Two-part curable resin composition and laminate

Abstract

The two-part curable resin composition includes a main agent and a curing agent. The main agent contains an acrylic resin containing a hydroxyl group. The hydroxyl group-containing acrylic resin is a copolymer of polymerization components including a hydroxyl group-containing (meth) acrylate and a vinyl monomer having an alicyclic structure. The vinyl monomer containing the alicyclic structure comprises a vinyl monomer containing a bicycloalkyl group and / or a vinyl monomer containing a cycloalkyl group. The content ratio of a vinyl monomer containing an alicyclic structure relative to the polymerization component is from 15.0% by mass to 60.0% by mass (inclusive). The glass transition temperature, SP value, and hydroxyl value of the hydroxyl group-containing acrylic resin are within predetermined ranges.

Description

Technical Field

[0001] The present invention relates to a two-component curable resin composition and a laminate. Background Art

[0002] Conventionally, in the fields of vehicle coatings and home appliance coatings, two-component curable resin compositions comprising a base component containing a hydroxyl group-containing acrylic resin and a curing agent are known.

[0003] As such a two-component curable resin composition, for example, a clear coating composition containing a hydroxyl group-containing acrylic resin and a polyisocyanate compound has been proposed (for example, see Patent Document 1).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2015-66543 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] Such a two-component curable resin composition can be applied to a substrate for use. Specifically, the two-component curable resin composition is applied to a substrate and then cured to form a coating layer composed of a cured product of the two-component curable resin composition.

[0009] On the other hand, depending on the type of substrate, the adhesion between the substrate and the coating layer may be reduced.

[0010] The present invention provides a two-component curable resin composition having excellent adhesion to various substrates, and a laminate comprising coating layers sequentially provided with cured products of the two-component curable resin composition.

[0011] Means for solving problems

[0012] The present invention [1] is a two-component curable resin composition comprising a main agent and a curing agent, wherein the main agent comprises a hydroxyl-containing acrylic resin, the hydroxyl-containing acrylic resin is a copolymer comprising a polymer component of a hydroxyl-containing (meth)acrylate and a vinyl monomer containing an alicyclic structure, the vinyl monomer containing an alicyclic structure is composed of a vinyl monomer containing a bicycloalkyl group and / or a vinyl monomer containing a cycloalkyl group, the content ratio of the vinyl monomer containing an alicyclic structure relative to the polymer component is 15.0% by mass or more and 60.0% by mass or less, the glass transition temperature of the hydroxyl-containing acrylic resin is 10°C or more, and the SP value of the hydroxyl-containing acrylic resin is 9.40 (cal / cm 3 ) 1 / 2 Above 11.00 (cal / cm3 ) 1 / 2 Hereinafter, the hydroxyl value of the hydroxyl-containing acrylic resin is less than 100 mgKOH / g.

[0013] The present invention [2] comprises the two-component curable resin composition described in [1] above, wherein the glass transition temperature of the hydroxyl group-containing acrylic resin is 60° C. or higher.

[0014] The present invention [3] comprises the two-component curable resin composition described in [1] or [2] above, wherein the content ratio of the vinyl monomer containing an alicyclic structure relative to the polymer components is 30.1% by mass or more, and the glass transition temperature of the hydroxyl-containing acrylic resin is 130°C or less.

[0015] The present invention [4] comprises the two-component curable resin composition according to any one of [1] to [3] above, wherein the curing agent contains a (poly)isocyanate.

[0016] The present invention [5] includes a laminate comprising, in this order, a substrate and a coating layer formed from a cured product of the two-component curable resin composition according to any one of [1] to [4].

[0017] The present invention [6] includes the laminate described in [5] above, wherein the substrate is one selected from the group consisting of nylon, stainless steel, and glass.

[0018] Effects of the Invention

[0019] In the two-component curable resin composition of the present invention, the main component comprises a hydroxyl-containing acrylic resin, which is a copolymer comprising a polymerized component of a hydroxyl-containing (meth)acrylate and a vinyl monomer containing an alicyclic structure. The proportion of the vinyl monomer containing an alicyclic structure relative to the polymerized component is within a specified range. The glass transition temperature, SP value, and hydroxyl value of the hydroxyl-containing acrylic resin are within a specified range. Therefore, the coating obtained using this two-component curable resin composition has excellent adhesion to various substrates.

