Two-component compositions, cured products, and articles

Abstract

To provide a composition capable of forming a coating film with excellent adhesion and water resistance on a PC substrate. [Solution] A two-component composition comprising a first composition containing polymer A having a diene structure and a second composition containing polymer B having a dienophile structure, wherein polymer A is a polymer obtained by adding sorbic acid to the glycidyl group in copolymer C containing glycidyl (meth)acrylate as a monomer unit, and polymer B is a polymer obtained by adding maleimide acid to the glycidyl group in copolymer C.

Description

Technical Field

[0001] The present disclosure relates to a two-component composition, a cured product, and an article.

Background Art

[0002] Paints used in automobiles, household electrical appliances, building materials, etc. are required to have various performances such as chemical resistance, scratch resistance, and substrate adhesion. Conventionally, as such paints, compositions that are cured by reacting a compound having an isocyanate group with a compound having a hydroxy group have been generally used. In recent years, due to problems such as the toxicity of compounds having an isocyanate group to the body, compositions that do not use such compounds have been studied.

[0003] For example, in Patent Document 1, as a curable composition using a Diels-Alder reaction, a thermosetting composition is disclosed that includes a compound (A) in which a plurality of conjugated carbon-carbon double bonds in the molecule are supported as sorbic acid esters and a compound (B) having two or more carbon-carbon double bonds in the molecule.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] According to the studies of the present inventors, when a composition using a Diels-Alder reaction is used as a paint, depending on the material of the substrate to be coated with the composition, the adhesion and water resistance may be insufficient. More specifically, when the composition is applied onto a substrate made of polycarbonate (PC) (hereinafter also referred to as a "PC substrate"), problems such as the coating film not adhering sufficiently to the PC substrate and, even if it adheres, peeling off when exposed to water (poor water resistance) may occur.

[0006] Therefore, one aspect of the present invention is to provide a composition capable of forming a coating film with excellent adhesion and water resistance on a PC substrate. [Means for solving the problem]

[0007] The present inventors have found that in a composition capable of forming a coating film using a polymer having a diene structure and a polymer having a dienophile structure and the Diels-Alder reaction, a coating film with excellent adhesion and water resistance can be formed on a PC substrate by using a copolymer containing glycidyl (meth)acrylate as a monomer unit as a base polymer, adding sorbic acid to the base polymer to impart a diene structure, and adding maleimide acid to the base polymer to impart a dienophile structure.

[0008] The present invention includes the following aspects. [1] A two-component composition comprising a first composition containing polymer A having a diene structure and a second composition containing polymer B having a dienophile structure, wherein polymer A is a polymer obtained by adding sorbic acid to a glycidyl group in copolymer C containing glycidyl (meth)acrylate as a monomer unit, and polymer B is a polymer obtained by adding maleimide acid to a glycidyl group in copolymer C. [2] The two-component composition according to [1], wherein the glass transition temperature of polymer C is 40°C or higher. [3] The two-component composition according to [1] or [2], wherein the weight-average molecular weight of polymer C is 50,000 or less. [4] A two-component composition according to any one of [1] to [3], used as a coating material. [5] A cured product of any two-component composition described in [1] to [4]. [6] An article comprising a base material and a cured product described in [5] placed on the base material. [Effects of the Invention]

[0009] According to one aspect of the present invention, a composition is available that can form a coating film with excellent adhesion and water resistance on a PC substrate. According to another aspect of the present invention, a coating film with excellent adhesion and water resistance can also be formed on a substrate made of acrylonitrile-butadiene-styrene (ABS) resin (hereinafter also referred to as "ABS substrate"). Furthermore, according to another aspect of the present invention, a coating film with excellent rubbing resistance (particularly rubbing resistance in the presence of chemicals such as alcohol; the same applies hereinafter) and sunscreen resistance can be formed on the ABS substrate. [Modes for carrying out the invention]

[0010] One embodiment of the present invention is a two-component composition comprising a first composition containing polymer A having a diene structure and a second composition containing polymer B having a dienophile structure.

