Polyurethane resin composition manufacturing raw materials

Abstract

This invention provides a raw material for manufacturing polyurea resin compositions that leverages the properties of polyurea resin, such as its solvent-free use, excellent film strength, and coating properties, while also improving chemical resistance, particularly in environments where high resistance to organic acids is required. [Solution] A raw material for producing a polyurea resin composition containing a polyisocyanate compound (A), an aspartic acid ester compound (B), and a polyol compound (C), Polyol compound (C) is a raw material for producing polyurea resin compositions, characterized by containing an ester bond.

Description

Technical Field

[0001] The present invention relates to raw materials for manufacturing a polyurea resin composition.

Background Art

[0002] A polyurea resin composition containing a polyisocyanate compound and an aspartic acid ester compound has a slower curing rate compared to other polyurea resins, can be used without a solvent, and has a lower viscosity compared to other materials, so it has been preferably used as a coating material using a brush or a roller, so-called hand-applied material. Further, a polyurea resin composition containing an aspartic acid ester compound has the feature of being excellent in mechanical strength and chemical resistance compared to a polyurethane resin composition.

[0003] On the other hand, due to its chemical structure, a polyurea resin containing an aspartic acid ester compound tends to result in a hard and brittle cured product. Therefore, techniques for improving physical properties by introducing a urethane structure into an isocyanate compound or mixing a polyol compound with a polyamine compound are known.

[0004] For example, Patent Document 1 discloses using a prepolymer obtained from a polyol compound having a specific structure and an aliphatic diisocyanate monomer as a polyisocyanate compound, and discloses a polyurea resin in which scratch resistance, which was a problem due to its hardness, is improved and which is further excellent in chemical resistance and weather resistance.

[0005] Patent Document 2 discloses a polyurea resin that provides a coating film excellent in wall coating properties and scratch resistance by containing a polyol compound having a specific structure.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

[0007] However, the coatings obtained from the resin compositions disclosed in both patent documents do not exhibit sufficient chemical resistance, especially in environments where high resistance to organic acids is required, such as sludge tanks, underground pits, and wastewater treatment tanks, and further improvements in resistance are needed.

[0008] The present invention has been made in view of the above circumstances, and the object of the present invention is to provide a raw material for producing a polyurea resin composition that improves chemical resistance while taking advantage of the properties of polyurea resin, such as being usable without solvents and having excellent coating strength and coating properties. [Means for solving the problem]

[0009] As a result of diligent research, the inventors of the present invention have found that the above problems can be solved by using polyisocyanate compounds, aspartic acid ester compounds, and polyol compounds of a specific structure as raw materials for producing polyurea resin compositions, and have completed the present invention.

[0010] In other words, the gist of the present invention is as follows: (1) A raw material for producing a polyurea resin composition containing a polyisocyanate compound (A), an aspartic acid ester compound (B), and a polyol compound (C), Polyol compound (C) is a raw material for producing polyurea resin compositions, characterized by containing an ester bond. (2) A polyisocyanate compound (A) is a raw material for producing the polyurea resin composition described in (1), wherein the number of functionalities is 3 or more. (3) A raw material for producing a polyurea resin composition according to (1) or (2), characterized in that the polyisocyanate compound (A) contains 70% by mass or more of isocyanurate. (4) A raw material for producing a polyurea resin composition according to (1) to (3), characterized in that the polyisocyanate compound (A) contains 70% by mass or more of aliphatic polyisocyanate. (5) A raw material for producing a polyurea resin composition according to (1) to (4), characterized in that the polyol compound (C) includes a castor oil polyol with a functional number of 3 or more and a modified version thereof. (6) A raw material for producing a polyurea resin composition according to (1) to (5), characterized in that the polyol compound (C) contains 70% by mass or more of a castor oil polyol with a functional number of 3 or more and a modified version thereof. (7) A raw material for producing a polyurea resin composition according to (5) or (6), further containing 0.1 to 5% by mass of polyolefin resin. (8) A polyurea resin composition and a coating film obtained from the resin composition manufacturing raw materials of (1) to (7). (9) The coating film according to (8), characterized in that the durometer hardness of the coating film after immersion in a 10% acetic acid aqueous solution at 25°C for 60 days is D30 or higher. [Effects of the Invention]

