Two-component mixed type polyurea resin composition manufacturing raw material and polyurea resin composition

Abstract

The present application relates to a raw material for producing a two-component hybrid polyurea resin composition, the raw material being characterized by containing a component (A) containing a polyisocyanate compound (a) and a component (B) containing an aromatic polyamine compound (b), the component (A) containing a polyisocyanate compound (a) and the component (B) containing an aromatic polyamine compound (b), and the aromatic polyamine compound (b) containing an aromatic polyamine compound (b) being contained in the component (A) and the component (B) immediately after the component (A) and the component (B) are mixed together. And the usable time for which the viscosity value measured without containing an organic solvent is up to two times is 10 minutes or more.

Description

Technical Field

[0001] The invention relates to a raw material for manufacturing a two-component mixed polyurea resin composition and a polyurea resin composition. Background Art

[0002] Conventionally, polyurea resins have been used as reinforcing materials for aged buildings and structures, and also as materials for imparting durability against natural disasters such as earthquakes, because of their excellent physical properties and the fact that they can be used without a solvent.

[0003] Since the isocyanate component and the amine component, which are the raw materials of the polyurea resin, react extremely quickly, in the coating of the polyurea resin, these raw material compounds are mixed and sprayed using a collision mixing type spraying device.

[0004] On the other hand, since spray coating equipment cannot be used for coating in closed spaces or coating on complex shapes, polyurea resins that can be applied manually (hereinafter referred to as manual coating) and have a long usable life have been developed.

[0005] As a polyurea resin composition that reduces the reactivity of an amine component and an isocyanate component and ensures a curing time after mixing, for example, Patent Document 1 discloses a polyurea resin obtained by reacting an amine having a polyalkylene, polyalkylene ether or alkylene polyester and an amino group bonded to an aromatic ring with a polyisocyanate.

[0006] Prior art literature Patent Literature Patent Document 1: Japanese Patent Publication No. 60-32641 Summary of the invention

[0007] Technical problem to be solved by the invention However, the polyurea resin disclosed in Patent Document 1 may have insufficient pot life when applied manually, and the coating film obtained by application may have poor thickness uniformity, or the coating liquid may drip when applied to a wall surface, resulting in insufficient wall surface coating.

[0008] The present invention is an invention for solving these problems, and provides a polyurea resin composition and a two-component mixed type polyurea resin composition production raw material. The polyurea resin composition has a usable time that allows manual coating, is excellent in thickness uniformity and wall coating properties during coating, and can form a coating film with little yellowing.

[0009] Technical solutions for solving technical problems The present inventors have found that the above-mentioned technical problems can be solved by using an isocyanate having a specific structure and an aromatic polyamine compound having a specific structure, thereby completing the present invention. That is, the gist of the present invention is as follows.

[0010] The two-component mixed type polyurea resin composition production raw material of the present invention is characterized in that it contains a component (A) and a component (B), wherein the component (A) contains a polyisocyanate compound (a), and the component (B) contains an aromatic polyamine compound (b), and the usable time until the viscosity value measured in a state without containing an organic solvent reaches twice immediately after the components (A) and (B) are mixed is 10 minutes or more.

[0011] According to the raw material for producing the two-component hybrid polyurea resin composition of the present invention, the polyisocyanate compound (a) preferably contains an aliphatic polyisocyanate compound or a derivative thereof in an amount exceeding 50% by mass, and the aromatic polyamine compound (b) contains a compound represented by the following general formula (1).

[0012] [(NH 2 ) m -C 6 H 5-m -COA-] n R (1) (In the formula, R represents an n-valent polyalkylene group, polyalkylene ether or polyalkylene polyester having an average molecular weight of 80 or more, and A represents an oxygen atom or an imino group. The polyalkylene group may also contain an unsaturated bond. In addition, m represents an integer of 1 to 3, and n represents an integer of 2 to 4.) According to the raw material for producing the two-component mixed polyurea resin composition of the present invention, the viscosity of the polyisocyanate compound (a) at 25° C. is preferably 3000 mPa·s or less.

[0013] According to the raw material for producing the two-component mixed polyurea resin composition of the present invention, the isocyanate group content of the polyisocyanate compound (a) is preferably 5 to 30% NCO.

[0014] The polyurea resin composition of the present invention is characterized by comprising a component (A) and a component (B), wherein the component (A) comprises a polyisocyanate compound (a) and the component (B) comprises an aromatic polyamine compound (b), and all of the following conditions (1) to (3) are satisfied.

[0015] (1) The usable time until the viscosity value measured in the absence of an organic solvent immediately after mixing the component (A) and the component (B) reaches twice is 10 minutes or more.

[0016] (2) The viscosity of the polyisocyanate compound (a) at 25° C. is 3000 mPa·s or less.

[0017] (3) The polyisocyanate compound (a) contains an aliphatic isocyanate compound or a derivative thereof.

[0018] According to the polyurea resin composition of the present invention, the thixotropic index (TI value) is preferably 2-30.

[0019] According to the polyurea resin composition of the present invention, the polyisocyanate compound (a) preferably contains an aliphatic polyisocyanate compound or a derivative thereof in an amount exceeding 50% by mass, and the aromatic polyamine compound (b) preferably contains a compound represented by the following general formula (1).

[0020] [(NH 2 ) m -C 6 H 5-m -COA-] n R (1) (In the formula, R represents an n-valent polyalkylene group, polyalkylene ether or polyalkylene polyester having an average molecular weight of 80 or more, and A represents an oxygen atom or an imino group. The polyalkylene group may also contain an unsaturated bond. In addition, m represents an integer of 1 to 3, and n represents an integer of 2 to 4.) According to the polyurea resin composition of the present invention, the isocyanate group content of the polyisocyanate compound (a) is preferably 5 to 30% NCO.

