Polyurea resin composition

Abstract

To provide a polyurea resin composition that exhibits a long pot life and high peel strength.SOLUTION: A polyurea resin composition comprises a main agent and a curing agent. The curing agent includes a first curing agent having an isocyanate group. The main agent includes a first main agent having an amino group. The first main agent contains an aspartic acid ester compound. The aspartic acid ester compound has a -NH-X-NH- structure in which respective amino groups of two molecules of aspartic acid ester are bound via a linking group X, and includes a first aspartic acid ester compound in which the linking group X is a divalent group corresponding to a dicyclohexylalkane, and a second aspartic acid ester compound in which the linking group X is a divalent group corresponding to a 2,2'-dialkyl-dicyclohexylalkane.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a polyurea resin composition. [Background technology]

[0002] Polyurethane resins have rubber-like elasticity and high strength, and are therefore used in a variety of applications, such as adhesives and paints.

[0003] Patent Document 1 proposes a two-component curing adhesive comprising a polyisocyanate composition (X) containing a polyisocyanate compound (A) and a polyol composition (Y) containing a polyol (B), in which the viscosity of the polyol composition at 50°C is 20 mPa·s or more and 180 mPa·s or less. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-24587 Summary of the Invention [Problem to be solved by the invention]

[0005] A one-component curable resin composition containing a curing agent is required to have a long pot life from the viewpoint of workability. On the other hand, high performance suitable for applications, such as high peel strength, is also required. Polyurethane resin compositions have excellent elasticity and relatively high strength, but curable resin compositions with even higher peel strength are required. [Means for solving the problem]

[0006] One aspect of the present disclosure is a polyurea resin composition including a base agent and a curing agent, the curing agent includes a first curing agent having an isocyanate group, The main agent includes a first main agent having an amino group. the first main agent contains an aspartic acid ester compound, The aspartic acid ester compound is The amino groups of the two aspartic acid ester molecules are linked via a linking group X to form an -NH-X-NH- structure; and a first aspartic acid ester compound in which the linking group X is a divalent group corresponding to a dicyclohexylalkane; and a second aspartic acid ester compound in which the linking group X is a divalent group corresponding to a 2,2'-dialkyl-dicyclohexylalkane. [Effects of the Invention]

[0007] A polyurea resin composition having a long pot life and high peel strength can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0008] Polyurethane resins are used in a variety of applications, including adhesives, paints, protective films, tires, shoe soles, clothing, etc. Cured polyurethane resins have relatively high peel strength, but materials with even higher peel strength are in demand.

[0009] In addition, polyurethane resins have a structure formed by the reaction of polyisocyanate and polyol, and are therefore poor in water resistance and susceptible to hydrolysis. Hydrolysis tends to progress more rapidly as temperatures increase. Therefore, for example, at temperatures higher than room temperature (e.g., 40°C) and under high humidity, the cured product is prone to deterioration, and properties such as peel strength are likely to decrease. Therefore, there is a demand for a curable resin composition that can maintain high peel strength even when the cured product is exposed to a high-humidity environment.

[0010] (Technology 1) In view of the above, the present disclosure relates to a polyurea resin composition. The polyurea resin composition of the present disclosure includes a main agent and a curing agent. The curing agent includes a first curing agent having an isocyanate group. The main agent includes a first main agent having an amino group. The first main agent includes an aspartic acid ester compound. The aspartic acid ester compound includes a first aspartic acid ester compound having an -NH-X-NH- structure in which the amino groups of two aspartic acid ester molecules are bonded via a linking group X, and the linking group X is a divalent group corresponding to a dicyclohexylalkane, and a second aspartic acid ester compound in which the linking group X is a divalent group corresponding to a 2,2'-dialkyl-dicyclohexylalkane.

[0011] By using a first aspartic acid ester compound and a second aspartic acid ester compound as the base compound, it is possible to achieve a good balance between reactivity with the isocyanate group of the first curing agent and a long pot life. By using the first aspartic acid ester compound, high peel strength (initial peel strength) of the cured product can be obtained. Thus, according to the present disclosure, a one-component polyurea resin composition can be provided that can achieve high peel strength while ensuring a long pot life.

[0012] Furthermore, the polyurea resin composition of the present disclosure can easily provide a cured product with high water resistance, and can easily maintain high peel strength even when exposed to a high humidity environment (e.g., when immersed in 40°C warm water for 24 hours).

[0013] (Technology 2) In the above (Technology 1), the linking group in the first aspartic acid ester compound may be a divalent group corresponding to dicyclohexylmethane. The linking group in the second aspartic acid ester compound may be a divalent group corresponding to 2,2'-dimethyl-dicyclohexylmethane. This provides a longer pot life and a higher peel strength of the cured product. Furthermore, the cured product is more likely to maintain a high peel strength even when exposed to a high-humidity environment for a long period of time.

[0014] (Technology 3) In the above (Technology 1) or (Technology 2), the content of the first aspartic acid ester compound in the base resin may be 50% by mass or more and 90% by mass or less. The content of the second aspartic acid ester compound in the base resin may be 5% by mass or more and 30% by mass or less. When the contents of each component contained in the base resin are within these ranges, a polyurea resin composition having an excellent balance between a long pot life and high peel strength can be obtained.

[0015] (Technology 4) In any one of the above (Technology 1) to (Technology 3), the first main agent may further contain a rubber-like component having a secondary amino group at its terminal, which results in a higher peel strength of the cured product.

[0016] (Technology 5) In the above (Technology 4), the content of the rubber component in the base resin may be 5% by mass or more and 20% by mass or less. When the content of the rubber component is in this range, a long pot life can be ensured and the cured product can be given appropriate flexibility, resulting in higher peel strength.

[0017] (Technology 6) In any one of the above (Technology 1) to (Technology 5), the first main agent may further contain a third aspartic acid ester compound. The third aspartic acid ester compound has an -NH-Y-NH- structure in which the amino groups of two aspartic acid ester molecules are bonded via an alkylene group serving as a linking group Y. The first main agent may or may not contain a third aspartic acid ester compound. When the first main agent contains a third aspartic acid ester compound, it is easy to increase the reaction rate and adjust the peel strength of the cured product while maintaining a relatively long pot life.

[0018] (Technology 7) In the above (Technology 6), the linking group in the third aspartic acid ester compound may be a 2-methyl-1,5-pentylene group. When a third aspartic acid ester compound having such a linking group is used, the reaction rate can be more easily controlled.