[0011] Polymer A is a polymer obtained by adding sorbic acid to the glycidyl group in copolymer C, which contains glycidyl (meth)acrylate as a monomer unit.

[0012] Copolymer C contains, as monomer units, glycidyl (meth)acrylate and one or more other monomers copolymerizable with glycidyl (meth)acrylate. The other monomers may be monomers having an ethylenically unsaturated group.

[0013] Other monomers are preferably monomers whose homopolymer glass transition temperature (Tg) is 60°C or higher. Specific examples of such other monomers include styrene, isobornyl (meth)acrylate, methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isopropyl methacrylate, and 3,3,5-trimethylcyclohexyl methacrylate.

[0014] The content of glycidyl (meth)acrylate may be 5% by mass or more, 8% by mass or more, 10% by mass or more, 12% by mass or more, or 14% by mass or more, and may be 70% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, or 45% by mass or less, based on the total mass of monomer units in copolymer C. From the viewpoint of forming a coating film with further excellent water resistance on a PC substrate, preferably, it may be 40% by mass or less, 35% by mass or less, or 30% by mass or less.

[0015] The content of other monomers may be 30% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, or 70% by mass or more, and may be 95% by mass or less, 92% by mass or less, 90% by mass or less, 88% by mass or less, or 86% by mass or less, based on the total mass of monomer units in copolymer C.

[0016] The weight average molecular weight (Mw) of copolymer C may be 3,000 or more, 5,000 or more, 7,000 or more, or 9,000 or more. From the viewpoint of forming a coating film with excellent sunburn resistance on an ABS substrate, preferably, it may be 12,000 or more, or 15,000 or more. From the viewpoint of forming a coating film with further excellent adhesion and water resistance on a PC substrate, preferably, it may be 50,000 or less, 40,000 or less, 30,000 or less, or 25,000 or less.

[0017] The weight average molecular weight (Mw) in this specification means the value measured under the following GPC measurement conditions. [GPC Measurement Conditions] Measuring device: High-speed GPC device ("HLC-822GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8 mm I.D. × 30 cm) × 1 piece [[ID=二十一]] [[ID=二十二]]"TSKgel G4000" (7.8 mm I.D. × 30 cm) × 1 piece [[ID=二十三]] [[ID=二十四]]"TSKgel G3000" (7.8 mm I.D. × 30 cm) × 1 piece [[ID=二十五]] One piece of 「TSKgel G2000」(7.8mm I.D.×30cm) Detector: RI (Differential Refractometer) Column temperature: 40 °C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg / mL) Standard sample: A calibration curve was prepared using the following monodisperse polystyrene. [Monodisperse Polystyrene] 「TSKgel Standard Polystyrene A-500」 manufactured by Tosoh Corporation 「TSKgel Standard Polystyrene A-1000」 manufactured by Tosoh Corporation 「TSKgel Standard Polystyrene A-2500」 manufactured by Tosoh Corporation 「TSKgel Standard Polystyrene A-5000」 manufactured by Tosoh Corporation 「TSKgel Standard Polystyrene F-1」 manufactured by Tosoh Corporation 「TSKgel Standard Polystyrene F-2」 manufactured by Tosoh Corporation 「TSKgel Standard Polystyrene F-4」 manufactured by Tosoh Corporation 「TSKgel Standard Polystyrene F-10」 manufactured by Tosoh Corporation 「TSKgel Standard Polystyrene F-20」 manufactured by Tosoh Corporation 「TSKgel Standard Polystyrene F-40」 manufactured by Tosoh Corporation 「TSKgel Standard Polystyrene F-80」 manufactured by Tosoh Corporation<​​​​​​​​The glass transition temperature (Tg) of copolymer C is preferably 40°C or higher, 50°C or higher, 60°C or higher, or 70°C or higher, and may be 105°C or lower, 100°C or lower, or 95°C or lower, from the viewpoint of being able to form a coating film with even better water resistance on a PC substrate, and a coating film with excellent water resistance, rubbing resistance, and sunscreen resistance on an ABS substrate.