[0011] The polyurea resin composition manufacturing raw material of the present invention can be used without solvents, and provides a polyurea resin composition that has excellent coating strength and coating properties, as well as even better chemical resistance of the coating film. [Modes for carrying out the invention]

[0012] In this invention, the number of functional groups refers to the number of functional groups contained in one molecule, and the same definition applies regardless of differences in molecular weight, such as monomers and polymers. If the compound is not a single compound but has a distribution in the number of functional groups, or if it is a mixture, the average value is used.

[0013] The polyurea resin composition of the present invention contains a polyisocyanate compound (A), an aspartic acid ester compound (B), and a polyol compound (C). <Polyisocyanate compound (A)> In the present invention, any monomer species can be used for the polyisocyanate compound (A). Examples of monomer species include, for example, 4,4'-phenylmethane diisocyanate and its isomers, 2,4-toluene diisocyanate and its isomers, xylylene diisocyanate, 1,4-phenylene diisocyanate and its isomers, naphthalene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 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 di Examples include socianates, 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 hydrogenated aromatic polyisocyanates, and their derivatives can be used in the same way. Furthermore, two or more of these may be used in combination. Among these, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), and isophorone diisocyanate are preferred in terms of pot life and curing time. The content of polyisocyanate compound (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0014] Examples of derivatives of polyisocyanate compounds include isocyanate-terminated prepolymers obtained by reacting polyisocyanate compounds with polyamines or polyols, allophanate compounds, urea compounds, carbodiimide compounds, biuret compounds, uretdione compounds, isocyanurate compounds, reaction products (adducts) with alcohol compounds, and those modified into a water-dispersible form.

[0015] Among them, isocyanate-terminated prepolymers, allophanate compounds, biuret compounds, and isocyanurate compounds are preferred, and isocyanurate compounds are particularly preferred.

[0016] Its content is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0017] The derivatives of the above aliphatic polyisocyanate compounds can be obtained by known methods.

[0018] In addition to the polyisocyanate compound (a) having a functionality of 3 or more, the polyisocyanate compound (A) can contain other isocyanate components according to the intended performance such as physical properties and pot life. Examples include monomers such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate, and bifunctional isocyanate-terminated prepolymers.

[0019] From the viewpoints of the strength of the coating film and the pot life of the resin composition, the isocyanate group content (NCO%) in the polyisocyanate compound (A) is preferably 5 to 50% by mass, more preferably 5 to 35% by mass, still more preferably 10 to 33% by mass, and particularly preferably 15 to 30% by mass.

[0020] From the viewpoint of paint uniformity and sagging prevention, the polyisocyanate compound (A) preferably has a viscosity of 1,000 to 30,000 mPa·s at 25°C, more preferably 1,500 to 25,000 mPa·s, and even more preferably 2,000 to 20,000 mPa·s.

[0021] From the viewpoint of chemical resistance, the number of functionalities in polyisocyanate compounds is preferably 3 to 10, preferably 3 to 7, and particularly preferably 3 to 5.

[0022] Examples of polyisocyanate compounds with three or more functionalities include allophanate compounds, urea compounds, carbodiimide compounds, biuret compounds, uretdione compounds, and isocyanurate compounds, as well as reaction products (adducts) with alcohol compounds with three or more functionalities, using each monomer species as a raw material.

[0023] Examples of commercially available polyisocyanate compounds (a) with three or more functionalities include "Basonat HI2000" from BASF, "Duranate 24A" from Asahi Kasei, "Coronate HXR" from Tosoh Corporation, "FD90B" from Vencorex, and "Takenate D-120N," "D-131N," and "D-370N" from Mitsui Chemicals. <Aspartate ester compound (B)> The aspartic acid ester compound (B) that constitutes the raw material for manufacturing the resin composition of the present invention is a compound represented by the following general formula (1).

