Curable composition, cured product thereof, and laminate

Abstract

To provide a curable composition which is applicable to a decorative paper or a decorative sheet and can be cured with less thermal energy than before, a cured product thereof, and a laminate including one or more of them.SOLUTION: The curable composition contains a curable component and a photopolymerization initiator. The curable component contains a polyisocyanate component (A) containing at least two isocyanate groups and a polyol component (B) containing at least two hydroxyl groups. At least one component selected from the component (A) and the component (B) further contains at least one (meth)acryloyl group, and / or the curable component further contains a (meth)acrylate component (C) containing at least one (meth)acryloyl group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a curable composition, a cured product thereof, and a laminate.

Background Art

[0002] Conventionally, in order to enhance the design and durability of housing building materials and furniture, etc., a resin-impregnated decorative board (hereinafter referred to as "decorative board") has been used as a surface material. The decorative board is obtained by integrating a resin-impregnated decorative paper (hereinafter referred to as "decorative paper") impregnated with melamine, which is a thermosetting resin, with a base material (such as a wood base material or an inorganic base material).

[0003] As a method for manufacturing decorative paper, for example, (1) an impregnating paper such as a porous base paper is immersed in a tank filled with a melamine resin to impregnate the paper with the melamine resin to obtain decorative paper, and then the decorative paper is overlaid on the upper surface of the base material and hot-pressed and formed under low pressure (low-pressure melamine method), (2) a method of laminating only melamine resin-impregnated decorative paper and phenol resin-impregnated decorative paper and hot-pressing and forming under high pressure (high-pressure melamine method) is known. These melamine decorative boards have high upper surface hardness, excellent stain resistance, abrasion resistance, heat resistance, and water resistance, and are difficult to be scratched. Therefore, the decorative board obtained by the low-pressure melamine method is used for furniture materials and interior materials, etc., and the decorative board obtained by the high-pressure melamine method is used for surface materials of furniture and doors, surface materials of shelves and counters, etc. because of its thin thickness. From the viewpoint of obtaining a decorative board excellent in surface smoothness and design, a decorative board in which a top coat layer is further provided on the surface of the decorative paper after manufacturing the decorative paper has also been proposed (for example, Patent Documents 1, 2, etc.).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] By the way, in the production of decorative boards, there is a problem that a large amount of thermal energy is consumed in the production process. That is, in order to produce a decorative board by impregnating, drying, and thermocompression bonding (180°C) petroleum-derived resins such as melamine resin and phenol resin as described above, the amount of thermal energy consumed in the production process becomes enormous. Therefore, there is a demand for a curable material that can produce decorative paper and decorative boards with less thermal energy than conventional thermosetting resins. In addition, since thermosetting resins such as melamine resin have a high proportion of petroleum-derived components, there is also a demand for a curable material that is environmentally friendly with less petroleum-derived components. In response to such problems, for example, Patent Document 3 proposes a manufacturing apparatus for decorative boards that can reduce the power consumption in the manufacturing process.

[0006] An object of the present disclosure is to provide a curable composition applicable to decorative paper and decorative boards, a curable composition that can be cured with less thermal energy than conventional ones, a cured product thereof, and a laminate containing one or more of these.

Means for Solving the Problems

[0007] As a result of intensive studies, the inventors of the present application have found that the above problems can be solved by using a dual-cure material capable of using both photocuring (ultraviolet curing, electron beam curing, etc.) and thermosetting as the curable component and controlling the ratio of thermosetting functional groups and photocurable functional groups in the curable component. Furthermore, surprisingly, it has been found that this curable material can be cured at a lower temperature than conventional ones, and can also be applied to all of the impregnating resin, top coat layer, and adhesive layer between the substrate of the decorative paper or decorative board. In addition, even if a biomass-derived material is selected as the curable component, the above effects can be maintained, so that it can be an environmentally friendly curable material with a low proportion of petroleum-derived components.

[0008] That is, the present invention has the following aspects. [1] It contains a curable component and a photoinitiator, The curable component contains a polyisocyanate component (A) containing at least two isocyanate groups, and a polyol component (B) containing at least two hydroxyl groups, and at least one component selected from the component (A) and the component (B) further contains at least one (meth)acryloyl group, and / or further contains a (meth)acrylate component (C) containing at least one (meth)acryloyl group, a curable composition. [2] The curable composition according to [1], wherein at least one component selected from the component (A) and the component (B) further contains at least one (meth)acryloyl group. [3] The curable component contains the component (C), and the component (C) contains a hydroxyl group-containing (meth)acrylate (C2) containing at least one (meth)acryloyl group and a hydroxyl group, the curable composition according to [1] or [2]. [4] The curable composition according to any one of [1] to [3], wherein the component (B) contains a (meth)acryloyl group-containing polyol (B2) having at least one (meth)acryloyl group and at least two hydroxyl groups. [5] The curable composition according to any one of [1] to [4], wherein the proportion of the biomass-derived component with respect to the total mass of the curable component is 10% by mass or more. [6] The curable composition according to any one of [1] to [5], wherein the average hydroxyl equivalent of the component (B) is 30 to 5,000. [7] The curable composition according to any one of [1] to [6], wherein the isocyanate index (average isocyanate group equivalent / average hydroxyl group equivalent) of the curable component is 0.01 to 2.0. [8] A cured product of the curable composition according to any one of [1] to [7]. [9] A laminate including at least one layer selected from the curable composition according to any one of [1] to [7] and the cured product according to [8].

[10] The laminate according to [9], which is a resin-impregnated decorative paper or a resin-impregnated decorative board. [Advantages of the Invention]

[0009] According to the present disclosure, it is possible to provide a curable composition that can be cured with less thermal energy than conventional ones, a cured product thereof, and a laminate containing one or more of these.