[0021] According to the polyurea resin composition of the present invention, it is preferred that the polyurea resin composition further contains an organic solvent, and the content of the organic solvent in the polyurea resin composition is 10% by mass or less.

[0022] The method for producing a polyurea resin composition of the present invention is characterized by mixing a component (A) containing a polyisocyanate compound (a) containing an aliphatic polyisocyanate compound or a derivative thereof in an amount exceeding 50% by mass and a component (B) containing an aromatic polyamine compound (b) represented by the following general formula (1).

[0023] [(NH 2 ) m -C 6 H 5-m -COA-] n R (1) (In the formula, R represents an n-valent polyalkylene group, polyalkylene ether or polyalkylene polyester having an average molecular weight of 80 or more, and A represents an oxygen atom or an imino group. The polyalkylene group may also contain an unsaturated bond. In addition, m represents an integer of 1 to 3, and n represents an integer of 2 to 4.) The coating material of the present invention is characterized by containing the above-mentioned polyurea resin composition.

[0024] The coating method of the present invention is characterized in that a coating material is prepared by mixing a component (A) containing a polyisocyanate compound (a) containing an aliphatic polyisocyanate compound or a derivative thereof in an amount exceeding 50% by mass, and a component (B) containing an aromatic polyamine compound (b) represented by the following general formula (1), and the prepared coating material is applied to an object to be coated.

[0025] [(NH 2 ) m -C 6 H 5-m -COA-] n R (1) (In the formula, R represents a polyalkylene, polyalkylene ether or polyalkylene polyester having an average molecular weight of 80 or more with a valence of n, and A represents an oxygen atom or an imino group. Among them, an unsaturated bond may be included in the polyalkylene. In addition, m represents an integer of 1 to 3, and n represents an integer of 2 to 4.) According to the coating method of the present invention, the method of applying the coating material is preferably brush coating, roll coating or trowel coating (referred to as "koteburi" in Japanese).

[0026] The coating film of the present invention is characterized in that it is formed by applying the above coating material.

[0027] Advantages of the Invention The raw materials for manufacturing the two-component mixed polyurea resin composition of the present invention have a good pot life even without dilution with an organic solvent or the like, and also have excellent coatability on the wall surface. In addition, the uniformity of the thickness of the obtained coating film is excellent, and the yellowing is less. Therefore, even in applications where it is exposed to rain and sunlight for a long time, it will not peel off from the substrate or crack, and can protect the substrate visually and physically for a long time. Detailed Embodiments

[0028] <Polyurea Resin Composition> The polyurea resin composition in the present invention contains a component (A) and a component (B), the component (A) contains a polyisocyanate compound (a), and the component (B) contains an aromatic polyamine compound (b).

[0029] In the present invention, the polyisocyanate compound (a) constituting the resin composition is a compound having two or more isocyanate groups in one molecule, and its form can be any of a monomer, an oligomer, and a polymer.

[0030] The polyisocyanate compound (a) preferably contains an aliphatic polyisocyanate compound or a derivative thereof in an amount exceeding 50% by mass. By containing an aliphatic polyisocyanate compound or a derivative thereof in an amount exceeding 50% by mass, the polyisocyanate compound (a) can suppress the reactivity with the aromatic polyamine compound (b) and ensure the time until curing. In addition, the thickness of the obtained coating film is uniform, and yellowing when exposed to sunlight can be reduced.

[0031] Examples of the aliphatic polyisocyanate compound 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 hexanoic acid methyl ester, lysine diisocyanate, trioxyethylene diisocyanate, isophorone diisocyanate, 1,4 - Bis(isocyanatomethyl)cyclohexane, 4,4'-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, 2,5- or 2,6-bis(isocyanatomethyl)norbornane (NBDI), and products obtained by hydrogenating aromatic polyisocyanates.

[0032] Derivatives of aliphatic polyisocyanate compounds include isocyanate-terminated prepolymers obtained by reacting aliphatic polyisocyanate compounds with polyamines or polyols, allophanate-modified products, urea-modified products, carbodiimide-modified products, biuret-modified products, uretdione-modified products and isocyanurate-modified products, as well as products modified to be water-dispersible.

[0033] When the polyisocyanate compound (a) contains a derivative of an aliphatic polyisocyanate compound such as an isocyanate-terminated prepolymer or a modified product, the properties such as tensile strength of the resulting coating film are improved.

[0034] The isocyanate-terminated prepolymer can be obtained, for example, by reacting a polyisocyanate monomer with a polyol or a polyamine in a nitrogen atmosphere and, if necessary, in the presence of a solvent or a known catalyst such as dioctyltin dilaurate at 60 to 100°C by a known method.

[0035] The polyisocyanate compound (a) may contain other isocyanate compounds in addition to aliphatic polyisocyanate compounds according to target performance such as physical properties and usable time, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, etc., which are aromatic polyisocyanates.

[0036] Among them, when 1,6-hexamethylene diisocyanate (HDI) is used as the aliphatic polyisocyanate compound, from the viewpoint of compatibility with HDI and compatibility with the aromatic polyamine compound (b), the isocyanate compound other than HDI is preferably 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-pentamethylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), and more preferably 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, 1,5-pentamethylene diisocyanate. In addition, two or more of them may be used in combination.

[0037] The viscosity of the polyisocyanate compound (a) at 25° C. is preferably 3000 mPa·s or less. If the viscosity of the polyisocyanate compound (a) at 25° C. exceeds 3000 mPa·s, it may be impossible to manually apply a coating material containing the polyurea resin composition.

[0038] In addition, the isocyanate group content of the polyisocyanate compound (a) is preferably 5 to 30% NCO. If the ratio of the isocyanate group in the polyisocyanate compound (a) is below the above range, the polyurea resin composition may not have sufficient physical properties, and if it is above the above range, sufficient usable time may not be obtained.