[0024] X(-NH-CH(CH2COOR 2 )COOR 1 ) n (1) (X is an organic group, n is an integer greater than or equal to 2, R 1 and R 2 These are organic groups of the same or different type. Examples of commercially available aspartic acid ester compounds (B) include "AmicureIC-221," "AmicureIC-321," and "AmicureIC-322" from Evonik, "FeisparticF220," "FeisparticF420," and "FeisparticF520" from Feiyang, and "DesmophenNH1420" and "DesmophenNH1520" from Covestro. <Other amine compounds> The raw materials for producing the polyurea resin composition of the present invention may contain other amine compounds other than the aspartic acid ester compound (B) for the purpose of adjusting the coating film properties and pot life.

[0025] Other amine compounds include aromatic amine compounds such as 4,4′-diamino-3,3′-dichlorodiphenylmethane and diethyltoluenediamine; polyetheramine compounds such as O,O′-bis(2-aminopropyl)propylene glycol and polyalkylene oxide-di-p-aminobenzoate; and aliphatic amine compounds such as hexamethylenediamine, nonanediamine, and reaction products of epoxy compounds and primary amines. Both primary and secondary amines can be used for these other amine compounds.

[0026] From the viewpoint of pot life, the content of the other amine compounds mentioned above is preferably 0 to 20 parts by mass per 100 parts by mass of the total amount of aspartic acid ester compound (B). <Polyol compound (C)> The raw material for producing the polyurea resin composition of the present invention contains a polyol compound (C) having an ester bond. As a result, the resulting polyurea resin composition can exhibit good chemical resistance.

[0027] Examples of polyol compounds (C) include castor oil polyols, polyester polyols, acrylic polyols, and partially saponified polyvinyl alcohol.

[0028] Among these, castor oil polyol is particularly preferred from the viewpoint of viscosity and the strength of the resulting coating film. The polyol compound (C) may be chemically modified. Known modification methods can be used. Examples include dimerization, trimerization, hydrogenation, oxidation, reduction, copolymerization of the unsaturated bond, and transesterification of the esterified portion.

[0029] The number-average molecular weight of the polyol compound (C) is not particularly limited, but from the viewpoint of pot life and hardness of the coating film, it is preferably 200 to 5,000, more preferably 400 to 4,000, and even more preferably 500 to 3,000.

[0030] The hydroxyl value of the polyol compound (C) is not particularly limited, but from the viewpoint of the appearance of the coating film, it is preferably 10 to 800 mg KOH / g, more preferably 30 to 600 mg KOH / g, and even more preferably 50 to 400 mg KOH / g.

[0031] <Raw materials for producing polyurea resin compositions> In the raw materials for producing the resin composition of the present invention, the molar ratio (amino group / hydroxyl group) of the amino group of the aspartic acid ester compound (B) and the hydroxyl group of the polyol compound (C) is preferably 99.5 / 0.5 to 45 / 55, more preferably 99.5 / 0.5 to 50 / 50, and even more preferably 99 / 1 to 60 / 40, from the viewpoint of chemical resistance and abrasion resistance of the coating film. In the raw materials for producing the resin composition of the present invention, the molar ratio (isocyanate group / (amino group + hydroxyl group)) of the isocyanate group of the polyisocyanate compound (A), the amino group of the aspartic acid ester compound (B), and the hydroxyl group of the polyol compound (C) is preferably 0.5 to 1.7, more preferably 0.6 to 1.5, even more preferably 0.7 to 1.4, and particularly preferably 0.8 to 1.3, from the viewpoint of coating film curing and chemical resistance.