[0019] (Technology 8) In the above (Technology 6) or (Technology 7), the content of the third aspartic acid ester compound in the base resin may be 20% by mass or less, which tends to achieve a longer pot life and higher peel strength.

[0020] (Technology 7) In any one of the above (Technology 1) to (Technology 6), the first curing agent is First isocyanate compound: an aliphatic polyisocyanate polymer; Second isocyanate compound: allophanate-modified aliphatic polyisocyanate; Third isocyanate compound: a polymeric polyisocyanate component containing an alicyclic polyisocyanate as a constituent unit; When such a first curing agent is used, the cured product has high water resistance and durability, as well as high peel strength. In addition, the workability is also excellent.

[0021] (Technology 8) In the above (Technology 7), the first isocyanate compound may include an isocyanurate trimer of 1,5-pentamethylene diisocyanate. The second isocyanate compound may include allophanate-modified 1,6-hexamethylene diisocyanate. The third isocyanate compound may include a polymeric polyisocyanate component containing isophorone diisocyanate as a constituent unit. Higher peel strength is easily obtained while maintaining a long pot life.

[0022] (Technology 9) In the above (Technology 7) or (Technology 8), the content of the first isocyanate compound in the first curing agent may be 35 mol% or more and 55 mol% or less. The content of the second isocyanate compound in the first curing agent may be 20 mol% or more and 40 mol% or less. The content of the third isocyanate compound in the first curing agent may be 10 mol% or more and 35 mol% or less. The content of each isocyanate compound in the first curing agent is the molar ratio of each isocyanate compound to the entire first curing agent, when the entire first curing agent is taken as 100 mol%. By keeping the content of each isocyanate compound within the above range, higher water resistance and peel strength of the cured product can be obtained while maintaining a long pot life. In addition, excellent workability can be easily ensured.

[0023] (Technology 10) In any one of the above (Technology 1) to (Technology 9), the polyurea resin composition may further contain a crystalline polyester, which makes it easier to obtain a cured product with higher peel strength.

[0024] (Technology 11) In the above (Technology 10), the proportion of the crystalline polyester may be 10 parts by mass or less per 100 parts by mass of the main agent, in which case the cured product can have higher water resistance.

[0025] (Technology 12) In any one of the above (Technology 1) to (Technology 11), the polyurea resin composition may be an adhesive resin composition. The polyurea resin composition of the present disclosure is useful as an adhesive resin composition because it has excellent peel strength (initial peel strength) of the cured product. In addition, the polyurea resin composition is also excellent in water resistance and durability, and the cured product easily maintains high peel strength even when exposed to a high humidity environment. For this reason, the polyurea resin composition is useful as an adhesive resin composition.

[0026] (Technology 13) In any one of the above (Technology 1) to (Technology 11), the polyurea resin composition may be a resin composition for paint. The polyurea resin composition of the present disclosure is useful as a resin composition for paint because it has excellent peel strength of the cured product. Furthermore, the polyurea resin composition is also excellent in water resistance and durability, and the cured product easily maintains high peel strength even when exposed to a high humidity environment. In addition, the cured product has high strength and excellent scratch resistance. For these reasons, the polyurea resin composition is useful as a resin composition for paint.

[0027] The polyurea resin composition of the present disclosure will be described in more detail below, including the above (Technology 1) to (Technology 13), with reference to the drawings as necessary. At least one of the above (Technology 1) to (Technology 13) may be combined with at least one of the elements described below, provided that there is no technical contradiction.

[0028] [Polyurea resin composition] The polyurea resin composition of the present disclosure includes a base agent and a curing agent. The base agent includes a first base agent having an amino group. The curing agent includes a first curing agent having an isocyanate group. The polyurea resin composition may further include another base agent (hereinafter sometimes referred to as a second base agent), another curing agent (hereinafter sometimes referred to as a second curing agent), a thermoplastic resin, an additive, etc., as necessary.

[0029] (Main ingredient) The main component of the polyurea resin composition is a component having active hydrogen that reacts with the isocyanate group of the first curing agent, and includes at least a first main component having an amino group.

[0030] The first main ingredient contains an aspartic acid ester compound. The aspartic acid ester compound contains a first aspartic acid ester compound and a second aspartic acid ester compound as essential components. The aspartic acid ester compound may further contain a third aspartic acid ester compound as an optional component. The aspartic acid ester compound may contain an aspartic acid ester compound (sometimes referred to as a fourth aspartic acid ester compound) other than the first to third aspartic acid ester compounds, as needed.

[0031] (Aspartic acid ester compounds) Both the first aspartic acid ester compound and the second aspartic acid ester compound have an -NH-X-NH- structure in which the amino groups of two aspartic acid ester molecules are linked via a linking group X. The third aspartic acid ester compound has an -NH-Y-NH- structure in which the amino groups of two aspartic acid ester molecules are linked via an alkylene group serving as a linking group Y. Thus, each aspartic acid ester compound has a secondary amino group. The use of the first aspartic acid ester compound allows for a relatively high reaction rate between the base resin and the curing agent while maintaining a long pot life, resulting in high initial peel strength. Furthermore, the cured product has high water resistance, making it easy to maintain high peel strength even when exposed to a high-humidity environment. The use of the second aspartic acid ester compound allows for a long pot life while ensuring high peel strength of the cured product. The use of the third aspartic acid ester compound allows for easy adjustment of the reaction rate and peel strength.

[0032] (First aspartic acid ester compound) The first aspartic acid ester compound is different from the second aspartic acid ester compound. In the first aspartic acid ester compound, the linking group X is a divalent group corresponding to a dicyclohexyl alkane. Examples of such dicyclohexyl alkanes include dicyclohexylmethane, 1,2-dicyclohexylethane, and 2,2-dicyclohexylpropane. The dicyclohexyl alkanes include dicyclohexyl C1-6 It may be an alkane, dicyclohexyl C 1-4 The dicyclohexyl alkane may be dicyclohexylmethane, which is easily available and can easily provide a higher peel strength and a long pot life. In the dicyclohexyl alkane, the cyclohexyl moiety preferably has no substituent.

[0033] The bonding position of the linking group X to the amino group may be the o-position or m-position relative to the alkane moiety (i.e., alkylene group) sandwiched between the two cyclohexyl groups in each cyclohexyl group, but is preferably the p-position.