[0039] The aromatic polyamine compound (b) constituting the resin composition of the present invention is a compound represented by the following general formula (1).

[0040] [(NH 2 ) m -C 6 H 5-m -COA-] n R (1) (In the formula, R represents an n-valent polyalkylene group, polyalkylene ether or polyalkylene polyester having an average molecular weight of 80 or more, and A represents an oxygen atom or an imino group. The polyalkylene group may also contain an unsaturated bond. In addition, m represents an integer of 1 to 3, and n represents an integer of 2 to 4.) Examples of commercially available products in which m=1, n=2, and R is a polyether in the aromatic amine compound (b) include: “Elastomer 1000P” (manufactured by KUMIAI Chemical Industry Co., Ltd., amine value 80 to 90), “VERSALINK P-1000” (manufactured by Nippon Air Products Co., Ltd., amine value 80 to 90), and “Porea SL-100A” (manufactured by KUMIAI Chemical Industry Co., Ltd.).

[0041] The polyurea resin composition of the present invention may contain other amine compounds in addition to the aromatic polyamine compound (b) in order to adjust the coating film properties and pot life.

[0042] As other amine compounds, there can be mentioned aromatic amine compounds such as 4,4'-diamino-3,3'-dichlorodiphenylmethane and diethyltoluenediamine, polyetheramine compounds such as O,O'-bis(2-aminopropyl)propylene glycol, hexamethylenediamine, nonanediamine, Michael adducts of α,β-unsaturated carbonyl compounds and primary amines (aspartic acid type amines), aliphatic amine compounds such as reaction products of epoxy compounds and primary amines, etc. As other amine compounds, either primary amines or secondary amines can be used.

[0043] The content of the other amine compound is preferably 0 to 20 parts by mass based on 100 parts by mass of the total of the aromatic polyamine compound (b). If the content of the other amine compound exceeds 20 parts by mass, the polyurea resin composition may not have a sufficient usable time.

[0044] In the resin composition of the present invention, the equivalent ratio (NCO / NH2) of the isocyanate group of the polyisocyanate compound (a) to the amino group of the aromatic polyamine compound (b) is preferably 0.6 to 1.5, more preferably 0.8 to 1.2, further preferably 0.9 to 1.1, and particularly preferably 0.95 to 1.05. If the equivalent ratio is less than 0.6, the physical properties of the obtained polyurea resin coating film may be reduced, while if the equivalent ratio exceeds 1.5, the physical properties of the obtained polyurea resin coating film may be reduced and side reactions such as foaming may be easily caused.

[0045] The viscosity of the polyurea resin composition of the present invention is preferably 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 having a sufficient thickness, and if it exceeds 500,000 mPa·s, it may be difficult to remove bubbles in the resin composition, or manual coating may become difficult.

[0046] The thixotropic index (TI value) of the polyurea resin composition of the present invention is preferably 2 to 30, more preferably 3 to 25. If the TI value is less than 2, the wall surface coating property may be reduced, and if it exceeds 30, the leveling property may be reduced.

[0047] In addition, the TI value in the present invention is obtained by (viscosity at a spindle speed of 0.3 rpm) ÷ (viscosity at a spindle speed of 6 rpm) using a B-type viscometer.

[0048] The polyurea resin composition of the present invention may contain a catalyst in order to improve the physical properties of the obtained coating film or to adjust the usable time or curing temperature.

[0049] Specific examples of the catalyst include: tertiary amines such as triethylamine, tributylamine, triethylenediamine, 2-dimethylaminoethyl ether, diazabicycloundecene, and N-methylmorpholine; metal catalysts such as dibutyltin diacetate, dibutyltin laurate, 3-diacetoxytetrabutylstannoxane, tin octenate, tin chloride, butyltin trichloride, bismuth trichloride, bismuth octenate, tetra(2-ethylhexyl)titanate, tetrabutoxytitanium, and metal salts of acetoacetic acid; quaternary ammonium salts such as tetramethylammonium chloride; acidic compounds such as hydrochloric acid, sulfuric acid, acetic acid, succinic acid, and trifluoromethanesulfonic acid; and the like.

[0050] The polyurea resin composition of the present invention may contain additives as necessary.

[0051] Examples of additives include alkaline inorganic compounds, pH adjusters, metal oxide particles, tackifiers, waxes, ultraviolet absorbers, surface conditioners, defoamers, thixotropy imparting agents, colorants, dispersants, fillers, diluents, etc. These additives may be used alone or in combination of two or more. In addition, they may be mixed with the polyisocyanate compound (a) and the aromatic polyamine compound (b) in advance.

[0052] The amount of additives added can be appropriately determined depending on the purpose.

[0053] Examples of the basic inorganic compound include hydroxides, oxides, (hydrogen) carbonates, etc. 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 them, hydroxides of alkali metals or alkaline earth metals are more preferred from the viewpoint of stability and influence on viscosity.

[0054] Examples of the pH adjuster 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.

[0055] Examples of the metal oxide fine particles include titanium oxide, magnesium oxide, ferrous oxide, ferric oxide, ferroferric oxide, aluminum oxide, vanadium oxide, and copper oxide.

[0056] Examples of the tackifier 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.

[0057] Examples of the waxes include paraffin waxes, amide waxes, olefin waxes, oxidized olefin waxes, montan waxes, copolymer waxes, and the like.

[0058] Examples of the ultraviolet absorber include hindered amine-based, cinnamic acid-based, benzophenone-based, triazine-based, and triazole-based ultraviolet absorbers.

[0059] Examples of the surface conditioning agent include silicone-based, acrylic polymer-based, vinyl-based, acetylene-based, fluorine-based, and alkylene oxide-based agents.

[0060] Examples of the defoaming agent include mineral oil-based, amide-based, metal soap-based, silicone-based, higher alcohols and their derivatives, fatty acid derivatives, polyolefin-based, etc. Among them, polyolefin-based is more preferred from the viewpoint of defoaming property and chemical resistance.