[0032] From the viewpoint of coating thickness and workability, the raw material for producing the polyurea resin composition of the present invention preferably has a viscosity of 100 to 50,000 mPa·s, more preferably 1,000 to 30,000 mPa·s, and particularly preferably 1,500 to 15,000 mPa·s at 25°C immediately after preparation under solvent-free conditions. <Defoaming material (D)> In the raw materials for producing the polyurea resin composition of the present invention, it is preferable to add an antifoaming agent from the viewpoint of the chemical resistance of the coating film. Specific examples of antifoaming agents include silicone-based antifoaming agents, mineral oil-based antifoaming agents, acetylene-based antifoaming agents, and olefin-based antifoaming agents. Among these, olefin-based antifoaming agents are preferred in the present invention from the viewpoint of compatibility with the coating film. The content of the antifoaming agent is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and particularly preferably 1 to 3% by mass, relative to the resulting polyurea resin composition.

[0033] The raw materials for producing the polyurea resin composition of the present invention may contain a catalyst to improve the properties of the resulting coating film or to adjust the pot life and curing temperature.

[0034] Specific examples of catalysts include tertiary amines such as triethylamine, tributylamine, triethylenediamine, 2-dimethylaminoethyl ether, diazabicycloundecene, and N-methylmorpholine; metal catalysts such as dibutyltin diacetate, dibutyltin laurate, 3-diacetoxytetrabutylstanoxane, tin octenoate, tin chloride, butyl tin trichloride, bismuth trichloride, bismuth octenoate, tetrakis(2-ethylhexyl) titanate, tetrabutoxytitanium, and metal salts of acetoacetic acid; and quaternary ammonium salts.

[0035] The raw materials for producing the polyurea resin composition of the present invention may contain additives as needed.

[0036] Examples of additives include silica, basic inorganic salts, pH adjusters, metal oxide fine particles, tackifiers, waxes, UV absorbers, leveling agents, wetting agents, anti-sagging agents, anti-dripping agents, paint spread improvers, thixotropy agents, pigments, dyes, dispersants, diluents, and fillers. These may be used individually or in combination of two or more types. Furthermore, the above additives can be pre-added to polyisocyanate compounds (A) or aspartate ester compounds (B).

[0037] The amount of additive added can be determined appropriately depending on the purpose.

[0038] The raw materials for producing the polyurea resin composition of the present invention may optionally include other resins. Examples of other resins include melamine resin, epoxy resin, polyurethane resin, polyester resin, and polyolefin resin.

[0039] Among these, polyurethane resin, polyester resin, and polyolefin resin are preferred from the viewpoint of compatibility, with polyolefin resin being particularly preferred.

[0040] The amount of other resins added can be determined as appropriate within a range that does not impair the effects of the present invention, but is generally preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1 to 5% by mass.

[0041] Furthermore, any common organic solvent can be used as a diluent for the polyurea resin composition raw material of the present invention, as long as it does not react with the polyisocyanate compound (A).

[0042] Organic solvents that can be used as diluents include hydrocarbon compounds such as toluene, xylene, and cyclohexane; carbonyl compounds such as acetone, 2-butanone, and isophorone; and ester compounds such as ethyl acetate and butyl acetate. These may be used individually or in combination of two or more.

[0043] From the viewpoint of the physical properties of the coating film, the content of organic solvents in the raw materials for manufacturing the resin composition is preferably 10% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less. <Polyurea resin composition> The polyurea resin composition of the present invention is obtained from the raw materials for producing the polyurea resin composition of the present invention. The polyurea resin composition of the present invention can be obtained by mixing at least a polyisocyanate compound (A), an aspartic acid ester compound (B), and a polyol compound (C). A known mixing method can be employed. In addition, other optional components (D), such as catalysts and additives, may be mixed as needed. Other optional components (D), such as catalysts and additives, may be blended in advance with one or more of the polyisocyanate compound (A), aspartic acid ester compound (B), and polyol compound (C), or may be mixed simultaneously with the said components. <Application> The polyurea resin composition of the present invention can be used to form coatings on materials such as metals like iron plates and steel plates, plastics, films, sheets, ceramics, glass, concrete, fibers, and paper by roll coating, curtain flow coating, spray coating, electrostatic coating, bell coating, dipping, roller coating, brush coating, gravure printing, etc., as a primer, intermediate coat, or topcoat, or for applications such as sizing agent, reinforcing material, and protective coating.