[0019] In this specification, the glass transition temperature (Tg) is given by FOX's formula: 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... (Tg: glass transition temperature to be determined, W1: weight fraction of the first monomer constituting copolymer C, Tg1: glass transition temperature of the homopolymer of the first monomer constituting copolymer C, W2: weight fraction of the second monomer constituting copolymer C, Tg2: glass transition temperature of the homopolymer of the second monomer constituting copolymer C, ...) It means the result obtained through calculation. The glass transition temperatures of the homopolymers of each monomer constituting copolymer C are based on the values ​​listed in Polymer Handbook (4th Edition) by J. Brandrup, E. Himmergut, and E. A. Grulke (Wiley Interscience), as well as experimental values ​​measured by differential scanning calorimetry (DSC) after synthesis of the homopolymers.

[0020] Copolymer C may be any copolymer, such as a random copolymer, a block copolymer, or a graft copolymer.

[0021] (Polymerization method) Any suitable method can be used to polymerize copolymer C, including solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerization methods. Among these, solution polymerization is preferred from the viewpoint of ease of handling.

[0022] (Radical polymerization initiator) Polymer C may contain a radical polymerization initiator, for example, when undergoing radical polymerization. The radical polymerization initiator may be, for example, a thermal polymerization initiator that generates free radicals when heated. These may be used individually or in combination of two or more.

[0023] Examples of the radical polymerization initiators include peroxide-based radical polymerization initiators and azo-based radical polymerization initiators. Among these, peroxide-based radical polymerization initiators are preferred.

[0024] Examples of the peroxide-based radical polymerization initiators include: hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkylperoxide compounds such as tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; diacyl peroxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl) peroxydicarbonate; and tert-butylperoxydicarbonate. Examples include peroxyester compounds such as oxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl)2-ethyl perhexanoate, tert-butyl 2-ethyl perhexanoate, tert-butyl 3,5,5-trimethyl perhexanoate, tert-butyl peroxy-2-ethylhexyl monocarbonate, and tert-butyl peroxymaleic acid.

[0025] Examples of the azo radical polymerization initiators include azonitrile compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitride), 1-[(1-cyano-1-methylethyl)azo]formamide, and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], and 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl) Examples include azoamide compounds such as [(2-methyl)ethyl]propionamide], 2,2'-azobis[2-methyl-N-[2-(1-hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(2-methylpropionamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); and alkylazo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane).

[0026] Examples of commercially available radical polymerization initiators include NOF Corporation's "Perbutyl C," "Perbutyl A," "Perbutyl P," "Perbutyl L," "Perbutyl O," "Perbutyl ND," "Perbutyl Z," "Perbutyl I," "Permil P," "Permil D," "Perhexyl D," "Perhexyl A," "Perhexyl I," "Perhexyl Z," "Perhexyl ND," "Perhexyl O," "Perhexyl PV," and "Perhexyl O."

[0027] The amount of radical polymerization initiator used can be any amount that is used normally. For example, it can be selected from a range of about 0.3 to 15 parts by mass, preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total amount of monomer components constituting the polymer C.

[0028] The polymerization temperature and polymerization time can be appropriately selected depending on the type of monomer used, the type of polymerization initiator, etc. For example, the polymerization temperature can be set to about 80 to 130°C, and the polymerization time can be set to about 5 to 20 hours.

[0029] (Chain transfer agent) Furthermore, various conventionally known chain transfer agents (molecular weight modifiers or degree of polymerization modifiers) can be used for polymerization as needed. Examples of such chain transfer agents include mercaptans such as n-lauryl mercaptan, t-lauryl mercaptan, glycidyl mercaptan, and 2-mercaptoethanol, with t-lauryl mercaptan being preferred. These may be used individually or in combination of two or more.

[0030] The amount of the chain transfer agent used can be any amount used normally, and can be selected from a range of about 0.1 to 10 parts by mass per 100 parts by mass of the total amount of monomer components constituting polymer C.