[0061] Examples of the thixotropy-imparting agent include acrylic polymers, organic urea compounds and modified products thereof, fumed silica, bentonite, organoclay, layered silicate, etc. Among them, organic urea compounds and modified products thereof are more preferred from the viewpoint of the effect relative to the amount added.

[0062] As coloring materials, inorganic pigments, organic pigments, and dyes can be used. Examples of inorganic pigments include red clay, loess, smectite, graphite, Prussian blue, zinc white, cobalt blue, chrome green, titanium white, etc. Examples of organic pigments include basic blue, cresol red, disazo yellow, phthalocyanine blue, quinacridone red, isoindoline yellow, etc. Examples of dyes include madder, sorrel, indigo, etc.

[0063] Examples of the dispersant include acrylic acid polymers, polycarboxylic acid compounds, phosphonic acid compounds, sulfonic acid compounds and neutralized compounds thereof, quaternary ammonium salt compounds, amide compounds, polyether compounds, and the like.

[0064] 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 them, talc, glass beads, and silica are preferred from the viewpoint of the amount added and the viscosity.

[0065] As the diluent, any general organic solvent may be used as long as it has no reactivity with the polyisocyanate compound (a).

[0066] Examples of organic solvents that can be used as diluents include hydrocarbon compounds such as toluene, xylene, and cyclohexane, carbonyl compounds such as acetone, 2-butanone, and isophorone, and ester compounds such as ethyl acetate and butyl acetate. These may be used alone or in combination of two or more.

[0067] The content of the organic solvent in the polyurea resin composition is preferably 10% by mass or less. If the content of the organic solvent exceeds 10% by mass, not only the physical properties of the resulting coating may be deteriorated, but also the original advantage of the polyurea resin that it can be produced without a solvent may be lost.

[0068] <Two-component mixed polyurea resin composition production raw materials> The raw material for producing a two-component hybrid polyurea resin composition of the present invention comprises a component (A) and a component (B), wherein the component (A) comprises a polyisocyanate compound (a), and the component (B) comprises an aromatic polyamine compound (b), and the time taken for the viscosity value measured in the absence of an organic solvent to double immediately after the components (A) and (B) are mixed is 10 minutes or more.

[0069] As a method for making the time until the viscosity value reaches twice the value 10 minutes or more, the following method can be mentioned: a substance containing an aliphatic polyisocyanate compound or a derivative thereof in an amount exceeding 50% by mass is used as the polyisocyanate compound (a) constituting the component (A), and a substance containing a compound represented by the following general formula (1) is used as the aromatic polyamine compound (b) constituting the component (B).

[0070] [(NH 2 ) m -C 6 H 5-m -COA-] n R (1) (In the formula, R represents an n-valent polyalkylene group, polyalkylene ether or polyalkylene polyester having an average molecular weight of 80 or more, and A represents an oxygen atom or an imino group. The polyalkylene group may also contain an unsaturated bond. In addition, m represents an integer of 1 to 3, and n represents an integer of 2 to 4.) The viscosity of the polyisocyanate compound (a) at 25° C. is preferably 3000 mPa·s or less, and the isocyanate group content is preferably 5 to 30% NCO.

[0071] <Production of Polyurea Resin Composition> The method for producing the polyurea resin composition of the present invention is a method of using a two-component mixed type polyurea resin composition producing raw material containing the component (A) and the component (B) and mixing the component (A) and the component (B).

[0072] The component (A) comprises a polyisocyanate compound (a) containing an aliphatic polyisocyanate compound or a derivative thereof in an amount exceeding 50% by mass. The component (B) contains an aromatic polyamine compound (b) represented by the following general formula (1).

[0073] [(NH 2 ) m -C 6 H 5-m -COA-] n R (1) (In the formula, R represents an n-valent polyalkylene group, polyalkylene ether or polyalkylene polyester having an average molecular weight of 80 or more, and A represents an oxygen atom or an imino group. The polyalkylene group may also contain an unsaturated bond. In addition, m represents an integer of 1 to 3, and n represents an integer of 2 to 4.) Component (A) and component (B) may each contain the above-mentioned additives such as an organic solvent.

[0074] The raw materials for producing the two-component mixed polyurea resin composition are composed of a component (A) containing a polyisocyanate compound (a) and a component (B) containing an aromatic polyamine compound (b). Therefore, the time until the viscosity value measured in a state without an organic solvent reaches twice (usable time) can be 10 minutes or more immediately after mixing the components (A) and (B), and a polyurea resin composition having a long usable time can be obtained. The usable time is preferably 10 to 360 minutes, more preferably 20 to 180 minutes, and even more preferably 30 to 120 minutes.

[0075] <Coating> The coating film of the present invention is formed by applying a coating material containing the polyurea resin composition of the present invention.

[0076] The coating film of the present invention can be formed by the following coating method: a component (A) containing a polyisocyanate compound (a) containing an aliphatic polyisocyanate compound or a derivative thereof in an amount exceeding 50% by mass and a component (B) containing an aromatic polyamine compound (b) represented by the following general formula (1) are mixed to prepare a coating, and the prepared coating is applied to a coating object.

[0077] [(NH 2 ) m -C 6 H 5-m -COA-] n R (1) (In the formula, R represents an n-valent polyalkylene group, polyalkylene ether or polyalkylene polyester having an average molecular weight of 80 or more, and A represents an oxygen atom or an imino group. The polyalkylene group may also contain an unsaturated bond. In addition, m represents an integer of 1 to 3, and n represents an integer of 2 to 4.) The polyurea resin composition of the present invention has a sufficient curing time, so as a method for coating, a known method can be used. It can be appropriately selected according to the target thickness, the shape of the coated object, etc. As examples, there can be cited methods such as dip coating (dip coating, dip coating), wire bar, Baker-type applicator, gravure roller, potting, brush coating, roller coating, or trowel coating.