[0044] The polyurea resin composition of the present invention can be suitably used to impart aesthetic properties, weather resistance, water resistance, chemical resistance, rust prevention, abrasion resistance, adhesion, and the like to the aforementioned materials.

[0045] Furthermore, the polyurea resin composition of the present invention is also useful as an adhesive, a tack, an elastomer, a foam, a surface treatment agent, and the like.

[0046] As described above, the polyurea resin composition of the present invention can be used as a paint to form a coating film, and can also be poured into a frame or mold to manufacture a molded article.

[0047] The polyurea resin composition of the present invention is reactive at room temperature, so heating is usually not necessary. However, heating may be used to accelerate curing after coating or other processes, or to improve low-temperature working conditions in winter or other seasons. The curing temperature can be appropriately determined based on the application method and curing time, and from a safety viewpoint, it is preferably 30 to 80°C.

[0048] As an apparatus for heating the resin composition of the present invention, known apparatuses can be used, taking into consideration the viscosity of the resulting polyurea resin and the shape of the object to be deposited. Specific examples of heating apparatuses include heating rollers, roller heaters, polyimide heaters, infrared radiation heaters, air high-temperature heaters, heat guns, dryers, drying ovens, baking ovens, constant-temperature dryers, and constant-temperature furnaces. [Examples]

[0049] The present invention will be further described in detail by examples and comparative examples, but the present invention is not limited in any way to the following examples.

[0050] In the examples and comparative examples, the following raw materials were used as is without purification or distillation. <Polyisocyanate compound (A)> A1: Nulate-modified HDI synthesized by the following method (isocyanate group content 21.9% by mass, viscosity 1,700 mPa·s, functional number 3.3) A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was placed under a nitrogen atmosphere, 200 parts by mass of HDI were added, and the temperature was then raised to 55°C. 0.5 parts by mass of a butyl cellosolve solution of 10 wt% 2-hydroxypropyltrimethylammonium p-tertiary butyl benzoate was added as a reaction catalyst. The reaction was continued at 60°C, and when the refractive index (at 25°C) reached 1.514, 0.5 parts by mass of a xylene solution of 3.4 wt% monochloroacetic acid was added to stop the reaction. Unreacted HDI was removed using a thin-film evaporator to obtain a nurate-modified HDI with an isocyanate group content of 21.9% by mass, a viscosity of 1,700 mPa·s, and a functional number of 3.3. A2: Biuret-modified HDI synthesized by the following method (isocyanate group content 23.5% by mass, viscosity 1,800 mPa·s, functional number 3.2) A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was placed under a nitrogen atmosphere. 100 parts by weight of HDI, 18 parts by weight of trimethyl phosphate, 25 parts by weight of methyl cellosolve acetate, and 1.3 parts by weight of water (HDI / water molar ratio = 8) were charged into the flask, and the reactor temperature was maintained at 160°C for 1 hour under stirring. Unreacted HDI was removed from the resulting reaction solution using a thin-film evaporator to obtain biuret-modified HDI with an isocyanate group content of 23.5% by weight, a viscosity of 1,800 mPa.s at 25°C, and a functional number of 3.2.