[0034] In the first aspartate ester, the total of four ester moieties in the two aspartate ester residues may be, for example, alkyl esters. The alkyl moiety of the alkyl ester may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. The number of carbon atoms in the alkyl moiety may be 1 to 6 or 1 to 4. The alkyl moiety may be either linear or branched. At least one of the structures of the four ester moieties may be different, or all may be the same.

[0035] The content of the first aspartic acid ester compound in the main component (the entire main component) may be 50% by mass or more, or may be 55% by mass or more. From the viewpoint of obtaining higher peel strength and easily ensuring a longer pot life, the content of the first aspartic acid ester compound in the main component is preferably 60% by mass or more. The content of the first aspartic acid ester compound in the main component (the entire main component) may be 90% by mass or less. In this case, a longer pot life is easily obtained.

[0036] (Second aspartic acid ester compound) In the second aspartic acid ester compound, the linking group X is a divalent group corresponding to a 2,2'-dialkyl-dicyclohexylalkane. For the dicyclohexylalkane in such a divalent group, the explanation and examples for the first aspartic acid ester compound can be referred to. The dicyclohexylalkane is a dicyclohexyl C 1-6 It may be an alkane, dicyclohexyl C 1-4 The alkyl group bonded to the cyclohexyl moiety may be an alkane. Examples of alkyl groups bonded to the cyclohexyl moiety include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. 1-6 It may be an alkyl group, 1-4 It may be an alkyl group. From the viewpoints of easy availability and the likelihood of achieving a longer pot life, the linking group X is preferably a divalent group corresponding to 2,2'-dimethyl-dicyclohexylmethane. In the 2,2'-dialkyl-dicyclohexylalkane, the cyclohexyl moiety preferably has no substituents other than the alkyl groups at the 2- and 2'-positions.

[0037] The bonding position of the linking group X to the amino group may be the o-position or m-position relative to the alkane moiety (i.e., alkylene group) sandwiched between the two cyclohexyl groups in each cyclohexyl group, but the p-position is preferred. Note that the positions of the alkyl groups at the 2- and 2'-positions correspond to the m-position relative to the alkylene group in each cyclohexyl group.

[0038] In the second aspartic acid ester, the total of four ester moieties in the two aspartic acid ester residues may be, for example, alkyl esters. The alkyl moiety of the alkyl ester may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. The number of carbon atoms in the alkyl moiety may be 1 to 6 or 1 to 4. The alkyl moiety may be either linear or branched. At least one of the structures of the four ester moieties may be different, or all may be the same.

[0039] From the viewpoint of ensuring a longer pot life, the content of the second aspartic acid ester compound in the main component (total main component) is preferably 5% by mass or more. From the viewpoint of easily ensuring a higher peel strength, the content of the second aspartic acid ester compound in the main component (total main component) may be 30% by mass or less, or may be 20% by mass or less.

[0040] (Tertiary aspartic acid ester compounds) The polyurea resin composition may or may not contain a tertiary aspartic acid ester compound.

[0041] In the third aspartic acid ester compound, the linking group Y is an alkylene group. The alkylene group may be linear or branched. Examples of the alkylene group include a methylene group, a 1,1-ethylene group, a 1,2-ethylene group, a propylene group, a trimethylene group, a 1,4-butylene group, a 1,3-butylene group, a 1,5-pentylene group, a 1,6-hexylene group, and a 2-methyl-1,5-pentylene group. The alkylene group may be a C 1-10 may be an alkylene group, C 1-8 may be an alkylene group, C 3-8 may be an alkylene group, C 4-6 It may be an alkylene group. Preferably, the linking group Y has no substituent. Note that this substituent does not include an alkyl group on the side chain of a branched alkylene group.

[0042] In the third aspartate ester, the total of four ester moieties in the two aspartate ester residues may be, for example, alkyl esters. The alkyl moiety of the alkyl ester may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. The number of carbon atoms in the alkyl moiety may be 1 to 6 or 1 to 4. The alkyl moiety may be either linear or branched. At least one of the structures of the four ester moieties may be different, or all may be the same.

[0043] From the viewpoint of easily obtaining a longer pot life and higher peel strength, the content of the third aspartic acid ester compound in the main component (total main component) is preferably 20% by mass or less. When the polyurea resin composition contains the third aspartic acid ester compound, from the viewpoint of easily obtaining the effect of increasing the reaction rate, the content of the second aspartic acid ester compound in the main component (total main component) may be 5% by mass or more, or may be 10% by mass or more.

[0044] (Quaternary aspartic acid ester compounds) The fourth aspartic acid ester compound includes aspartic acid ester compounds other than the first to third aspartic acid ester compounds. Such aspartic acid ester compounds are compounds having a structure derived from an aspartic acid ester. An example of the fourth aspartic acid ester compound is α-(2-{[1,2-bis(ethoxycarbonyl)ethyl]amino}(methyl)ethyl)-ω-(2-{[1,2-bis(ethoxycarbonyl)ethyl]amino}(methyl)ethoxy)poly[oxy(methyl)ethylene] (CAS#: 152637-10-0).

[0045] The total amount of the first aspartic acid ester compound, the second aspartic acid ester compound, and the third aspartic acid ester compound may be 50% by mass or more, 75% by mass or more, or 90% by mass or more of the total aspartic acid ester compounds. The aspartic acid ester compounds may be composed solely of the first aspartic acid ester compound and the second aspartic acid ester compound, or may be composed solely of the first to third aspartic acid ester compounds.

[0046] (rubber-like component) The first main agent may contain a rubber-like component (sometimes referred to as the "first rubber-like component") having a secondary amino group at its terminal. The use of the first rubber-like component can improve initial adhesive strength and ensure high peel strength of the cured product. Because the first rubber-like component has a secondary amino group at its terminal, it is incorporated into the reaction with the first curing agent. This improves the water resistance of the cured product compared to when a non-reactive rubber-like component is used, and the cured product can maintain high peel strength even when exposed to a high-humidity environment.

[0047] The first rubber component may have, for example, a polybutadiene moiety. Examples of such a first rubber component include butadiene-acrylonitrile copolymers having terminal secondary amino groups. The terminal secondary amino groups may be aliphatic or may form a nitrogen-containing ring.

[0048] Examples of the first rubber component include, but are not limited to, "Hypro (registered trademark) ATBN 1300x16 (manufactured by CVC THERMOSET SPECIALITIES)" and "Hypro (registered trademark) ATBN 1300x42 (manufactured by CVC THERMOSET SPECIALITIES)."