[0078] Alternatively, a cured product may be three-dimensionally formed using a 3D printer or the like.

[0079] The thickness of the coating film can be appropriately selected depending on the target physical properties, the material of the substrate, etc., and is usually preferably 10 to 10,000 μm, more preferably 50 to 8,000 μm, and even more preferably 100 to 5,000 μm from the viewpoint of economy and physical properties.

[0080] As a method for obtaining the above-mentioned thickness, coating may be performed once or repeatedly in multiple times.

[0081] The polyurea resin composition of the present invention has excellent physical strength, elongation, and chemical resistance, and can therefore be suitably used as a substrate protection or a specific substance penetration prevention layer, etc. Specific examples include coating floors, linings, roof waterproofing, exterior wall coatings, bridge deck waterproofing, waterproof coatings, anti-corrosion coatings, protective coatings for the inside and outside of steel pipes, metal pipes, and tanks, reinforcement and repair of buildings, protection of resin parts and metal parts, and water tanks.

[0082] The polyurea resin composition of the present invention may be compounded with a flat body such as fibers (including long fibers and short fibers), nonwoven fabrics (including long fibers and short fibers), cloth, wire mesh, screen, or perforated metal.

[0083] As the method of compounding, a known method can be used.

[0084] The coating amount when combined with the above-mentioned flat body can be appropriately selected according to the target physical properties, the material of the substrate, etc., and is usually preferably 0.01 to 5 kg / m 2 , more preferably 0.03 to 4 kg / m 2 , more preferably 0.05 to 3 kg / m 2 .

[0085] The polyurea resin composition of the present invention can also be poured into a metal frame to produce a molded body.

[0086] In order to improve the releasability between the metal frame and the polyurea resin composition, a release agent may be used. As the release agent, a known release agent may be used, and the release agent may be applied to the metal frame before the polyurea resin composition is poured, or may be mixed when the polyisocyanate compound (a) and the aromatic polyamine compound (b) are mixed. In addition, when the release agent does not have reactivity with the polyurea resin composition, it may be mixed with one or both of the polyisocyanate compound (a) and the aromatic polyamine compound (b) in advance.

[0087] The polyurea resin composition of the present invention is reactive at room temperature and therefore generally does not need to be heated, but may be heated to accelerate curing after coating, etc. The curing temperature may be appropriately determined according to the construction method and curing time, and is preferably 40 to 80°C from the viewpoint of safety.

[0088] As a device for heating the resin composition of the present invention, a known device can be used in consideration of the viscosity of the obtained polyurea resin, the shape of the adherend, etc. Specific examples of the heating device include a heating roller, a roller heater, a polyimide heater, an infrared radiation heater, a high-temperature air heater, a hot air gun, a dryer, a drying furnace, a sintering furnace, a constant temperature dryer, a constant temperature furnace, etc.

[0089] The curing time can be appropriately selected according to the characteristics of the material, machinery, and process, but from the viewpoint of productivity, it is preferably less than 3 hours, more preferably less than 2 hours, and even more preferably less than 1 hour.

[0090] To adjust the curing time, the above-mentioned catalysts can also be used.

[0091] Example The present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0092] The raw materials used in Examples and Comparative Examples are shown below. Note that the raw materials were used directly without being purified or distilled.

[0093] <Polyisocyanate compound (a)> ·HDI: 1,6-hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd., 49.9% NCO, viscosity 3 mPa·s) ·24A-100: Biuret-modified hexamethylene diisocyanate (Asahi Kasei Industries, Ltd., "Duranate 24A-100", 23.5% NCO, viscosity 1800 mPa·s) ·WL72-100: Water-dispersible modified hexamethylene diisocyanate (Asahi Kasei Industries, Ltd., "Duranate WL72-100", 21.3% NCO, viscosity 1000 mPa·s) WT20-100: Water-dispersible modified hexamethylene diisocyanate (Asahi Kasei Industries, Ltd., "Duranate WT20-100", 14.1% NCO, viscosity 1400 mPa·s) ·WB40-100: Water-dispersible modified hexamethylene diisocyanate (Asahi Kasei Industries, Ltd., "Duranate WB40-100", 16.6% NCO, viscosity 4500 mPa·s) ·HXR: Urate-modified hexamethylene diisocyanate ("Coronate HXR" manufactured by Tosoh Corporation, 21.9% NCO, viscosity 1500 mPa·s) PP-45: Isocyanate-terminated HDI prepolymer (4.5% NCO, viscosity 3000 mPa·s) synthesized by the following method 47.2 parts by mass of polypropylene polyol (ADEKA POLYETHER P-1000 manufactured by ADEKA Corporation, molecular weight 1000, difunctional, hydroxyl value 110) and 42.5 parts by mass of polyethylene glycol (polyethylene glycol 4000 manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 3200, difunctional, hydroxyl value 35) were mixed, and 10.2 parts by mass of 1,6-hexamethylene diisocyanate (Duranate 50M-HDI manufactured by Asahi Kasei Industries, Ltd., 50.0% NCO) was added thereto, and the mixture was mixed and stirred at 80° C. for 3 hours under a nitrogen atmosphere for synthesis.