[0051] A3: HDI / TDI nurate synthesized by the following method (isocyanate group content 21.8%, viscosity 4,700 mPa·s, functional number 3.6) A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was placed under a nitrogen atmosphere. 96.6 parts by mass of HDI and 100 parts by mass of 2,4-TDI were added, and the temperature was then raised to 55°C. 0.5 parts by mass of a butyl cellosolve solution of 10 wt% 2-hydroxypropyltrimethylammonium p-tertiary butyl benzoate was added as a reaction catalyst. The reaction was continued at 60°C, and when the refractive index (at 25°C) reached 1.514, 0.5 parts by mass of a xylene solution of 3.4 wt% monochloroacetic acid was added to stop the reaction. Next, after removing HDI and TDI using a thin-film evaporator, 20 parts by mass of ethyl acetate was added as a solvent to obtain HDI / TDI nurate. A4: Isocyanate-terminated HDI prepolymer synthesized by the following method (isocyanate group content 20.5% by mass, viscosity 2,000 mPa·s, functional number 2) A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was placed under a nitrogen atmosphere. 100 parts by mass of hexamethylene diisocyanate (HDI) and 21.5 parts by mass of polypropylene glycol (number average molecular weight 750) were charged into the flask, and the reactor temperature was maintained at 95°C for 90 minutes under stirring to carry out the urethane reaction. After filtering the cooled reaction solution, unreacted HDI was removed using a thin-film evaporator. An isocyanate-terminated HDI prepolymer was obtained with an isocyanate group content of 20.5% by mass, a viscosity of 3,000 mPa·s at 25°C, a number-average molecular weight of 1520, and a functional number of 2. A5: Isocyanate-terminated HDI prepolymer synthesized by the following method (isocyanate group content 18.2% by mass, viscosity 21,310 mPa·s, functional number 2) A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet, and dropping funnel was placed in a nitrogen atmosphere, and 100 parts of HDI and 5.0 parts of polycaprolactonetriol with a number-average molecular weight of 300 were charged. Next, the reactor temperature was maintained at 90°C for 1 hour under stirring, and the urethane reaction was carried out. Next, the reactor temperature was lowered and maintained at 80°C, and the isocyanurate reaction catalyst tetramethylammonium capryate was added to carry out the isocyanurate reaction. Next, when the refractive index of the reaction solution increased to 0.0172, phosphoric acid was added to stop the reaction. Next, the reactor temperature was raised and maintained at 90°C for 1 hour. Next, the reaction solution was cooled and filtered, and unreacted HDI was removed using a thin-film evaporator to obtain an isocyanate-terminated HDI prepolymer with an NCO content of 18.2% by mass, a viscosity of 21310 mPa.s at 25°C, a number-average molecular weight of 1240, and a functional number of 2. <Amine compounds> B1: Aspartic acid ester compound (Feispartic F520, manufactured by Feiyang, amine value 190 mg KOH / g, viscosity 1,400 mPa·s) B2: Diethyltoluenediamine (manufactured by Tokyo Chemical Industry Co., Ltd., amine value 629 mgKOH / g, viscosity 121 mPa·s) B3: Aspartate ester compound (Desmophen 1420, manufactured by Covestro; amine value 201 mg KOH / g; viscosity 1,400 mPa·s) B4: Aspartate ester compound (Desmophen 1520, manufactured by Covestro; amine value 191 mg KOH / g; viscosity 1,300 mPa·s) <Polyol compound (C)> C1: Polyester polyol (Kuraray Polyol F-1010, manufactured by Kuraray Co., Ltd., hydroxyl value 168 mg KOH / g, viscosity 7,200 mPa·s, trifunctional) C2: Castor oil polyol (Polycastor #10, manufactured by Ito Oil Co., Ltd., hydroxyl value 156 mg KOH / g, viscosity 450 mPa·s, 5-functional) C3: Castor oil polyol (URIC F7500, manufactured by Ito Oil Co., Ltd., hydroxyl value 305 mgKOH / g, viscosity 550 mPa·s, trifunctional) C4: Ethylenediamine propylene oxide adduct (ADEKA "EDP-1100", hydroxyl value 217 mgKOH / g, viscosity 750 mPa·s, tetrafunctional) <Defoaming material (D)> D1: Liquid polyolefin resin oligomer (Lucant LX010, manufactured by Mitsui Chemicals, Inc.) The various physical properties were measured using the following evaluation method. (1) Isocyanate group content The result was obtained according to the back titration method of dinormalbutylamine with hydrochloride, as specified in JIS K 7301. (2) Functional number of isocyanates Derivatives were obtained by adding a large excess of methanol or ethanol to an isocyanate compound and curing it at 60°C for one week. The molecular weight of each derivative was measured by LC / MS, and the number of functions was determined using the following formula. Functionality = [(Molecular weight of ethanol derivative) - (Molecular weight of methanol derivative)] / 14 The LC / MS conditions are as follows: (Device name) JMS-LX2000 manufactured by JEOL Ltd. (LC measurement) Module 1 manufactured by Waters Japan Ltd. was used, with a column: ODS (Symmetry C-18), 3.9 mm × 150 mm (Waters Japan Ltd.), column temperature 40°C, detector: ultraviolet absorbance detector, detection wavelength: 254 nm. The mobile phase medium (%) was set in a gradient, with ACN (%A) / water (%B) = 70 / 30, and then linearly set to %A / %B = 100 / 0 over 30 minutes. After that, the measurement cycle time was set to %A / %B = 100 / 0 for a total of 60 minutes, and the measurement was performed with a medium flow rate of 1 ml / min. (MS measurement) Mass scan range: 20-1500, scan cycle time: 2.5s, acceleration voltage: 3kV, resolution: 500, ESI capillary voltage: 2.0kV, ESI capillary temperature: 270℃ (2) Amine value The result was obtained according to the indicator titration method specified in JIS K 7237. (3) Hydroxyl value The result was determined according to the indicator titration method specified in JIS K 1557-1:2007. (4) Molar ratio (amino group / hydroxyl group), molar ratio (isocyanate group / (amino group + hydroxyl group)) The values ​​were calculated from the amount of each component in the resin composition and the isocyanate group content, amine value, and hydroxyl value of each component determined in (1) to (3) above. (5) 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.). Measurements were taken twice: immediately after mixing all components and one hour later. The results were evaluated using the following criteria. (Immediately after mixing) 4: Viscosity less than 10,000 mPa·s 3: Viscosity of 10,000 mPa·s or more, and less than 15,000 mPa·s 2: Viscosity of 15,000 mPa·s or more, and less than 20,000 mPa·s 1: Viscosity of 20,000 mPa·s or higher (1 hour after mixing) 4. Viscosity less than 30,000 mPa·s 3: Viscosity of 30,000 mPa·s or more, and less than 50,000 mPa·s 2: Viscosity of 50,000 mPa·s or more, and less than 70,000 mPa·s 1: Viscosity of 70,000 mPa·s or higher, or solidified within 1 hour. In practical terms, a rating of 3 or higher is preferable.