[0049] The first rubber component may be used alone or in combination of two or more.

[0050] The weight average molecular weight (Mw) of the first rubbery component may be from 1000 to 7000, from 3000 to 5000, or from 3500 to 4500. When the Mw of the first rubbery component is within this range, it is easy to impart appropriate flexibility to the cured product and to obtain higher peel strength.

[0051] In this specification, the weight average molecular weight Mw is a weight average molecular weight measured using gel permeation chromatography (GPC) and converted into polystyrene.

[0052] In this specification, Mw can be determined, for example, by the following procedure. The component for which Mw is to be measured is dissolved in a solvent to prepare a measurement sample. The solvent is selected from liquid media that can dissolve the component depending on the type of component. GPC is measured using the measurement sample under the following conditions to determine Mw. Equipment: SHODEX SYSTEM-21H Detector: RI detector Mobile phase: tetrahydrofuran Flow rate: 1mL / min Column: SHODEX KF-806M, KF-804, KF-803 Column temperature: 40℃ Reference material: Standard polystyrene (select a commercially available standard polystyrene with a Mw close to that of the component to be measured.)

[0053] The content of the first rubber component in the main component (total main component) may be 3% by mass or more, or 5% by mass or more. When the content of the first rubber component is within this range, the cured product exhibits appropriate elasticity, further increasing the initial peel strength of the cured product. The content of the first rubber component in the main component (total main component) may be 25% by mass or less, or 20% by mass or less. When the content of the first rubber component is within this range, a longer pot life is likely to be obtained.

[0054] The content of the first rubber component in the base material (the entire base material) may be 3% by mass or more and 25% by mass or less (or 20% by mass or less), or 5% by mass or more and 25% by mass or less (or 20% by mass or less).

[0055] The polyurea resin composition may contain a rubber-like component (sometimes referred to as a second rubber-like component) in addition to the first rubber-like component. The second rubber-like component may be a rubber-like component having a reactive functional group other than a secondary amino group at its terminal (e.g., a primary amino group, a carboxy group, or a hydroxy group), or may be a rubber-like component having no reactive functional group. The proportion of the first rubber-like component in the total amount of rubber-like components contained in the polyurea resin composition (the total amount of the first rubber-like component and the second rubber-like component) may be 50% by mass or more, 75% by mass or more, or 90% by mass or more. The proportion of the first rubber-like component in the total amount of rubber-like components is 100% by mass or less. The rubber-like component may be composed solely of the first rubber-like component.

[0056] (others) The base agent may optionally contain a component having a secondary amino group in addition to the first base agent (such as an aspartic acid ester compound) and the first rubber-like component. The base agent may also contain a component having a primary amino group, but from the viewpoint of easily ensuring a longer pot life, the content of the component having a primary amino group is preferably 10% by mass or less, more preferably 5% by mass or less or 1% by mass or less. It is also preferable if the base agent consists solely of a component having a secondary amino group.

[0057] The total amount of the first main component and the first rubber component in the main component is preferably more than 90% by mass. The total amount of the aspartic acid ester compound and the first rubber component in the main component is 100% by mass or less. The main component may be composed solely of aspartic acid ester compounds (particularly, first and second aspartic acid ester compounds, or first to third aspartic acid esters), or may be composed solely of an aspartic acid ester and the first rubber component.

[0058] The polyurea resin composition may optionally contain, in addition to the first main component, a component that reacts with a curing agent having an isocyanate group. Because such a component reacts with an isocyanate group, it is generally classified as a main component (sometimes referred to as a second main component). Examples of the second main component include components having a reactive functional group (excluding an amino group) with active hydrogen, such as a hydroxy group or a carboxy group. From the viewpoint of enhancing the reactivity of the aspartic acid ester compound, a component having a hydroxy group is preferred. These components may contain one reactive functional group with active hydrogen, such as a hydroxy group, that reacts with an isocyanate group, but preferably two or more.

[0059] The compound (polyol compound) having two or more hydroxy groups is preferably an oligomer or polymer type polyol compound. Examples of such polyol compounds include polyether polyol, polyester polyol, polyether ester polyol, polyurethane polyol, polyester urethane polyol, polyether urethane polyol, and polycarbonate polyol. The polyol compound may have an aromatic ring, an aliphatic ring, and / or a heterocyclic ring (e.g., a heterocyclic ring containing a heteroatom (e.g., oxygen, nitrogen, and / or sulfur) as a ring constituent element).

[0060] The polyol compound may be linear or branched. The polyol compound may be, for example, a polyester polyol having a dendritic branched structure in which a plurality of polyoxycarboxylic acid units are linked. Such polyester polyols include compounds called polyester polyols having a hyperbranched structure. Generally, AB polyols such as polyoxycarboxylic acids having a plurality of hydroxy groups are used. m In the polyester polyol having a hyperbranched structure formed by linking AB type monomers (m is an integer of 2 or more), mThe residues of the dendritic monomer are classified into three types of units: terminal units (terminal portions) in which m B groups remain, linear units (unbranched portions) in which m B groups are connected via one B group residue and the remaining (m-1) B groups remain, and dendritic units (branched portions) in which m B groups are connected via two or more B group residues. Thus, hyperbranched structures differ from dendrimers in the presence of linear units.

[0061] From the viewpoint of easily ensuring a higher peel strength of the cured product, the proportion of the second main component (such as a polyol compound) in the total main components (the first main component and the second main component) is preferably less than 10% by mass, more preferably 5% by mass or less or 1% by mass or less.

[0062] (hardening agent) The curing agent includes at least a first curing agent having an isocyanate group. The first curing agent is also called an isocyanate compound. As the first curing agent, a monoisocyanate compound having one isocyanate group may be used, or a polyisocyanate compound having two or more isocyanate groups may be used. As the first curing agent, it is preferable to use at least a polyisocyanate compound. As the first curing agent, a polyisocyanate compound and a monoisocyanate compound may be used in combination.

[0063] The isocyanate compound may be at least one selected from the group consisting of aliphatic isocyanate compounds, alicyclic isocyanate compounds, and aromatic isocyanate compounds. The isocyanate compound may be modified or unmodified. Modified isocyanate compounds also include multimers of isocyanate compounds (e.g., aliphatic polyisocyanate multimers). Examples of modified isocyanate compounds include allophanate-modified isocyanate compounds, polyol-modified isocyanate compounds, urethane-modified isocyanate compounds, and isocyanurate-modified isocyanate compounds (e.g., isocyanurate multimers of isocyanate compounds). The multimer may be, for example, a dimer or more and a decamer or a dimer or more and a hexamer.