[0020] The laminate of the present invention comprises a coating layer formed from a cured product of the two-component curable resin composition of the present invention, and therefore has excellent adhesion to various substrates. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] [ Figure 1 ] Figure 1 One embodiment of the method for producing a laminate of the present invention is shown. Figure 1 A represents the first step of preparing a base material. Figure 1 B represents the second step of applying a two-component curable resin composition on the surface (one surface in the thickness direction) of the substrate to form a coating film. Figure 1 C represents the third step of heating the coating film to form a coating layer. DETAILED DESCRIPTION

[0022] A two-component curable resin composition contains a base and a curing agent. The base and curing agent are prepared as separate packages. When using a two-component curable resin composition, the base and curing agent are mixed.

[0023] 1. Main agent

[0024] The main agent contains an acrylic resin containing hydroxyl groups.

[0025] <Hydryl-containing acrylic resin>

[0026] The hydroxyl group-containing acrylic resin is a copolymer comprising a hydroxyl group-containing (meth)acrylate and a polymerization component of a vinyl monomer containing an alicyclic structure. In addition, the (meth)acrylate means acrylate and / or methacrylate.

[0027] [Hydryl-containing (meth)acrylate]

[0028] Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, polyhydroxyalkyl maleates, and polyhydroxyalkyl fumarates. A preferred example of the hydroxyl group-containing (meth)acrylate is 2-hydroxyethyl (meth)acrylate. A more preferred example of the hydroxyl group-containing (meth)acrylate is 2-hydroxyethyl methacrylate.

[0029] The hydroxyl group-containing (meth)acrylate can be used alone or in combination of two or more.

[0030] The content ratio of the hydroxyl group-containing (meth)acrylate relative to the polymerization component is, for example, 5.0 mass % or more, preferably 8.0 mass % or more, and, for example, 20.0 mass % or less, preferably 15.0 mass % or less.

[0031] [Vinyl monomer containing an alicyclic structure]

[0032] The vinyl monomer containing an alicyclic structure is composed of a vinyl monomer containing a bicycloalkyl group and / or a vinyl monomer containing a cycloalkyl group.

[0033] Examples of bicycloalkyl-containing vinyl monomers include isobornyl (meth)acrylate, bicycloheptyl (meth)acrylate, bicyclooctyl (meth)acrylate, and decahydro-2-naphthyl (meth)acrylate. Preferred bicycloalkyl-containing vinyl monomers include isobornyl (meth)acrylate. More preferred bicycloalkyl-containing vinyl monomers include isobornyl methacrylate.

[0034] Examples of the vinyl monomer containing a cycloalkyl group include cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate. Preferred examples of the vinyl monomer containing a cycloalkyl group include cyclohexyl (meth)acrylate. More preferred examples of the vinyl monomer containing a cycloalkyl group include cyclohexyl methacrylate.

[0035] As the vinyl monomer containing an alicyclic structure, from the viewpoint of improving the adhesion to various substrates, preferably, a vinyl monomer containing a bicycloalkyl group is used.

[0036] The vinyl monomer containing an alicyclic structure can be used alone or in combination of two or more. Preferably, a vinyl monomer containing a bicycloalkyl group is used alone, and a vinyl monomer containing a cycloalkyl group is used alone. That is, preferably, the vinyl monomer containing an alicyclic structure is composed of a vinyl monomer containing a bicycloalkyl group or a vinyl monomer containing a cycloalkyl group. More preferably, a vinyl monomer containing a bicycloalkyl group is used alone. That is, more preferably, the vinyl monomer containing an alicyclic structure does not contain a vinyl monomer containing a cycloalkyl group, but is composed of a vinyl monomer containing a bicycloalkyl group.

[0037] The content ratio of the vinyl monomer containing an alicyclic structure relative to the polymer components is 15.0 mass% or more, preferably 20.0 mass% or more, more preferably 30.0 mass% or more, further preferably greater than 30.0 mass%, particularly preferably 30.1 mass% or more, most preferably 40.0 mass% or more, further preferably 45.0 mass% or more, and further, 60.0 mass% or less, preferably 55.0 mass% or less.

[0038] When the content ratio of the vinyl monomer containing an alicyclic structure is within the above range, adhesion to various substrates can be improved.

[0039] On the other hand, when the content ratio of the vinyl monomer containing an alicyclic structure is outside the above range, the adhesion to various substrates cannot be improved.

[0040] [Other vinyl monomers containing a ring structure]

[0041] The vinyl monomer containing an alicyclic structure may contain other vinyl monomers containing a ring structure.