[0094] ·D-370N: Isocyanurate-modified 1,5-pentane diisocyanate ("STABiOD-370N" manufactured by Mitsui Chemicals, Inc., 25.0% NCO, viscosity 2000 mPa·s) MR-200: Diphenylmethane diisocyanate (Tosoh Corporation "Millionate MR-200", 30.9% NCO, viscosity cannot be measured because it is a solid) ·TDI: Toluene diisocyanate (2,4-, 2,6-mixed product) (manufactured by Tokyo Chemical Industry Co., Ltd., 48.2% NCO, viscosity 3 mPa·s) ·IPDI: Isophorone diisocyanate (mixed isomers) (manufactured by Tokyo Chemical Industry Co., Ltd., 37.8% NCO, viscosity 14 mPa·s) <Aromatic polyamine compound (b)> SL-100A: Poly(tetramethylene / 3-methyltetramethylene ether) glycol bis(4-aminobenzoate) (Porea SL-100A manufactured by KUMIAI Chemical Industry Co., Ltd., amine value 87 mgKOH / g, molecular weight 1238, viscosity 7500 mPa·s) 250P: Polytetrahydrofuran-di-p-aminobenzoate ("Elastomer 250P" manufactured by KUMIAI Chemical Industry Co., Ltd., amine value 221 mgKOH / g, molecular weight 488, viscosity 205000 mPa·s) 650P: Polytetrahydrofuran-di-p-aminobenzoate ("Elastomer 650P" manufactured by KUMIAI Chemical Industry Co., Ltd., amine value 126 mgKOH / g, molecular weight 888, viscosity 8000 mPa·s) 1000P: Polytetrahydrofuran-di-p-aminobenzoate ("Elastomer 1000P" manufactured by KUMIAI Chemical Industry Co., Ltd., amine value 84 mgKOH / g, molecular weight 1238, viscosity 6000 mPa·s) ·HMBA: Heptamethylene-1,7-bis(4-aminobenzamide) synthesized by the following method (amine value 317 mgKOH / g, molecular weight 354, viscosity 100000 mPa·s) Heptamethylene-1,7-bis(4-aminobenzamide) was synthesized by the same operation as described in the synthesis example of Japanese Patent Publication No. 60-32641 except that polytetramethylene glycol was changed to 1,7-heptamethylenediamine.

[0095] <Other amine compounds> · DETDA: A mixture of 2,4- or 2,6-diamino-3,5-diethyltoluene ("HARTCURE 10" manufactured by Kumiai Chemical Industry Co., Ltd., amine value 629 mgKOH / g, molecular weight 178) MBCA: a mixture of isomers of 4,4′-methylenebis(cyclohexylamine) (manufactured by Tokyo Chemical Industry Co., Ltd., amine value 534 mgKOH / g, molecular weight 210) ·D-230: O,O′-bis(2-aminopropyl)propylene glycol ("Polyetheramine D-230" manufactured by Mitsui Fine Chemicals, amine value 467 mgKOH / g, molecular weight 230) <Additives> · PFA-250: Fatty acid amide wax ("DISPARLON PFA-250" manufactured by Kusumoto Chemicals Co., Ltd.) 1958: Layered silicate (Garamite 1958, manufactured by BYK) The measurement of various physical properties was performed by the following evaluation methods.

[0096] (1) Isocyanate group content (%NCO) It was determined by the back titration method of di-n-butylamine with hydrochloric acid in accordance with JIS K 7301.

[0097] (2) Amine value It was determined by the indicator titration method of JIS K 7237.

[0098] (3) NCO / NH2 equivalent ratio The isocyanate group content and the amine value determined in (1) and (2) above were calculated.

[0099] (4) Viscosity The rotational viscosity (mPa·s) at a temperature of 25° C. was measured using a B-type viscometer (BROOKFIELD DIAL VISCOMETER model LVT, manufactured by Brookfield Engineering Laboratories, Inc.).

[0100] (5) Available time Components (A) and (B) were placed in a glass container (100 mL capacity) and rapidly mixed at 25°C using a metal stirring rod until the mixture looked homogeneous. The same operation as the viscosity measurement method was then performed to determine the time from when the viscosity value immediately after mixing reached twice the value, which was taken as the usable time. The usable time was determined according to the following criteria.

[0101] 4: The usable time is 30 minutes or more and 120 minutes or less.

[0102] 3: The usable time is 20 minutes or more and less than 30 minutes, or more than 120 minutes and 180 minutes or less.

[0103] 2: The usable time is 10 minutes or more and less than 20 minutes, or more than 180 minutes and less than 360 minutes.

[0104] 1: The usable time is less than 10 minutes or more than 360 minutes.

[0105] Practically, the usable time needs to be evaluated as "2" or more, and more preferably "3" or more.

[0106] (6) Thixotropic index (TI value) The viscosity of the polyurea resin composition was measured using a B-type viscometer "DV-I" manufactured by Brookfield at a spindle speed of 6 rpm. Next, a polyurea resin of the same composition was prepared again, and the viscosity of the polyurea resin composition was measured at a spindle speed of 0.3 rpm. The TI value was calculated using the following calculation formula.

[0107] (viscosity at spindle speed 0.3rpm) ÷ viscosity at spindle speed 6rpm) It should be noted that “-” means that the usable time is too short to be measured.

[0108] (7) Surface uniformity of coating Leveling was evaluated based on JIS K 5400, and the presence or absence of bubbles was visually evaluated.

[0109] (Leveling evaluation) Place component (A) and component (B) in a glass container (100 mL capacity) and mix quickly at 25°C using a metal stirring rod until it looks uniform. Spread it on a 200×100×2 mm glass plate and move it at a constant speed while pressing a leveling tester (gap size 4 mm) on the test plate. After curing at 25°C for 24 hours, if the unevenness of the coating film made by the leveling tester is the same as or smaller than that of the sample, it is set to "1", otherwise it is set to "0". In addition, the case where the usable time is too short and it has been cured before the test and cannot be evaluated is set to "-". It should be noted that the sample is a cured product made in Example 1.

[0110] (Presence or absence of bubbles) Component (A) and component (B) were placed in a glass container (100 mL capacity) and rapidly mixed at 25°C using a metal stirring rod until the mixture looked uniform. The mixture was spread on a 200×100×2 mm glass plate and cured at 25°C for 24 hours. The presence or absence of bubbles in the obtained cured product was visually evaluated according to the following criteria.