[0031] (Other crosslinking agents (hardening agents)) The coating composition may further contain other curing agents (crosslinking agents) as needed. The crosslinking agent is not particularly limited, but examples include epoxy crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate crosslinking agents, and carbodiimide crosslinking agents. The crosslinking agent can be used as appropriate depending on the type of functional group contained in the coating composition used. It is preferable not to use isocyanate crosslinking agents because they have problems such as shortening the pot life of the coating composition. These may be used individually or in combination of two or more.

[0032] Polymer A is obtained by reacting the glycidyl group in copolymer C with the carboxyl group of sorbic acid. That is, polymer A is given by the following formula (1):

[0033] [ka] (In the formula, R 1 (This represents a hydrogen atom or a methyl group.) It is a polymer having structural units represented by .

[0034] The amount of sorbic acid added may be 3 parts by mass or more, 5 parts by mass or more, or 10 parts by mass or more, and may be 50 parts by mass or less, 45 parts by mass or less, 40 parts by mass or less, or 35 parts by mass or less, based on 100 parts by mass of the total mass of monomer units in copolymer C.

[0035] The concentration of the diene structure in polymer A may be 0.3 mmol / g or more, or 0.5 mmol / g or more, and may be 4 mmol / g or less, 3 mmol / g or less, 2.5 mmol / g or less, 2.1 mmol / g or less, or 2 mmol / g or less.

[0036] The first composition may further contain an organic solvent capable of dissolving polymer A. Examples of such organic solvents include n-butyl acetate, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, n-pentane, n-hexane, cyclohexane, n-heptane, benzene, toluene, xylene, carbon tetrachloride, dichloromethane, chloroform, trichloroethane, dimethylformamide, N-methylpyrrolidone, acetonitrile, diacetone alcohol, n-butanol, propylene glycol monomethyl ether acetate, and the like. The amount of these solvents used is not particularly limited and can be selected as appropriate.

[0037] The first composition may further contain additives. Examples of additives include silane coupling agents, lubricants, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light stabilizers, fluorescent whitening agents, foaming agents, pH adjusters, leveling agents, gelation inhibitors, dispersion stabilizers, antioxidants, radical scavengers, heat resistance modifiers, inorganic fillers, organic fillers, plasticizers, reinforcing agents, antibacterial agents, antifungal agents, rust inhibitors, thermoplastic resins, thermosetting resins, pigments, dyes, conductivity modifiers, antistatic agents, moisture permeability enhancers, water repellents, oil repellents, hollow foams, water-containing compounds, flame retardants, water absorbents, moisture absorbents, deodorants, foam stabilizers, defoamers, antifungal agents, preservatives, antialgal agents, pigment dispersants, blocking inhibitors, and hydrolysis inhibitors. The amounts of these additives are not particularly limited and can be selected as appropriate.

[0038] Polymer B is a polymer obtained by adding maleimide acid to the glycidyl group in copolymer C. The details of copolymer C are the same as those of polymer C described in polymer A.

[0039] Maleimide acids are compounds having a maleimide group and a carboxyl group. Maleimide acids are, for example, represented by the following formula (2):

[0040] [ka] (In the formula, R 2 (This represents an alkylene group.) It can be expressed as follows.

[0041] R 2 The alkylene group represented by may be linear or branched. The number of carbon atoms in the alkylene group may be 1 or more, 2 or more, 3 or more, or 4 or more, and may be 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

[0042] Polymer B is obtained by reacting the glycidyl group in copolymer C with the carboxyl group in maleimide acid. For example, if maleimide acid is the compound represented by formula (2) above, polymer B is obtained by the following formula (3):

[0043] [ka] (In the formula, R 2 R in equation (2) above is 2 It is synonymous with R 3 (This represents a hydrogen atom or a methyl group.) It is a polymer having structural units represented by .

[0044] The amount of maleimid acid added may be 5 parts by mass or more, 8 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more, and may be 110 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less, based on 100 parts by mass of the total mass of monomer units in copolymer C.