[0042] Other ring structure-containing vinyl monomers are vinyl monomers having a ring structure other than the above-mentioned alicyclic structure-containing vinyl monomers, and examples thereof include tricycloalkyl group-containing vinyl monomers and aromatic ring-containing vinyl monomers.

[0043] Examples of the tricycloalkyl group-containing vinyl monomer include adamantyl (meth)acrylate.

[0044] Examples of the aromatic ring-containing vinyl monomer include styrene, vinyltoluene, and α-methylstyrene.

[0045] The content ratio of the other ring structure-containing vinyl monomers relative to the polymerization components is, for example, 1 mass % or more, preferably 10 mass % or more, and for example, 20 mass % or less.

[0046] [Comonomer]

[0047] The polymerization component may contain a copolymerizable monomer that is copolymerizable with the hydroxyl group-containing (meth)acrylate, the alicyclic structure-containing vinyl monomer, and other ring structure-containing vinyl monomers.

[0048] Examples of the copolymerizable vinyl monomer include alkyl (meth)acrylates, cyano group-containing vinyl monomers, and carboxyl group-containing vinyl monomers.

[0049] Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, and hexyl (meth)acrylate. Examples of the cyano group-containing vinyl monomer include (meth)acrylonitrile. Examples of the carboxyl group-containing vinyl monomer include (meth)acrylic acid, fumaric acid, maleic acid, and itaconic acid.

[0050] As the copolymerizable vinyl monomer, preferably, an alkyl (meth)acrylate is mentioned. As the copolymerizable vinyl monomer, more preferably, an alkyl (meth)acrylate having 1 to 4 carbon atoms is mentioned. As the copolymerizable vinyl monomer, more preferably, methyl (meth)acrylate and butyl (meth)acrylate are mentioned. As the copolymerizable vinyl monomer, methyl methacrylate and butyl acrylate are mentioned particularly preferably.

[0051] The copolymerizable vinyl monomers can be used alone or in combination of two or more.

[0052] The content ratio of the copolymerizable vinyl monomer relative to the polymerization component is, for example, 40.0 mass % or more, and for example, 85.0 mass % or less, preferably 75.0 mass % or less, more preferably 65.0 mass % or less, further preferably 55.0 mass % or less, and particularly preferably 45.0 mass % or less.

[0053] From the perspective of reducing environmental impact, the aforementioned hydroxyl-containing (meth)acrylate, alicyclic vinyl monomer, other cyclic vinyl monomer, and copolymerizable monomer are biomass-derived monomers. Specifically, the hydroxyl-containing acrylic resin is preferably a copolymer containing polymerized components of biomass-derived monomers. The biomass content of such a hydroxyl-containing acrylic resin is, for example, 15% or greater, preferably 20% or greater, more preferably 25% or greater, further preferably 30% or greater, and particularly preferably 35% or greater.

[0054] The hydroxyl group-containing acrylic resin can be obtained by polymerizing a polymerizable component.

[0055] The polymerization method is not particularly limited. Examples of the polymerization method include bulk polymerization and solution polymerization.

[0056] When solution polymerization is employed as the polymerization method, polymerization components and, if necessary, a polymerization initiator are mixed in a solvent (eg, butyl acetate) to carry out polymerization.

[0057] Examples of the polymerization initiator include known thermal polymerization initiators (for example, azo-based radical polymerization initiators (for example, azobisisobutyronitrile) and peroxide-based radical polymerization initiators (for example, tert-butyl peroxy-2-ethylhexanoate).

[0058] Thereby, a hydroxyl group-containing acrylic resin (a solution of a hydroxyl group-containing acrylic resin) can be obtained.

[0059] In the solution containing the hydroxyl group-containing acrylic resin, the solid content concentration of the hydroxyl group-containing acrylic resin is, for example, 20 mass % or more, preferably 40 mass % or more, and for example, 70 mass % or less.

[0060] The glass transition temperature of the hydroxyl group-containing acrylic resin is 10°C or higher, preferably 30°C or higher, more preferably 50°C or higher, further preferably 56°C or higher. From the viewpoint of further improving adhesion, it is particularly preferably 60°C or higher, most preferably 70°C or higher, and further preferably 75°C or higher. For example, it is 130°C or lower, preferably 115°C or lower, more preferably 105°C or lower, further preferably 95°C or lower, and particularly preferably 85°C or lower.

[0061] When the glass transition temperature is equal to or higher than the lower limit, adhesion to various substrates can be improved.