[0064] From the viewpoint of easily adjusting the peel strength, durability, water resistance, etc. of the cured product, it is preferable to use a combination of multiple isocyanate compounds. More specifically, the first curing agent is First isocyanate compound: an aliphatic polyisocyanate polymer; Second isocyanate compound: allophanate-modified aliphatic polyisocyanate; It is preferable to include a third isocyanate compound: a polymeric polyisocyanate component containing an alicyclic polyisocyanate as a structural unit. The first isocyanate compound and the second isocyanate compound are different components. The use of the first isocyanate compound facilitates the growth of a crosslinked structure, improving the durability and water resistance of the cured product and resulting in higher peel strength. The use of the second isocyanate compound facilitates the achievement of a longer pot life, improving workability, and increasing the elasticity of the cured product. The use of the third isocyanate compound ensures a longer pot life while maintaining high peel strength of the cured product. When the peel strength of the cured product is high, the reactivity between the first main agent and the first curing agent is high, which tends to shorten the pot life. In the present disclosure, by combining a first aspartic acid ester compound, a second aspartic acid ester compound, and, if necessary, a first rubber-like component, high peel strength of the cured product and a long pot life can be achieved. Even when primary, secondary, and tertiary isocyanate compounds are used in combination, high durability and water resistance of the cured product are ensured, higher peel strength is obtained, a longer pot life is ensured, and workability is improved.

[0065] Examples of the aliphatic polyisocyanate of the first isocyanate compound include alkylene diisocyanates. Examples of the alkylene diisocyanate include ethylene diisocyanate, propylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate (PDI), and 1,6-hexamethylene diisocyanate (HDI). The number of carbon atoms in the alkylene moiety of the alkylene diisocyanate may be 2 or more and 10 or less, 3 or more and 8 or less, or 4 or more and 6 or less. The alkylene moiety may be linear or branched.

[0066] Examples of the polymer include a polymer of the above-mentioned aliphatic polyisocyanate and an amino group-containing compound (for example, an isocyanurate trimer of an aliphatic polyisocyanate). As the first polyisocyanate compound, a single aliphatic polyisocyanate polymer may be used, or two or more aliphatic polyisocyanate polymers may be used in combination. From the viewpoint of further improving the peel strength and water resistance of the cured product, an isocyanurate trimer of 1,5-pentamethylene diisocyanate may be used as the first isocyanate compound. Examples of such first isocyanate compounds include Stabio D-370N and D-376N manufactured by Mitsui Chemicals, Inc.

[0067] The aliphatic polyisocyanate polymer preferably has two or more isocyanate groups, more preferably three or more isocyanate groups. The aliphatic polyisocyanate polymer may have four or less isocyanate groups. The aliphatic polyisocyanate polymer may have three isocyanate groups.

[0068] The content of the first isocyanate compound in the first curing agent may be 35 mol% or more, or may be 40 mol% or more. When the content of the first isocyanate compound is in this range, the cured product has a higher peel strength and high water resistance. The content of the first isocyanate compound in the first curing agent may be 70 mol% or less, or may be 55 mol% or less. When the content of the first isocyanate compound is in this range, the cured product has a relatively high flexibility, so that a higher peel strength is obtained and a longer pot life is easily ensured.

[0069] The content of the first isocyanate compound in the first curing agent may be 35 mol% or more and 70 mol% or less (or 55 mol% or less), or 40 mol% or more and 70 mol% or less (or 55 mol% or less).

[0070] Examples of the allophanate-modified aliphatic polyisocyanate of the second isocyanate compound include allophanate-modified products of the aliphatic polyisocyanate as the first isocyanate compound (such as allophanate-modified alkylene diisocyanates). The description of the first isocyanate compound can also be referenced for the number of carbon atoms and structure of the alkylene moiety. As the second isocyanate compound, a single allophanate-modified aliphatic polyisocyanate may be used, or two or more allophanate-modified aliphatic polyisocyanates may be used in combination. From the viewpoints of obtaining a longer pot life and easily ensuring high workability, a second isocyanate compound containing an allophanate-modified 1,6-hexamethylene diisocyanate may be used as the second isocyanate compound.

[0071] The content of the second isocyanate compound in the first curing agent may be 20 mol% or more, 30 mol% or more, or even 35 mol% or more. When the content of the second isocyanate compound is within this range, a longer pot life is likely to be obtained, high workability is likely to be ensured, and the elasticity of the cured product can be increased. The content of the second isocyanate compound in the first curing agent may be 45 mol% or less, or even 40 mol% or less. When the content of the second isocyanate compound is within this range, high curability is likely to be obtained, and the cured product can have higher peel strength and high water resistance.

[0072] The allophanate-modified aliphatic polyisocyanate preferably has two or more isocyanate groups. The allophanate-modified aliphatic polyisocyanate may have three or less isocyanate groups. An allophanate-modified aliphatic polyisocyanate having two isocyanate groups may also be used.

[0073] The content of the second isocyanate compound in the first curing agent may be 20 mol% or more and 45 mol% or less (or 40 mol% or less), 30 mol% or more and 45 mol% or less (or 40 mol% or less), or 35 mol% or more and 45 mol% or less (or 40 mol% or less).

[0074] The polymeric polyisocyanate component of the third isocyanate compound contains an alicyclic polyisocyanate as a constituent unit, in other words, the polymeric polyisocyanate component contains residues of an alicyclic polyisocyanate.

[0075] Examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), cyclohexane 1,3-diisocyanate, and cyclohexane 1,4-diisocyanate. The alicyclic ring of the alicyclic polyisocyanate may be 4 to 10-membered, 5 to 8-membered, or 5 or 6-membered. The alicyclic ring may have a substituent such as an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. The alkyl group may be C 1-6 may be an alkyl group, 1-4 The alkyl group may be a straight chain or a branched chain.

[0076] The polymeric polyisocyanate component may contain one molecule of alicyclic polyisocyanate as a constituent unit, or may contain two or more molecules of alicyclic polyisocyanate. The polymeric polyisocyanate component has two or more isocyanate groups. Among these, it is preferable to use a polymeric polyisocyanate component having two to three isocyanate groups (particularly a polymeric diisocyanate component having two isocyanate groups). The polymeric polyisocyanate component may have an isocyanate group on a side chain, pendant from the main chain (at a position other than the terminal), or at the terminal. As such, the polymeric polyisocyanate component has an isocyanate group involved in the curing reaction and can be further polymerized, and therefore can also be called a prepolymer.