[0045] The concentration of the dienophile structure in polymer B may be 0.6 mmol / g or more, 1.0 mmol / g or more, or 1.5 mmol or more, and may be 4.6 mmol or less, 4.0 mmol or less, or 3.6 mmol or less.

[0046] The second composition may further contain an organic solvent capable of dissolving polymer B. The organic solvent described in the first composition can be used as the organic solvent.

[0047] The second composition may further contain additives. The additives described in the first composition can be used as additives.

[0048] The two-component composition described above is suitably used as a coating material (paint), and may be used, for example, as a coating material (paint) applied to a substrate as described later, and is particularly suitably used as a coating material (paint) applied to a PC substrate. That is, one embodiment of the present invention is the use (application) of the above two-component composition as a coating material (paint), and may be used, for example, as a coating material (paint) applied to a substrate as described later, and is preferably used (application) as a coating material (paint) applied to a PC substrate.

[0049] To adjust the viscosity of the two-component composition (coating material) to a level suitable for coating, the first and second compositions may be diluted with a solvent when mixed, if necessary. Examples of suitable solvents include acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, n-pentane, n-hexane, cyclohexane, n-heptane, benzene, toluene, xylene, carbon tetrachloride, dichloromethane, chloroform, trichloroethane, dimethylformamide, N-methylpyrrolidone, acetonitrile, diacetone alcohol, n-butanol, propylene glycol monomethyl ether acetate, and the like. The amount of these solvents used is not particularly limited and can be selected as appropriate.

[0050] The two-component composition (coating material) may further contain other curing agents (crosslinking agents) as needed. The crosslinking agent is not particularly limited, but examples include epoxy crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, metal chelate crosslinking agents, carbodiimide crosslinking agents, etc. The crosslinking agent can be used as appropriate depending on the type of functional group contained in the coating composition used. These may be used alone or in combination of two or more.

[0051] By mixing the first and second compositions constituting the two-component composition and heating them, a Diels-Alder reaction proceeds between polymer A having a diene structure and polymer B having a dienophile structure, resulting in a cured product of the two-component composition (a mixture of the first and second compositions). That is, one embodiment of the present invention is a cured product of a two-component composition (a mixture of the first and second compositions). Since this Diels-Alder reaction proceeds at relatively low temperatures (e.g., 80°C or below), the two-component composition according to one embodiment is advantageous in that it hardens when heated at relatively low temperatures (e.g., 80°C or below).

[0052] The two-component composition (a mixture of a first composition and a second composition) is, for example, coated onto a substrate and then heated and cured. That is, one embodiment of the present invention is an article comprising a substrate and a cured product of a two-component composition (a mixture of a first composition and a second composition) disposed on the substrate.

[0053] The two-component composition can form a coating film with excellent adhesion and water resistance on a PC substrate, but the substrate material is not limited to polycarbonate. Examples of substrate materials include various plastics such as polycarbonate, acrylonitrile-butadiene-styrene copolymer, PC-ABS polymer alloy, polymethyl methacrylate, polyethylene terephthalate, polyamide, and polypropylene, as well as fiber-reinforced plastics made by adding fillers such as glass fibers to these plastics; various metals such as iron, copper, zinc, aluminum, and magnesium, and their alloys; and wood.

[0054] Examples of items include interior and exterior materials for various vehicles such as automobiles and railway cars; interior and exterior materials for buildings such as industrial machinery, exterior walls, roofs, glass, decorative panels, and wooden floors; civil engineering components such as soundproof walls and drainage ditches; casings for home appliances such as televisions, refrigerators, washing machines, and air conditioners; casings for electronic devices such as personal computers, smartphones, mobile phones, digital cameras, and game consoles; and casings for office automation equipment such as printers and fax machines. [Examples]