[0062] On the other hand, when the glass transition temperature is lower than the lower limit, the adhesion to various substrates cannot be improved.

[0063] Moreover, when the said glass transition temperature is below the said upper limit, the adhesiveness with various base materials can be improved.

[0064] The glass transition temperature can be calculated using the FOX equation. In the FOX equation, the Tg of the polymerized components (each monomer) can be determined using the values ​​listed in Table 10-2 (Main raw material monomers for acrylic resins for coatings) on pages 168-169 of New Polymer Library, Volume 7, Introduction to Synthetic Resins for Coatings (written by Kyozo Kitaoka, Polymer Publishing Company, Kyoto, 1974).

[0065] The SP value of acrylic resin containing hydroxyl groups is 9.40 (cal / cm 3 ) 1 / 2 Above, in addition, 11.00 (cal / cm 3 ) 1 / 2 Below, preferably 10.50 (cal / cm 3 ) 1 / 2 Below, more preferably 10.00 (cal / cm 3 ) 1 / 2 Below, more preferably 9.80 (cal / cm 3 ) 1 / 2 the following.

[0066] When the SP value is equal to or greater than the lower limit, adhesion to various substrates can be improved.

[0067] On the other hand, when the SP value is less than the lower limit, the adhesion to various substrates cannot be improved.

[0068] Moreover, when the said SP value is less than or equal to the said upper limit, the adhesiveness with various base materials can be improved.

[0069] On the other hand, when the SP value exceeds the upper limit, the adhesion to various substrates cannot be improved.

[0070] The SP value can be determined by a known method (described in RF Fedors, Polym. Eng. Sci., 14, (2), pp. 147-154 (1974)).

[0071] The hydroxyl value of the hydroxyl-containing acrylic resin is less than 100 mgKOH / g, preferably 80 mgKOH / g or less, more preferably 60 mgKOH / g or less, further preferably 50 mgKOH / g or less, and is, for example, 10 mgKOH / g or more, preferably 30 mgKOH / g or more.

[0072] When the hydroxyl value is less than the upper limit, adhesion to various substrates can be improved.

[0073] On the other hand, when the hydroxyl value is equal to or greater than the upper limit, adhesion to various substrates cannot be improved.

[0074] Moreover, when the said hydroxyl value is more than the said lower limit, the adhesiveness with various base materials can be improved.

[0075] In addition, the hydroxyl value can be calculated|required based on JIS K 0070-1992 (acetylation method), for example.

[0076] As described above, in this two-component curable resin composition, adhesion can be improved by setting the ratio of the alicyclic vinyl monomer content relative to the polymerized components, the glass transition temperature of the hydroxyl-containing acrylic resin, the SP value of the hydroxyl-containing acrylic resin, and the hydroxyl value of the hydroxyl-containing acrylic resin within predetermined ranges. In particular, to further improve adhesion, the ratio of the alicyclic vinyl monomer content relative to the polymerized components is set to 30.1% by mass or greater, and the glass transition temperature of the hydroxyl-containing acrylic resin is set to 130°C or less.

[0077] The polystyrene-equivalent weight average molecular weight (Mw) of the hydroxyl group-containing acrylic resin measured by gel permeation chromatography (GPC) is, for example, 5,000 or more, preferably 10,000 or more, and, for example, 100,000 or less, preferably 50,000 or less.

[0078] In addition, when using two or more hydroxyl-containing acrylic resins in combination, it is adjusted so that the average value of the weight average molecular weight (Mw) of these hydroxyl-containing acrylic resins may be within the above-mentioned range.

[0079] The hydroxyl group-containing acrylic resin can be used alone or in combination of two or more.

[0080] The content ratio of the hydroxyl group-containing acrylic resin relative to the main agent is, for example, 80 mass % or more, preferably 90 mass % or more, more preferably 95 mass % or more, and for example, 100 mass % or less.

[0081] <Other ingredients>

[0082] The main agent may contain other components together with the hydroxyl group-containing acrylic resin as needed.

[0083] Examples of other components include castor oil, polyacrylic acid resin, polyester resin, and low-molecular-weight polyol.

[0084] From the viewpoint of improving adhesion, the main agent preferably does not contain other components but is composed of a hydroxyl group-containing acrylic resin.

[0085] <Preparation of main agent>

[0086] The main agent can be prepared by mixing a hydroxyl group-containing acrylic resin (a solution of a hydroxyl group-containing acrylic resin) and other components as needed.