[0077] The polymeric polyisocyanate component contains an alicyclic polyisocyanate as a structural unit, and other structural units are not particularly limited. For example, a compound polymerized by reacting an alicyclic polyisocyanate with a compound reactive with isocyanate (e.g., a polyol) can be used as the polymeric polyisocyanate component. If necessary, the polymeric polyisocyanate component may further contain a polyisocyanate other than the alicyclic polyisocyanate as a structural unit. From the viewpoint of easily adjusting the pot life and peel strength of the cured product, a polymeric polyisocyanate component containing isophorone diisocyanate as a structural unit may be used as the third isocyanate compound.

[0078] Examples of the polymeric polyisocyanate component include, but are not limited to, "Desmodur VP LS 2371," "Desmodur E 40480 MPA," "Desmodur NZ 300," and "Desmodur NZ 486 BA," manufactured by Sumika Covestro Urethane Co., Ltd.

[0079] The polymeric polyisocyanate component may be used alone or in combination of two or more.

[0080] The content of the third isocyanate compound in the first curing agent may be 10 mol% or more, or may be 15 mol% or more. When the content of the third isocyanate compound is in this range, a longer pot life is likely to be obtained, and the flexibility of the cured product is increased, making it easier to obtain higher peel strength. The content of the third isocyanate compound in the first curing agent may be 35 mol% or less, or may be 25 mol% or less. When the content of the third isocyanate compound is in this range, the flexibility of the cured product is relatively high, making it easier to obtain higher peel strength and ensure a longer pot life.

[0081] The content of the third isocyanate compound in the first curing agent may be 10 mol% or more and 35 mol% or less (or 25 mol% or less), or may be 15 mol% or more and 35 mol% or less (or 25 mol% or less).

[0082] The viscosity of the polymeric polyisocyanate component at 23°C may be 1000 mPa·s or more and 20000 mPa·s or less.

[0083] The first curing agent may contain an isocyanate compound other than the first to third isocyanate compounds. Examples of such an isocyanate compound (sometimes referred to as a fourth isocyanate compound) include modified isocyanates other than the second isocyanate compound, alicyclic isocyanates, aromatic isocyanates, and polymeric polyisocyanate components other than the third isocyanate compound. Examples of aromatic isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, and naphthalene diisocyanate (e.g., aromatic polyisocyanates). Examples of polymeric polyisocyanate components other than the third isocyanate compound include polymeric polyisocyanate components containing at least one selected from the group consisting of aliphatic polyisocyanates and aromatic polyisocyanates as a constituent unit. Examples of the polymeric polyisocyanate component containing an aliphatic polyisocyanate as a constituent unit include a polymeric polyisocyanate component containing 1,6-hexamethylene diisocyanate as a constituent unit.

[0084] The molar ratio of the total amount of the first to third isocyanate compounds in the first curing agent may be, for example, 50 mol % or more, 75 mol % or more, or 90 mol % or more. The molar ratio of the total amount of the first to third isocyanate compounds in the first curing agent is 100 mol % or less. The first curing agent may be composed only of the first to third isocyanate compounds.

[0085] In addition to the first curing agent, the polyurea resin composition may contain other curing agents besides the first curing agent, a curing accelerator, a polymerization catalyst, a polymerization initiator, etc. These components may be referred to as a second curing agent. The proportion of the first curing agent in the entire curing agent (total amount of the first curing agent and the second curing agent) may be 50 mass% or more, 75 mass% or more, or 90 mass% or more. The proportion of the first curing agent in the entire curing agent is 100 mass% or less. The curing agent may be composed of only the first curing agent.

[0086] (others) The polyurea resin composition may contain a thermoplastic resin. From the viewpoint of easily ensuring a higher peel strength of the cured product, it is preferable to use a crystalline polyester as the thermoplastic resin. Examples of the crystalline polyester include crystalline polyethylene terephthalate.

[0087] The proportion of the thermoplastic resin (such as crystalline polyester) may be 15 parts by mass or less, or 10 parts by mass or less, relative to 100 parts by mass of the base material. When the polyurea resin composition contains a crystalline polyester, the proportion of the thermoplastic resin (such as crystalline polyester) may be 0.1 parts by mass or more relative to 100 parts by mass of the base material.

[0088] The polyurea resin composition may contain additives as needed, including, but not limited to, silane coupling agents, carbon black, antifoaming agents, leveling agents, pigments, stress relaxation agents, and ion scavengers.

[0089] The polyurea resin composition may contain a solvent (such as an organic solvent) as needed. In this case, a longer pot life is likely to be obtained. The polyurea resin composition may be a solvent-free type that does not contain a solvent. By adjusting the type and amount of the solvent, it is possible to adjust the pot life while ensuring high peel strength of the cured product.

[0090] The polyurea resin composition is produced (or prepared) by, for example, mixing the constituent components. For example, after mixing the components other than the curing agent, the curing agent may be added and the whole may be mixed. The preparation of the polyurea resin composition may be carried out under an inert gas atmosphere or atmospheric pressure, as necessary. The preparation of the polyurea resin composition (for example, at least a part of the steps) may be carried out under heating, as necessary.

[0091] The polyurea resin composition of the present disclosure has a long pot life and yet provides a cured product with high peel strength. Furthermore, the cured product has high water resistance, and even when exposed to a high humidity environment, deterioration of the cured product is suppressed, maintaining high peel strength (in other words, high peel strength retention). Furthermore, the cured product has excellent strength and excellent scratch resistance. Therefore, the polyurea resin composition is particularly useful as an adhesive resin composition or a coating resin composition. However, the uses of the polyurea resin composition are not limited to these.

[0092] [Example] The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to the following examples.

[0093] Examples 1 to 23 and Comparative Examples 1 to 13 (1) Preparation of Polyurea Resin Composition The components classified as the base resin shown in the table were blended in the mass ratios shown in the table, and the curing agent shown in the table was further blended. The equivalent ratio of the isocyanate group (NCO) contained in the curing agent to the active hydrogen (NH + OH) of the amino group and hydroxy group contained in the base resin was NCO / (NH + OH) = 1.05. In this way, a one-component liquid polyurea resin composition was prepared.