[0052] (6) Tensile strength All components were quickly mixed using a metal spatula to a total volume of 60g. The resulting mixture was poured into a metal frame measuring 1mm thick, 15cm long, and 10cm wide, and left to stand at 25°C for 48 hours to produce a 1mm thick cured polyurea resin plate. The prepared cured plate was punched out into a dumbbell shape (size 5) to obtain test specimens. The tensile strength (N / mm²) of the test specimens was measured using a benchtop precision universal testing machine (Shimadzu Corporation, Autograph AGS-X) at 25°C. 2 ) Measurements were taken using 5 samples, with a gripping distance of 80 mm and a tensile speed of 500 mm / min. The average value of the 5 measurements was used.

[0053] (7) Chemical resistance A polyurea resin composition was coated onto a metal plate to a thickness of 2 mm using a Baker-type applicator and cured at 25°C for 24 hours. The cured material was then peeled from the metal plate, cut into 40 mm × 40 mm × 2 mm specimens, and immersed in a 5% by mass or 10% by mass aqueous acetic acid solution at 25°C for 60 days. The specimens were then evaluated according to the following criteria. 1: One or more signs of blistering, cracking, or leaching were observed in the test specimen. 2: No swelling, cracking, or leaching was observed in the test specimen, and the weight change before and after immersion was 20% or more. 3: No swelling, cracking, or leaching was observed in the test specimen, and the weight change before and after immersion was 15% or more but less than 20%. 4. No swelling, cracking, or leaching was observed in the test specimen, and the weight change before and after immersion was between 10% and 15%. 5: No blistering, cracking, or leaching was observed in the test specimen, and the weight change before and after immersion was less than 10%. In practical terms, a rating of 3 or higher is preferable. (8) Durometer hardness The durometer hardness was measured using an AKASHI durometer hardness tester, in accordance with JIS K 6253.

[0054] Example 1 23.3 g of polyisocyanate compound (A1) (0.121 moles of isocyanate groups), 28.6 g of aspartate ester compound (B1) (0.097 moles of amino groups), and 8.1 g of polyol compound (C1) (0.024 moles of hydroxyl groups) were mixed at 25°C for 20 seconds using a metal stirring rod until a uniform appearance was obtained to obtain a polyurea resin composition (molar ratio (amino groups / hydroxyl groups) = 80 / 20, molar ratio (isocyanate groups / (amino groups + hydroxyl groups)) = 1.0). Examples 2-13, Comparative Examples 1-8 A polyurea resin composition was obtained in the same manner as in Example 1, except that the isocyanate compounds, amine compounds, polyol compounds, defoaming agents, and other components of the types listed in Table 1 were used in the proportions listed in Table 1.

[0055] Tables 1 and 2 show the composition of the polyurea resin compositions in the examples and comparative examples, and the properties of the obtained polyurea resin compositions.

[0056] [Table 1]

[0057] [Table 2]

[0058] As shown in Tables 1 and 2, the polyurea resin compositions of the examples exhibited good chemical resistance to 10% acetic acid while maintaining good viscosity and tensile strength of the coating film under solvent-free conditions.

[0059] In Comparative Example 1, which did not contain amine compounds and was a polyurethane resin, the resulting coating film had inferior strength and chemical resistance.

[0060] Comparative Example 2, which used an aromatic diamine instead of an aspartic acid ester compound, showed inferior viscosity and chemical resistance, while Comparative Examples 3 and 4, which used polyols without ester bonds, showed poor chemical resistance to high concentrations of acetic acid.

Claims

1. A raw material for producing a polyurea resin composition, comprising a polyisocyanate compound (A), an aspartic acid ester compound (B), and a polyol compound (C), A raw material for producing polyurea resin compositions, characterized in that the polyol compound (C) contains an ester bond.

2. A raw material for producing a polyurea resin composition according to claim 1, wherein the polyisocyanate compound (A) has three or more functional properties.

3. The raw material for producing a polyurea resin composition according to claim 2, characterized in that the isocyanurate content of the polyisocyanate compound (A) is 70% by mass or more.

4. The raw material for producing a polyurea resin composition according to claim 2, characterized in that the polyisocyanate compound (A) contains 70% by mass or more of aliphatic polyisocyanate. Raw materials for manufacturing resin compositions

5. The raw material for producing a polyurea resin composition according to claim 1 or 2, characterized in that the polyol compound (C) includes a castor oil polyol with three or more functionalities and a modified version thereof.

6. The raw material for producing a polyurea resin composition according to claim 5, characterized in that the polyol compound (C) contains 70% by mass or more of a castor oil polyol with three or more functionalities and a modified version thereof.

7. The raw material for producing a polyurea resin composition according to claim 5, further containing 0.1 to 5% by mass of polyolefin resin.

8. A polyurea resin composition and a coating film obtained from the resin composition manufacturing raw materials of claims 1 to 7.

9. The coating film according to claim 7, characterized in that the durometer hardness of the coating film after immersion in a 10% acetic acid aqueous solution at 25°C for 60 days is D30 or higher.

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