[0111] 4: No bubbles were confirmed, or the coating film was slightly cloudy due to fine bubbles.

[0112] 3: Turbidity of the coating film can be confirmed by fine bubbles.

[0113] 2: The presence of bubbles was visually confirmed, but the thickness of the coating film remained uniform.

[0114] 1: Pits formed by bubbles exist on the surface, and the thickness cannot be uniform.

[0115] -: The usable time is too short and it has already solidified before testing, so it cannot be evaluated.

[0116] Practically, an evaluation of "2" or more is required, and more preferably "3" or more.

[0117] (8) Wall coating property (flow-down property (original Japanese: たるみ性)) Based on JIS K 5551, the wall coating property is evaluated by the flow-down property.

[0118] Using a sag tester (coating film thicknesses of 100, 200, 300, 400, 500 μm), the coating composition is applied to a 200 mm × 150 mm metal plate. Immediately, the side with the thicker coating film is placed downward, and the metal plate is vertically erected in such a way that the trajectory line of the sag tester becomes horizontal and is cured. The thickness at which no flow (flow-down) of the liquid is observed is evaluated according to the following criteria.

[0119] 1: Even when the coating film thickness is 200 μm or less, the trajectory line shows flow-down. 2: The trajectory line does not show flow-down before the coating film thickness reaches 200 μm and shows flow-down at 300 μm. 3: The trajectory line does not show flow-down before the coating film thickness reaches 300 μm and shows flow-down at 400 μm. 4: The trajectory line does not show flow-down before the coating film thickness reaches 400 μm and shows flow-down at 500 μm. 5: Even when the coating film thickness is 500 μm, the trajectory line does not show flow-down. Practically, an evaluation of "2" or more is required, and more preferably an evaluation of "3" or more.

[0120] It should be noted that "-" indicates that the pot life is too short to be measured.

[0121] (9) Tensile strength and elongation at break The polyurea resin composition is poured into a 30 cm × 30 cm metal frame and cured at 25°C for 24 hours to obtain a cured product with a thickness of 1 mm. It is punched with a test piece punching die to obtain a dumbbell-shaped tensile test piece (Type A1) specified in JIS K7139. For this test piece, using a universal testing machine manufactured by INTESCO Co., Ltd., the tensile strength and elongation at break are determined under the conditions of 23°C, a test speed of 5 mm / minute, and a distance between chucks of 115 mm. The evaluation is carried out according to the following criteria.

[0122] (Tensile strength) 4: 30 MPa or more 3: 20 MPa or more and less than 30 MPa 2: 10 MPa or more and less than 20 MPa 1: Less than 10 MPa (Elongation at break) 3: 5% or more 2: 3% or more and less than 5% 1: Less than 3% Practically, an evaluation of "2" or higher is required.

[0123] (10) Acid resistance The polyurea resin composition was applied to a metal plate with a thickness of 1 mm using a Baker-type applicator and cured at 25° C. for 24 hours. The cured product was then peeled off the metal plate, cut into 20 mm × 20 mm × 1 mm pieces as test pieces, and immersed in a 10 mass % sulfuric acid aqueous solution at 25° C. for 60 days. The case where blistering, cracking, softening, and dissolution did not occur in the test piece was set to "1", and the case where any one or more of the above occurred was set to "0".

[0124] (11) Resistance to organic acids The test piece obtained in the same manner as in (10) above was immersed in a 5 mass % acetic acid aqueous solution at 25° C. for 60 days. Then, the case where blistering, cracking, softening, and dissolution did not occur in the test piece was rated as “1”, and the case where any one or more of these occurred was rated as “0”.

[0125] (12) Alkali resistance The test piece obtained in the same manner as in (10) above was immersed in a saturated aqueous solution of calcium hydroxide at 25° C. for 60 days. Then, the case where blistering, cracking, softening, and dissolution did not occur in the test piece was marked as “1”, and the case where any one or more of the above occurred was marked as “0”.

[0126] (13) Yellowing resistance The polyurea resin composition was applied to a concrete block with a Baker-type applicator to a thickness of 1 mm and cured at 25° C. for 24 hours. Then, accelerated weather resistance and accelerated light resistance tests were performed using the xenon lamp method of JIS K 5600-7-7 (radiation intensity 60 W / m 2 , wavelength 300 to 400 nm, cycle A, 300 hours). The test pieces before and after the test were checked, and a value of "1" was set when no yellowing was observed, and a value of "0" was set when yellowing was observed.

[0127] Example 1 The polyisocyanate compound (a) of component (A) HDI and the aromatic polyamine compound (b) of component (B) SL-100A were mixed at 25° C. using a metal stirring rod so that the equivalent ratio (NCO / NH 2 ) was 1.05 until the appearance was uniform.

[0128] Then, the obtained polyurea resin composition was applied onto a substrate by the method described in the above evaluation test, and cured to obtain a coating film.

[0129] Examples 2 to 23, Comparative Examples 1 to 6 Component (A) and component (B) were mixed in the same manner as in Example 1, except that component (A) and component (B) were prepared to have the compositions described in Tables 1 and 3, to obtain a polyurea resin composition and a coating film.

[0130] Embodiments 24 to 28 A polyurea resin composition and a coating film were obtained in the same manner as in Example 3 except that PFA-250 and 1958 were mixed as additives in the contents described in Table 3.

[0131] Tables 1 to 4 show the compositions of the raw materials for producing the polyurea resin compositions in Examples and Comparative Examples and the properties of the obtained polyurea resin compositions.