[0087] 2. Curing agent

[0088] The curing agent contains (poly)isocyanate (isocyanate and / or polyisocyanate). The curing agent is preferably composed of polyisocyanate.

[0089] Examples of the polyisocyanate include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and aromatic aliphatic polyisocyanate.

[0090] Examples of aliphatic polyisocyanates include aliphatic diisocyanates. Examples of aliphatic diisocyanates include 1,6-hexamethylene diisocyanate (1,6-HDI), 1,5-pentamethylene diisocyanate (1,5-PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2-, 2,3-, or 1,3-butanediisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate. Preferred aliphatic polyisocyanates include 1,6-HDI and 1,5-PDI. More preferred aliphatic polyisocyanates include 1,6-HDI.

[0091] Examples of the alicyclic polyisocyanate include alicyclic diisocyanates. Examples of the alicyclic diisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate) or a mixture thereof (H 12 MDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof (H6XDI), bis(isocyanatomethyl)norbornane (NBDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

[0092] Examples of aromatic polyisocyanates include aromatic diisocyanates. Examples of aromatic diisocyanates include 4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate or mixtures thereof (MDI), 2,4- or 2,6-toluene diisocyanate or mixtures thereof (TDI), o-dimethyldiphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), m- or p-phenylene diisocyanate or mixtures thereof, 4,4'-diphenyl diisocyanate, and 4,4'-diphenyl ether diisocyanate.

[0093] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates. Examples of aromatic aliphatic diisocyanates include xylylenediisocyanate (1,2-, 1,3-, or 1,4-xylylenediisocyanate or a mixture thereof) (XDI), 1,3- or 1,4-tetramethylxylylenediisocyanate or a mixture thereof (TMXDI), and ω,ω'-diisocyanato-1,4-diethylbenzene.

[0094] The polyisocyanate also includes derivatives of the polyisocyanate.

[0095] As the derivative of polyisocyanates, for example, can enumerate isocyanurate derivatives, allophanate derivatives, polyol derivatives, biuret derivatives, urea derivatives, oxadiazinetrione derivatives, carbodiimide derivatives, uretdione derivatives and uretonimine derivatives of above-mentioned polyisocyanates.As the derivative of polyisocyanates, preferably can enumerate isocyanurate derivatives and biuret derivatives.As the derivative of polyisocyanates, more preferably can enumerate isocyanurate derivatives.

[0096] As the polyisocyanate, preferably, a polyisocyanate derivative can be mentioned. As the polyisocyanate, more preferably, an isocyanurate derivative of 1,6-HDI, a biuret derivative of 1,6-HDI, and an isocyanurate derivative of 1,5-PDI can be mentioned. As the polyisocyanate, more preferably, an isocyanurate derivative of 1,6-HDI and a biuret derivative of 1,6-HDI can be mentioned.

[0097] The polyisocyanate may be used alone or in combination of two or more.

[0098] 3. Additives

[0099] The two-component curable resin composition may contain additives at appropriate ratios as needed.

[0100] Examples of additives include catalysts (e.g., dioctyltin dilaurate, bismuth carboxylate, titanium, aluminum catalysts, and amine catalysts), plasticizers, antiblocking agents, heat stabilizers, light stabilizers, antioxidants, release agents, pigments, pigment dispersants, dyes, lubricants, fillers, thixotropic agents, leveling agents, and anti-hydrolysis agents.

[0101] The timing of adding the additives can be appropriately set. Specifically, the additives may be added to the base agent and / or curing agent in advance, or may be added when the base agent and curing agent are mixed.

[0102] The additives may be used alone or in combination of two or more.

[0103] Preparation of 4.2 Liquid Curable Resin Composition

[0104] In a two-component curable resin composition, the base and curing agent are prepared separately and mixed immediately before use. In addition, when the base and / or curing agent are prepared as a solution, the two-component curable resin composition is prepared as a solution.

[0105] Regarding the mixing ratio of the main agent and the curing agent, especially when the curing agent is a polyisocyanate, the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate in the curing agent to the hydroxyl group of the hydroxyl-containing acrylic resin in the main agent is, for example, greater than 0.7, preferably greater than 0.9, and for example, less than 2.0, preferably less than 1.5, and more preferably less than 1.1.

[0106] In this way, a two-component curable resin composition was prepared.

