechanical strength and also in tack-free time.

Claims

1. A raw material for producing a polyurea resin composition, comprising a polyisocyanate compound (A) and a polyamine compound (B), the polyisocyanate compound (A) contains a carbodiimide-modified aromatic polyisocyanate compound or a derivative thereof, and does not contain a prepolymer composed of a polyisocyanate component and a diol component; A raw material for producing a polyurea resin composition, wherein the polyamine compound (B) is a compound represented by the following general formula: 【Chemistry 1】 (wherein R1 is a polyalkylene ether group having an alkylene ether group of 1 to 20 carbon atoms as a constituent unit, the polyalkylene ether group having an average molecular weight of 100 to 3000, and two identical atomic groups being bonded to one carbon atom in all carbon atoms in the alkylene ether group)

2. a polyamine compound (B1) having a polyalkylene ether group with an average molecular weight of 100 to 500; and a polyamine compound (B2) having a polyalkylene ether group with an average molecular weight of more than 500 and not more than 3,000.

3. The raw material for producing a polyurea resin composition according to claim 1 or 2, further comprising a polyol compound (C).

4. A polyurea resin composition obtained from the raw material for producing the polyurea resin composition according to claim 1 or 2.

5. A paint comprising the polyurea resin composition according to claim 4.

6. A coating film comprising the coating material according to claim 5.

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