[0132] [Table 1]

[0133] [Table 2]

[0134] [Table 3]

[0135] [Table 4]

[0136] The polyurea resin composition of the embodiment has a long usable life and can be applied manually. In addition, the surface of the coating film is uniform. If the aliphatic polyisocyanate compound constituting the polyurea resin composition is hexamethylene diisocyanate or a modified isocyanate compound, the obtained coating film is more excellent in uniformity and various physical properties when the coating film is formed.

[0137] In Comparative Examples 1 to 3 in which the polyisocyanate compound constituting the polyurea resin composition does not contain an aliphatic polyisocyanate compound or contains a small amount of an aliphatic polyisocyanate compound, and Comparative Examples 4 to 6 in which the polyurea resin composition does not contain an aromatic polyamine compound, the usable time is sometimes short, and it is difficult to apply the composition manually, and the resulting coating film cannot fully satisfy the properties such as acid resistance, organic acid resistance, alkali resistance, and yellowing resistance.

Claims

1. A two-component mixed polyurea resin composition manufacturing raw material, characterized in that: The invention comprises a component (A) and a component (B), wherein the component (A) comprises a polyisocyanate compound (a), and the component (B) comprises an aromatic polyamine compound (b). The usable time until the viscosity value measured in the absence of an organic solvent immediately after mixing the component (A) and the component (B) reaches twice is 10 minutes or more.

2. The two-component mixed polyurea resin composition manufacturing raw material according to claim 1, characterized in that: The polyisocyanate compound (a) contains an aliphatic polyisocyanate compound or a derivative thereof in an amount exceeding 50% by mass, The aromatic polyamine compound (b) includes a compound represented by the following general formula (1): [(NH2) m -C6H 5-m -COA-] n R (1) In formula (1), R represents an n-valent polyalkylene group, polyalkylene ether or polyalkylene polyester having an average molecular weight of 80 or more, A represents an oxygen atom or an imino group; wherein the polyalkylene group may or may not contain an unsaturated bond; and m represents an integer of 1 to 3, and n represents an integer of 2 to 4.

3. The two-component mixed polyurea resin composition manufacturing raw material according to claim 1 or 2, characterized in that: The viscosity of the polyisocyanate compound (a) at 25° C. is 3000 mPa·s or less.

4. The raw material for producing a two-component mixed polyurea resin composition according to any one of claims 1 to 3, characterized in that: The isocyanate group content of the polyisocyanate compound (a) is 5 to 30% NCO.

5. A polyurea resin composition, characterized in that: The invention comprises a component (A) and a component (B), wherein the component (A) comprises a polyisocyanate compound (a), and the component (B) comprises an aromatic polyamine compound (b), and all of the components satisfy the following conditions (1) to (3): (1) The usable time until the viscosity value measured in the absence of an organic solvent reaches twice immediately after mixing the components (A) and (B) is 10 minutes or more; (2) the viscosity of the polyisocyanate compound (a) at 25° C. is 3000 mPa·s or less; (3) The polyisocyanate compound (a) contains an aliphatic isocyanate compound or a derivative thereof.

6. The polyurea resin composition according to claim 5, characterized in that The thixotropic index (TI) value of the polyurea resin composition is 2-30.

7. The polyurea resin composition according to claim 5 or 6, characterized in that: The polyisocyanate compound (a) contains an aliphatic polyisocyanate compound or a derivative thereof in an amount exceeding 50% by mass, The aromatic polyamine compound (b) includes a compound represented by the following general formula (1): [(NH2) m -C6H 5-m -COA-] n R (1) In formula (1), R represents an n-valent polyalkylene group, polyalkylene ether or polyalkylene polyester having an average molecular weight of 80 or more, A represents an oxygen atom or an imino group; wherein the polyalkylene group may or may not contain an unsaturated bond; and m represents an integer of 1 to 3, and n represents an integer of 2 to 4.

8. The polyurea resin composition according to any one of claims 5 to 7, characterized in that The isocyanate group content of the polyisocyanate compound (a) is 5 to 30% NCO.

9. The polyurea resin composition according to any one of claims 5 to 8, characterized in that The polyurea resin composition further contains an organic solvent, and the content of the organic solvent in the polyurea resin composition is 10% by mass or less.

10. A method for producing a polyurea resin composition, characterized in that: Mix ingredients (A) and (B). The component (A) contains a polyisocyanate compound (a), wherein the polyisocyanate compound (a) contains an aliphatic polyisocyanate compound or a derivative thereof in an amount exceeding 50% by mass. The component (B) contains an aromatic polyamine compound (b) represented by the following general formula (1): [(NH2) m -C6H 5-m -COA-] n R (1) In formula (1), R represents an n-valent polyalkylene group, polyalkylene ether or polyalkylene polyester having an average molecular weight of 80 or more, A represents an oxygen atom or an imino group; wherein the polyalkylene group may or may not contain an unsaturated bond; and m represents an integer of 1 to 3, and n represents an integer of 2 to 4.

11. A coating, characterized in that: A polyurea resin composition according to any one of claims 5 to 9.

12. A coating method, characterized in that: The components (A) and (B) are mixed to prepare a coating material, and the prepared coating material is applied to a coating object. The component (A) comprises a polyisocyanate compound (a), wherein the polyisocyanate compound (a) contains an aliphatic polyisocyanate compound or a derivative thereof in an amount exceeding 50% by mass. The component (B) contains an aromatic polyamine compound (b) represented by the following general formula (1): [(NH2) m -C6H 5-m -COA-] n R (1) In formula (1), R represents an n-valent polyalkylene group, polyalkylene ether or polyalkylene polyester having an average molecular weight of 80 or more, A represents an oxygen atom or an imino group; wherein the polyalkylene group may or may not contain an unsaturated bond; and m represents an integer of 1 to 3, and n represents an integer of 2 to 4.

13. The coating method according to claim 12, characterized in that: The coating is applied by brush, roller or trowel.

14. A coating film, characterized in that: The coating material according to claim 11 is applied.

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