[0107] 5. Method for producing a laminate (method for using a two-component curable resin composition)

[0108] The two-component curable resin composition is used, for example, to coat the surface of a substrate. By coating the substrate, a laminate is produced.

[0109] Reference Figure 1 A~ Figure 1 C. One embodiment of a method for producing a coating film and a laminate will be described.

[0110] Figure 1 A~ Figure 1 In C, the vertical direction on the paper is the vertical direction (thickness direction), the upper side on the paper is the upper side (one side in the thickness direction), and the lower side on the paper is the lower side (the other side in the thickness direction). In addition, the horizontal direction and the depth direction on the paper are plane directions perpendicular to the vertical direction. Specifically, follow the direction arrows in each figure.

[0111] The manufacturing method of the laminate 1 includes: a first step of preparing a substrate 2; a second step of applying a two-liquid curable resin composition on the surface (one surface in the thickness direction) of the substrate 2 to form a coating film 3; and a third step of heating the coating film 3 to form a coating layer 4.

[0112] [Step 1]

[0113] In the first step, if Figure 1 As shown in A, first, a substrate 2 is prepared.

[0114] The substrate 2 is an object to be coated, to whose surface (one surface in the thickness direction) various physical properties are imparted by the coating layer 4 .

[0115] It should be noted that Figure 1 In A, the substrate 2 has a flat plate shape, but the shape of the substrate 2 is not particularly limited, and various shapes can be selected.

[0116] The substrate 2 is not particularly limited, and examples thereof include resins, metals, and glass.

[0117] Examples of the resin include polyester resins, (meth) acrylic resins (including acrylic resins and / or methacrylic resins), polyolefin resins, polycarbonate resins, polyamide resins, polyimide resins, acrylonitrile-styrene-butadiene copolymer resins (ABS resins), polystyrene resins, polyvinylidene chloride, styrene-acrylonitrile copolymer resins, and cellulose acetate. Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of the (meth) acrylic resin include polymethyl methacrylate resin (PMMA). Examples of the polyolefin resin include polyethylene resin and polypropylene resin. Examples of the polyamide resin include nylon. Examples of the resin include polyamide resins. Examples of the resin include nylon.

[0118] Examples of the metal include iron, aluminum, zinc, steel plates, and stainless steel. Preferably, the metal is stainless steel.

[0119] From the viewpoint of heat resistance and chemical resistance, the substrate 2 is preferably one selected from the group consisting of nylon, stainless steel, and glass.

[0120] In addition, the substrate 2 may be subjected to surface treatment as needed. In addition, a primer layer may be formed in advance on the substrate 2 as needed.

[0121] [Step 2]

[0122] In the second step, Figure 1As shown in B, a two-component curable resin composition is applied to the surface (one surface in the thickness direction) of the substrate 2 to form a coating film 3 .

[0123] Examples of the coating method include spray coating, dip coating, roll coating, gravure coating, spin coating, bar coating, and doctor blade coating. Preferred coating methods include bar coating and spray coating.

[0124] As a result, a coating film 3 is formed on the surface (one surface in the thickness direction) of the substrate 2 , which is a coating material of the two-component curable resin composition (solution of the two-component curable resin composition).

[0125] [Step 3]

[0126] In the third step, Figure 1 As shown in C, the coating film 3 is heated to form a coating layer 4.

[0127] As heating conditions, the heating temperature is, for example, 120° C. or lower, preferably 90° C. or lower, and for example, 60° C. or higher. The heating time is, for example, 1 minute or longer, preferably 5 minutes or longer, more preferably 10 minutes or longer, and for example, 60 minutes or shorter, preferably 40 minutes or shorter.

[0128] It should be noted that heating may be performed in two or more stages. In addition, heating may be performed under reduced pressure or in an inert atmosphere.

[0129] Thereby, the coating film 3 is dried and cured, and the coating layer 4 composed of the cured product of the coating film 3 (two-component curable resin composition) is formed.

[0130] The thickness of the coating layer 4 is 5 μm or more, preferably 10 μm or more, and for example, 50 μm or less, preferably 20 μm or less.

[0131] In the above manner, the laminated body 1 including the substrate 2 and the coating layer 4 in this order is manufactured.

[0132] In the above description, the coating layer 4 is disposed on the surface of the substrate 2 (one surface in the thickness direction), but the coating layer 4 may be disposed on both surfaces of the substrate 2 (one surface in the thickness direction and the other surface in the thickness direction).