[0055] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0056] [Manufacturing of Polymer A] (Manufacturing Example 1) In a flask equipped with a condenser, thermometer, dropping funnel, and stirrer, 262.5 parts by mass of n-butyl acetate was added, and the temperature inside the flask was raised to 90°C. Next, a mixture of 430 parts by mass of methyl methacrylate (MMA), 70.0 parts by mass of glycidyl methacrylate (GMA), 183.7 parts by mass of n-butyl acetate, and 35.0 parts by mass of t-butyl peroxy-2-ethylhexanoate (Perbutyl O) was added dropwise over 2 hours. Two hours after the end of the dropwise addition, the temperature inside the flask was raised to 120°C, and the polymerization reaction was carried out for 2 hours. Next, n-butyl acetate was added to obtain a solution of copolymer C (weight-average molecular weight (Mw): 9,000, glass transition temperature (Tg): 95°C) with a non-volatile content of 50% by mass.

[0057] To 492.0 parts by mass of the obtained solution, 25.8 parts by mass of sorbic acid (SBA), 0.5 parts by mass of dibutylhydroxytoluene (BHT), 0.1 parts by mass of hydroquinone monomethyl ether (MEHQ), 1.4 parts by mass of tetrabutylphosphonium bromide, and 24.2 parts by mass of n-butyl acetate were added. The temperature in the flask was raised to 110°C and the reaction was allowed to proceed for 10 hours to obtain a solution of polymer A-1 having a diene structure with a non-volatile content of 55% by mass.

[0058] (Manufacturing Examples 2-9) Solutions of polymers A-2 to A-9 were obtained in the same manner as in Production Example 1, except that the monomer composition of copolymer C, the amount of initiator added when synthesizing copolymer C, and the amount of sorbic acid (SBA) added were changed as shown in Table 1. In Table 1, St represents styrene, BA represents n-butyl acrylate, and BMA represents n-butyl methacrylate.

[0059] [Manufacturing of Polymer B] (Manufacturing example 10) To 500.0 parts by mass of a solution of copolymer C (weight-average molecular weight (Mw): 9,000, glass transition temperature (Tg): 95°C) with a non-volatile content of 50% by mass, obtained in the same manner as in Production Example 1, 52.0 parts by mass of maleimidocaproic acid (MCA), 0.5 parts by mass of dibutylhydroxytoluene (BHT), 0.1 parts by mass of MEHQ, 1.4 parts by mass of tetrabutylphosphonium bromide, and 197.2 parts by mass of n-butyl acetate were added. The temperature in the flask was raised to 110°C and the mixture was reacted for 10 hours to obtain a solution of polymer B-1 having a dienophile structure with a non-volatile content of 40% by mass.

[0060] (Manufacturing examples 11-17) Solutions of polymers B-2 to B-8 were obtained in the same manner as in Production Example 10, except that the monomer composition of copolymer C and the amount of maleimidocaproic acid (MCA) added were changed as shown in Table 2.

[0061] [Manufacturing of comparative polymer b] A solution of comparative polymer b was obtained in the same manner as in Production Example 12, except that acrylic acid (AA) was used instead of maleimidocaproic acid (MCA).

[0062] [Table 1]

[0063] [Table 2]

[0064] (Example 1) [Evaluation of properties for PC substrates] A solution containing polymer A-1 having a diene structure (first composition) and a solution containing polymer B-1 having a dienophile structure (second composition) were mixed and adjusted with butyl acetate and isooctanolic acid to obtain a coating solution with a non-volatile content of 30-40% by mass. The solution containing polymer A-1 and the solution containing polymer B-1 were mixed so that the amount of diene structure (moles) of polymer A-1 and the amount of dienophile structure (moles) of polymer B-1 were in a 1:1 (molar ratio). Subsequently, the coating solution was applied to a PC substrate (Takiron CI Co., Ltd., polycarbonate (product name: PC1600)) using a bar coater to a film thickness of 15-20 μm. After standing for 10 minutes, it was dried at 80°C for 30 minutes, and then stood at room temperature (25°C) for about 7 days to obtain a coating film (cured product).

[0065] (Adhesive) The obtained coating film (cured product) was subjected to a grid test (1 mm, 100 squares, 4 directions) in accordance with ASTM D3359, and its adhesion to the PC substrate was evaluated according to the criteria of 5B, 4B, 3B, 2B, 1B, and 0B.