[0094] The following components were used as the components shown in the tables. In Tables 1 and 2, the first isocyanate compound:second isocyanate compound:third isocyanate compound=45 mol %:40 mol %:15 mol %. In Tables 3 to 5, the molar ratios of the isocyanate compounds were the values ​​shown in the tables.

[0095] (a) First aspartic acid ester compound: Desmophen NH1420, manufactured by Covestro AG (b) Secondary aspartic acid ester compound: Desmophen NH1520, manufactured by Covestro AG (c) Tertiary aspartic acid ester compound: Desmophen NH1220, manufactured by Covestro AG (d1) Polyamide resin 1: Vegichem Green V-115 (containing primary amino groups), manufactured by Tsuno Foods Co., Ltd. (d2) Polyamide resin 2: Vegichem Green V-125 (containing primary amino groups), manufactured by Tsuno Foods Co., Ltd. (d3) Polyamide resin 3: Vegichem Green V-140 (containing primary amino groups), manufactured by Tsuno Foods Co., Ltd. (d4) Polyamide resin 4: Vegichem Green G-152 (containing primary amino groups), manufactured by Tsuno Foods Co., Ltd. (d5) Polyamide resin 5: Vegichem Green G-250 (containing primary amino groups), manufactured by Tsuno Foods Co., Ltd. (d6) Polyamide resin 6: Vegichem Green G-747 (containing primary amino groups), manufactured by Tsuno Foods Co., Ltd. (e) First rubber component: Amino-terminated butadiene-acrylonitrile copolymer (containing secondary amine at the end), Hypro ATBN 1300X16, manufactured by Huntsman Product Portfolio (f) Multifunctional polyester polyol: Desmophen XP2488, manufactured by Covestro AG (g) First isocyanate compound: PDI-based polyisocyanate (isocyanurate trimer), trifunctional, Stabio D-376N, manufactured by Mitsui Chemicals, Inc. (h) Secondary isocyanate compound: allophanate-modified HDI polyisocyanate, bifunctional, Tolonate X FLO100, manufactured by Vencorex (i) Tertiary isocyanate compound: IPDI-based prepolymer, bifunctional, Desmodur VPLS2371, manufactured by Sumika Covestro Urethane Co., Ltd. (j) Quaternary isocyanate compound: HDI-based prepolymer, bifunctional, Desmodur E30600, manufactured by Sumika Covestro Urethane Co., Ltd. (k) Thermoplastic resin: crystalline polyester, Yuric SE-2606, manufactured by Ito Oil Mills Co., Ltd.

[0096] (2) Evaluation (a) Pot life The base resin and curing agent were mixed, and the change in viscosity of the mixture over time was measured at a temperature of 25°C using a commercially available viscometer (B-type viscometer, manufactured by Eiko Seiki Co., Ltd.). The time it took for the viscosity to double compared to the initial viscosity was defined as the pot life, and the pot life was evaluated according to the following criteria. A: More than 10 minutes B: 2 minutes or more but less than 10 minutes C: Less than 2 minutes

[0097] (b) Peel strength, peel strength after water resistance test, and peel strength retention rate A first sample for measuring peel strength was prepared according to the following procedure. First, a polyurea resin composition was applied to one surface (one side) of a polyethylene terephthalate (PET) substrate and an ethylene-vinyl acetate copolymer (EVA) substrate using a spatula to a film thickness of 260 μm. After application, an open time of 30 minutes was allowed at 25°C. Next, the substrates were laminated together so that the coating films were in contact with each other, and pressed together using a roller. Each substrate measured 250 mm long, 25 mm wide, and 2 mm thick. After pressing, the sample was fixed with a clip and left to stand at 25°C for 24 hours to obtain a first sample for peel strength measurement.

[0098] Using the first sample, a T-peel test was performed in accordance with JIS T8101: 2020. The initial peel strength (N / mm) was determined and evaluated (rated) according to the following criteria. A:100N / 25mm or more B: 20N / 25mm or more and less than 100N / 25mm C: Less than 20N / 25mm

[0099] The first sample prepared in the same manner as above was immersed in warm water at 40°C for 24 hours and dried at room temperature under reduced pressure. Then, a T-peel test was performed in the same manner as above to determine the peel strength after the water resistance test and evaluate it according to the same criteria as above.

[0100] The percentage (%) of the peel strength after the water resistance test was calculated based on the initial peel strength being 100%, and was evaluated as the retention rate according to the following criteria. A: 70% or more B: Less than 70%

[0101] (c) Scratch resistance The polyurea resin composition was applied to the surface (one side) of the substrate film using an applicator so that the film thickness after drying would be 25 μm. The resulting coating was dried at 25°C for 24 hours to form a coating. A PET film (200 mm length x 200 mm width x 50 μm thickness) was used as the substrate film. A coating measuring 150 mm length x 150 mm width was formed in the center of the substrate film in the longitudinal direction. The surface of the resulting coating was scratched with a fingernail, and the presence or absence of scratches and the recovery of the scratches after 24 hours at 25°C after scrubbing were visually evaluated. Evaluation was performed according to the following criteria. A: It won't scratch B: Scratches occur but recovers over time C: Scratched and not restored over time

[0102] The evaluation results are shown in Tables 1 to 5. In the tables, E1 to E23 are examples, and C1 to C13 are comparative examples.

[0103] [Table 1]

[0104] As shown in Table 1, by using a first aspartic acid ester compound and a second aspartic acid ester compound, both of which have a secondary amino group, it is possible to ensure high initial peel strength while maintaining a long pot life (E1, E2, E4, and E5). When a third aspartic acid ester compound is used in addition to the first and second aspartic acid ester compounds, it is easy to adjust the reaction rate and peel strength, and it is easy to balance a relatively long pot life with a relatively high peel strength (E3, E6, and E7). Furthermore, in the examples, relatively high water resistance of the cured product is obtained, and high peel strength retention is easily achieved (E1 to E5). In contrast, when a first aspartic acid ester compound and a third aspartic acid ester compound are used, or when a second aspartic acid ester compound and a third aspartic acid ester compound are used, the pot life is shortened or the peel strength is reduced (C10 to C13).

[0105] From the viewpoint of easily ensuring a longer pot life and higher peel strength of the cured product, the content of the tertiary aspartic acid ester compound in the base resin is preferably 20% by mass or less. From the viewpoint of easily ensuring a moderate strength of the cured product and suppressing peeling at the interface with the substrate, thereby easily ensuring higher peel strength, the content of the secondary aspartic acid ester compound in the base resin is preferably 30% by mass or less.