[0133] 6. Effects

[0134] In the two-component curable resin composition, the main component comprises a hydroxyl-containing acrylic resin, which is a copolymer comprising a polymerized component comprising a hydroxyl-containing (meth)acrylate and a vinyl monomer containing an alicyclic structure. The proportion of the vinyl monomer containing an alicyclic structure relative to the polymerized component is within a specified range. The glass transition temperature, SP value, and hydroxyl value of the hydroxyl-containing acrylic resin are within a specified range. Therefore, the coating 4 obtained using this two-component curable resin composition has excellent adhesion to various substrates 2.

[0135] The laminate 1 includes a coating layer 4 formed of a cured product of a two-component curable resin composition. Therefore, the laminate 1 has excellent adhesion to various substrates 2.

[0136] Example

[0137] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. It should be noted that, unless otherwise specified, "parts" and "%" are based on mass. In addition, the specific numerical values ​​of the mixing ratio (containing ratio), physical property values, parameters, etc. used in the following description can be replaced by the upper limit value (numerical value defined in the form of "below", "less than") or the lower limit value (numerical value defined in the form of "above", "greater than") of the corresponding mixing ratio (containing ratio), physical property values, parameters, etc. described in the above-mentioned "Specific Implementation Methods".

[0138] <Ingredient Details>

[0139] The abbreviations of the components used in each Example and each Comparative Example are described in detail.

[0140] HEMA: 2-Hydroxyethyl Methacrylate

[0141] IBX: Isobornyl methacrylate

[0142] CHMA: Cyclohexyl methacrylate

[0143] ADMA: Adamantyl methacrylate

[0144] St:Styrene

[0145] MMA: Methyl Methacrylate

[0146] BA: Butyl acrylate

[0147] EMA: ethyl methacrylate

[0148] 2EHA: 2-ethylhexyl acrylate

[0149] TKA-100: Isocyanurate derivative of 1,6-HDI, manufactured by Asahi Kasei Corporation

[0150] 24A-100: 1,6-HDI biuret derivative, manufactured by Asahi Kasei Corporation

[0151] D-370N: Isocyanurate derivative of 1,5-PDI, manufactured by Mitsui Chemicals, Inc.

[0152] PMMA: polymethyl methacrylate resin

[0153] PC: Polycarbonate

[0154] PC / ABS: Alloy of polycarbonate and ABS (ROA EFN800-04, manufactured by Sumitomo Bakelite)

[0155] SUS304: stainless steel

[0156] 66Ny: Nylon

[0157] <Preparation of 2-component curable resin composition>

[0158] Examples 1 to 11 and Comparative Examples 1 to 11

[0159] (Preparation of Main Agent (Hydryl-Containing Acrylic Resin))

[0160] Under nitrogen, 710.4 parts by mass of butyl acetate was heated to 100°C. Next, a solution prepared by dissolving 14.2 parts by mass of azobisisobutyronitrile in a total of 1000 parts by mass of the polymer components, which were mixed at the mass % values ​​listed in Tables 1 and 2, was added over 4 hours. Note that the values ​​listed in Tables 1 and 2 are in mass %.

[0161] After the addition, 1.64 parts by mass of tert-butyl peroxy-2-ethylhexanoate (PERBUTYL O (NOF Corporation)) was added at 100°C for 1 hour, followed by two steps of further reacting at 100°C for 1 hour. Then, 229.0 parts by mass of butyl acetate was added to obtain a solution of a hydroxyl-containing acrylic resin (solids content: 52%). This solution was used as the main agent.

[0162] (Preparation of Curing Agent)

[0163] The curing agents listed in Tables 1 and 2 were prepared.

[0164] (Preparation of two-component curable resin composition)

[0165] 30 parts by mass of the base agent (a solution of a hydroxyl-containing acrylic resin (52% solids concentration)), 2.27 parts by mass of the curing agent (TKA-100), and 39.17 g of butyl acetate were mixed. Next, 0.18 parts by mass of NEOSTANN U810 (dioctyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.), diluted to 1% by weight with butyl acetate, was added. This yielded a two-component curable resin composition. The equivalent ratio (NCO / OH) was as described in Tables 1 and 2.

[0166] In Example 2, 30 parts by mass of a base agent (a solution of a hydroxyl-containing acrylic resin (solids concentration 52%), 2.16 parts by mass of a curing agent (24A-100), and 40.17 g of butyl acetate were mixed. Subsequently, 0.18 parts by mass of NEOSTANN U810 (dioctyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.), diluted to 1% by weight with butyl acetate, was added. This yielded a two-component curable resin composition.