[0066] (water resistance) The obtained coating film (cured product) was immersed in water (40°C) for 240 hours, and then a grid test (1 mm, 100 squares, 4 directions) was performed in accordance with ASTM D3359. The adhesion (water resistance) to the PC substrate after immersion was evaluated according to the criteria of 5B, 4B, 3B, 2B, 1B, and 0B.

[0067] [Evaluation of properties for ABS substrate] Except for using an ABS substrate (Acrylonitrile-butadiene-styrene copolymer (product name: Kobe Polyethylene Sheet ABS-BKWB) manufactured by Showa Denko Materials Co., Ltd.) instead of a polycarbonate (PC) substrate, a coating film (cured product) was obtained on the ABS substrate in the same manner as the evaluation of properties for the PC substrate.

[0068] (Adhesion and water resistance) The obtained coating film (cured product) was evaluated for its adhesion to the ABS substrate and water resistance, similar to the evaluation of its properties on the PC substrate.

[0069] (Rubber resistance) A rubbing test was performed on the obtained coating film (cured product) by pressing a felt soaked in ethanol (reagent grade 1, 95% or higher) against it and applying a load of 1 kg, repeating the process up to 500 times. The condition of the coating film after the rubbing test was visually observed, and the rubbing resistance was evaluated according to the following criteria. A: The surface of the ABS substrate was not visible even after 500 back-and-forth cycles. B: The surface of the ABS substrate became visible after 350 to 500 back-and-forth cycles. C: The surface of the ABS substrate was visible after fewer than 350 back-and-forth cycles.

[0070] (Sunscreen resistance) Apply a uniform layer of sunscreen cream (Coppertone Sport Ultra Sweatproof SPF30, manufactured by SSL Healthcare Japan Co., Ltd.) to the resulting coating (cured product) (0.5g / 100cm 2 After drying at 55°C for 4 hours, the sunscreen cream was washed with a neutral detergent (Kao Corporation, product name "Kyukyutto"). The appearance of the coating after washing was observed, and the sunscreen resistance was evaluated according to the following criteria. A: The area where sunscreen cream residue is present is less than 5% of the total surface area of ​​the coating. B: The area where sunscreen cream residue is present is between 5% and 20% of the total surface area of ​​the coating. C: The area where sunscreen cream residue is present is 20% or more of the total surface area of ​​the coating.

[0071] (Examples 2-13) Except for changing the types of polymers A and B as shown in Tables 3 to 5, the coating film (cured product) was prepared and evaluated in the same manner as in Example 1.

[0072] (Comparative Example 1) The coating film (cured product) was prepared and evaluated in the same manner as in Example 4, except that a solution of comparative polymer b was used instead of a solution of polymer B (second composition).

[0073] (Comparative Example 2) The coating film (cured product) was prepared and evaluated in the same manner as in Example 4, except that N,N'-hexamethylenebismaleimide was used as a curing agent instead of the polymer B solution.

[0074] The evaluation results for the above examples and comparative examples are shown in Tables 3 to 5.

[0075] [Table 3]

[0076] [Table 4]

[0077] [Table 5]

Claims

1. A first composition containing polymer A having a diene structure, A two-component composition comprising: a second composition containing polymer B having a dienophilic structure; The polymer A is a polymer obtained by adding sorbic acid to the glycidyl group in copolymer C, which contains glycidyl (meth)acrylate as a monomer unit. A two-component composition in which polymer B is a polymer obtained by adding maleimide acid to the glycidyl group in copolymer C.

2. The two-component composition according to claim 1, wherein the glass transition temperature of the polymer C is 40°C or higher.

3. The two-component composition according to claim 1, wherein the weight-average molecular weight of polymer C is 50,000 or less.

4. A two-component composition according to any one of claims 1 to 3, used as a coating material.

5. A cured product of a two-component composition according to any one of claims 1 to 3.

6. Substrate and An article comprising a cured product according to claim 5 disposed on the substrate.

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