[0106] When a polyamide resin having a primary amino group is used instead of an aspartic acid ester compound, the reaction rate increases, but the pot life tends to be shorter. If the pot life is extremely short, the coating may harden before the substrates are bonded together.

[0107] [Table 2]

[0108] When the base agent contains a first rubber-like component, the initial peel strength can be significantly improved while maintaining a relatively long pot life (comparison between E2 and E8 to E13). From the viewpoint of easily obtaining a longer pot life, the content of the first rubber-like component in the base agent is preferably 20% by mass or less. Both the first rubber-like component and the aspartic acid ester compound have secondary amino groups, but the secondary amino groups in the aspartic acid ester compound are more likely to have a longer pot life due to the influence of surrounding steric hindrance. Even when a second base agent having hydroxy groups, such as a multifunctional polyester polyol, is used, a certain level of peel strength can be obtained while ensuring a relatively long pot life (E14 and E15). However, from the viewpoint of easily obtaining a higher peel strength and a high peel strength retention rate, the content of the second base agent is preferably, for example, less than 10% by mass.

[0109] [Table 3]

[0110] Compared with when the first curing agent uses two types of isocyanate compounds, such as a first and a second isocyanate compound or a first and a third isocyanate compound, when the first curing agent uses a first to a third isocyanate compound, a high peel strength tends to be obtained (comparison of E8, E15, and E16 with E18 and E19). Even when the first to the third isocyanate compounds are used, the content of the first polyisocyanate compound in the first curing agent is preferably 55 mol% or less from the viewpoint of ensuring even higher peel strength and a longer pot life (comparison of E8, E15, and E16 with E17).

[0111] [Table 4]

[0112] As shown in Table 4, when a thermoplastic resin (specifically, crystalline polyester) is used, the initial peel strength tends to improve and the water resistance tends to decrease slightly. From the viewpoint of ensuring higher water resistance and obtaining a high retention rate of peel strength, the amount of thermoplastic resin (such as crystalline polyester) per 100 parts by mass of the base resin is preferably 15 parts by mass or less, or 10 parts by mass or less.

[0113] [Table 5]

[0114] As shown in Table 5, even when a polymeric polyisocyanate component containing an aliphatic polyisocyanate as a constituent unit is used as the fourth isocyanate compound instead of the third isocyanate compound, high peel strength and its retention rate can be obtained while ensuring a relatively long pot life. From the viewpoint of ensuring a longer pot life, the use of the third isocyanate compound is preferable to the use of the fourth isocyanate compound. Furthermore, the use of the third isocyanate compound makes it easier to obtain superior scratch resistance than the use of the fourth isocyanate compound. [Industrial Applicability]

[0115] The polyurea resin composition of the present disclosure has a long pot life and high peel strength of the cured product. Therefore, it is also useful as an adhesive resin composition or a coating resin composition. However, the uses of the polyurea resin composition are not limited to these and can be used for various other purposes.

Claims

1. A polyurea resin composition comprising a base agent and a curing agent, the curing agent includes a first curing agent having an isocyanate group, The main agent includes a first main agent having an amino group. The first main ingredient is an aspartic acid ester compound Including, The aspartic acid ester compound is The amino groups of the two aspartic acid ester molecules have a —NH—X—NH— structure bonded via a linking group X, and a first aspartic acid ester compound in which the linking group X is a divalent group corresponding to a dicyclohexylalkane; a second aspartic acid ester compound in which the linking group X is a divalent group corresponding to a 2,2'-dialkyl-dicyclohexylalkane.

2. In the first aspartic acid ester compound, the linking group is a divalent group corresponding to dicyclohexylmethane, The polyurea resin composition according to claim 1, wherein in the second aspartic acid ester compound, the linking group is a divalent group corresponding to 2,2'-dimethyl-dicyclohexylmethane.

3. the content of the first aspartic acid ester compound in the base material is 50% by mass or more and 90% by mass or less, The polyurea resin composition according to claim 1 or 2, wherein the content of the second aspartic acid ester compound in the base resin is 5% by mass or more and 30% by mass or less.

4. The polyurea resin composition according to claim 1 or 2, wherein the first main component further comprises a rubber-like component having a secondary amino group at its terminal.

5. The polyurea resin composition according to claim 4 , wherein the content of the rubber component in the base resin is 5% by mass or more and 20% by mass or less.

6. the first main agent further contains a third aspartic acid ester compound, The polyurea resin composition according to claim 1 or 2, wherein the third aspartic acid ester compound has a -NH-Y-NH- structure in which the amino groups of two aspartic acid ester molecules are bonded via an alkylene group as a linking group Y.

7. The polyurea resin composition according to claim 6, wherein in the third aspartic acid ester compound, the linking group is a 2-methyl-1,5-pentylene group.

8. The polyurea resin composition according to claim 6 , wherein the content of the third aspartic acid ester compound in the base resin is 20% by mass or less.

9. The first curing agent is a first isocyanate compound: an aliphatic polyisocyanate polymer; a second isocyanate compound: an allophanate-modified aliphatic polyisocyanate; a third isocyanate compound: a polymeric polyisocyanate component containing an alicyclic polyisocyanate as a constituent unit; The polyurea resin composition according to claim 1 or 2, comprising:

10. the first isocyanate compound comprises an isocyanurate trimer of 1,5-pentamethylene diisocyanate; the second isocyanate compound comprises an allophanate-modified 1,6-hexamethylene diisocyanate; The polyurea resin composition according to claim 9 , wherein the third isocyanate compound includes a polymeric polyisocyanate component containing isophorone diisocyanate as a constituent unit.

11. the content of the first isocyanate compound in the first curing agent is 35 mol% or more and 55 mol% or less, the content of the second isocyanate compound in the curing agent is 20 mol% or more and 40 mol% or less, The polyurea resin composition according to claim 9 , wherein the content of the third isocyanate compound in the curing agent is 10 mol % or more and 35 mol % or less.

12. The polyurea resin composition according to claim 1 or 2, further comprising a crystalline polyester.

13. The polyurethane resin composition according to claim 12, wherein the proportion of the crystalline polyester is 10 parts by mass or less relative to 100 parts by mass of the main component.

14. 3. The polyurea resin composition according to claim 1, which is an adhesive resin composition.

15. 3. The polyurea resin composition according to claim 1, which is a resin composition for use as a paint.

Images