[0167] Separately, in Example 3, 30 parts by mass of a base agent (a solution of a hydroxyl-containing acrylic resin (solids concentration 52%)), 2.05 parts by mass of a curing agent (24A-100), and 40.48 g of butyl acetate were mixed. Subsequently, 0.18 parts by mass of NEOSTANN U810 (dioctyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.), diluted to 1% by weight with butyl acetate, was added. This yielded a two-component curable resin composition.

[0168] <Evaluation>

[0169] [Manufacturing of Laminated Body]

[0170] (Step 1)

[0171] As substrates, PMMA, PC, PC / ABS, glass, SUS304, and 66Ny were prepared.

[0172] (Step 2)

[0173] A solution of a two-component curable resin composition was applied to one surface in the thickness direction of each substrate using a bar coater #40 to form a coating film.

[0174] (Step 3)

[0175] The coating film was heated at 80° C. for 30 minutes to be cured, thereby forming a coating layer (film thickness of about 10 μm).

[0176] [Adhesion]

[0177] On the laminate of each embodiment and comparative example, a knife was used to cross-cut (100 squares) in a 1 mm × 1 mm checkerboard pattern in a manner that reached the substrate. Then, the adhesive tape was adhered to the surface and the state of the coating after instant peeling was observed visually. The adhesion was evaluated based on the following benchmarks. The results are shown in Tables 1 and 2.

[0178] {Benchmark}

[0179] ⊚: The number of squares that were closely bonded without peeling was 76 or more and 100 or less.

[0180] ○: The number of squares that were closely bonded without peeling was 51 or more and 75 or less.

[0181] △: The number of squares that were closely bonded without peeling was 26 or more and 50 or less.

[0182] ×: The number of squares that were closely bonded without peeling was 0 or more and 25 or less.

[0183] Then, the scores were scored with "⊚" representing 3 points, "∘" representing 2 points, "△" representing 1 point, and "×" representing 0 points, and the total score of each substrate was calculated as the score. The results are shown in Tables 1 and 2.

[0184] [Table 1]

[0185]

[0186] [Table 2]

[0187]

[0188] It should be noted that the above invention is provided as an exemplary embodiment of the present invention, but it is only for illustration and is not to be construed as limiting. Modifications of the present invention that can be understood by those skilled in the art are also included in the appended claims.

[0189] Industrial applicability

[0190] The two-component curable resin composition and laminate of the present invention are preferably used in the fields of vehicle coatings and home appliance coatings.

[0191] Description of Reference Numerals

[0192] 1 laminate

[0193] 2. Base material

[0194] 4 coating

Claims

1. 2 Liquid curable resin composition, comprising a main agent and a curing agent, The main agent comprises an acrylic resin containing a hydroxyl group, The hydroxyl-containing acrylic resin is a copolymer comprising a polymerization component of a hydroxyl-containing (meth)acrylate and a vinyl monomer containing an alicyclic structure. The vinyl monomer containing an alicyclic structure is composed of a vinyl monomer containing a bicycloalkyl group and / or a vinyl monomer containing a cycloalkyl group. The content ratio of the vinyl monomer containing an alicyclic structure relative to the polymer components is 15.0% by mass or more and 60.0% by mass or less, The glass transition temperature of the acrylic resin containing hydroxyl groups is above 10°C. The SP value of the acrylic resin containing hydroxyl groups is 9.40 (cal / cm 3 ) 1 / 2 Above 11.00 (cal / cm 3 ) 1 / 2 the following, The hydroxyl value of the acrylic resin containing hydroxyl groups is less than 100 mgKOH / g.

2. The two-component curable resin composition according to claim 1, wherein The glass transition temperature of the hydroxyl group-containing acrylic resin is 60° C. or higher.

3. The two-component curable resin composition according to claim 1, wherein The content ratio of the vinyl monomer containing an alicyclic structure relative to the polymer components is 30.1% by mass or more, The glass transition temperature of the hydroxyl group-containing acrylic resin is 130° C. or lower.

4. The two-component curable resin composition according to claim 1, wherein The curing agent comprises a (poly)isocyanate. 5 . A laminate comprising a substrate and a coating layer formed from a cured product of the two-component curable resin composition according to claim 1 . The laminate according to claim 5 , wherein: The substrate is one selected from the group consisting of nylon, stainless steel, and glass.

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