Brief Description of the Drawings

[0010]

Figure 1

Modes for Carrying Out the Invention

[0011] Hereinafter, an embodiment of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not inhibit the effects of the present disclosure. Each configuration and their combinations, etc. in each embodiment are examples, and within a range not departing from the gist of the present disclosure, addition, omission, substitution, and other changes of the configuration are possible as appropriate. The present disclosure is not limited by the embodiments, but is limited only by the claims. Each aspect disclosed in this specification can be combined with any other features disclosed in this specification. When a specific description described for one embodiment also applies to other embodiments, the description may be omitted in other embodiments. In the present disclosure, the expression "X to Y" for a numerical range means "X or more and Y or less".

[0012] [Curable Composition] The first embodiment in the present disclosure includes a curable component and a photopolymerization initiator. The curable component includes a polyisocyanate component (A) containing at least two isocyanate groups and a polyol component (B) containing at least two hydroxyl groups. One or more components selected from the component (A) and the component (B) further include at least one (meth)acryloyl group, and / or further include a (meth)acrylate component (C) containing at least one (meth)acryloyl group. According to the first embodiment, a curable composition that can be cured with less thermal energy than before can be provided.

[0013] <Curable component> The curable composition according to the first embodiment includes a polyisocyanate component (A) containing at least two isocyanate groups and a polyol component (B) containing at least two hydroxyl groups. One or more components selected from the component (A) and the component (B) further include at least one (meth)acryloyl group, and / or further include a (meth)acrylate component (C) containing at least one (meth)acryloyl group, and includes a curable component.

[0014] (Polyisocyanate component (A)) The curable component includes a polyisocyanate component (A) containing at least two isocyanate groups (hereinafter, may also be referred to as "component (A)"). Here, the "polyisocyanate component (A)" contains a polyisocyanate having at least two isocyanate groups (for example, polyisocyanate (A1) and / or (meth)acryloyl group-containing polyisocyanate (A2) described later, etc.) in an amount of 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more based on the total mass of the component (A).

[0015] In one embodiment, the number of isocyanate groups in component (A) (hereinafter referred to as "the number of isocyanate groups (a)") may be 2 to 4, or may be 2 to 3.5. If the number of isocyanate groups (a) is within the above range, it becomes easier to balance photocuring and thermosetting, and a curable composition that can be cured with less thermal energy can be easily obtained. When component (A) contains polyisocyanate (A1) and (meth)acryloyl group-containing polyisocyanate (A2) described later, the number of isocyanate groups (a) is the total value of the number of isocyanate groups of polyisocyanate (A1) and (A2).

[0016] The number of isocyanate groups (a) of component (A) can be calculated from the following formula (1). Number of isocyanate groups (a) = (number average molecular weight (Mn) of component (A)) × (isocyanate group concentration in component (A) (mass%)) / 4202 ··· (1) In formula (1), the number average molecular weight (Mn) of component (A) can be measured using GPC with solvent: THF, column temperature: 40 °C, and standard substance: polyethylene oxide. The isocyanate group concentration in component (A) can be analyzed by, for example, IR (infrared spectroscopy) or the following titration method etc.

[0017] ·Measurement of isocyanate group concentration The measurement of the isocyanate group concentration (mass%) by the titration method is carried out as follows. The measurement is carried out while stirring with a stirrer using a 100 mL glass flask. First, the blank value is measured as follows. Add 15 mL of a THF solution of dibutylamine (0.1 N) to 15 mL of THF. Further add 3 drops of bromophenol blue (1 mass% methanol dilution) to color it blue, and then titrate with an HCl aqueous solution having a normality of 0.1 N. Let the titration amount of the HCl aqueous solution at the time when discoloration is observed be Vb (mL). Next, measure the actual isocyanate group concentration. First, weigh Ws (g) of the sample, dissolve it in 15 mL of THF, and add 15 mL of a THF solution of dibutylamine (0.1 N). After confirming that the sample has been dissolved, add 3 drops of bromophenol blue (1 mass% methanol dilution) to color it blue, and then titrate with an aqueous HCl solution having a normality of 0.1 N. Let the titration volume of the aqueous HCl solution at the point where color change is observed be Vs (mL). Calculate the isocyanate group concentration in the sample from the following formula (2). Isocyanate group concentration (mass%) = [(Vb - Vs) × 1.005 × 0.42] / Ws ···(2) When using a commercially available product as component (A), the aforementioned isocyanate group concentration and number average molecular weight may adopt the manufacturer's nominal values.

[0018] In one embodiment, the isocyanate group concentration in component (A) may be 5 to 30 mass%, may be 10 to 30 mass%, may be 15 to 30 mass%, or may be 20 to 30 mass%. Further, the number average molecular weight (Mn) of component (A) may be 100 to 1,000, may be 150 to 1,000, may be 150 to 800, or may be 450 to 700. If the number average molecular weight (Mn) and isocyanate group concentration of component (A) are within the above ranges, the curability is likely to be good.

[0019] In one embodiment, the average isocyanate group equivalent of component (A) may be 80 to 1,000 g / mol, may be 90 to 750 g / mol, or may be 100 to 500 g / mol. If the average isocyanate group equivalent of component (A) is within the above range, the curability is likely to be good. Note that the "average isocyanate group equivalent" (hereinafter, may also be referred to as "NCO equivalent") may adopt the value measured in accordance with the standard of JIS K 1603-1, or may adopt the value calculated from the following formula (3). NCO equivalent = (molecular weight of isocyanate group (NCO group) (42)) / (isocyanate group concentration (mass%)) × 100 ···(3)

[0020] Component (A) can contain one or more polyisocyanates (A1) selected from polyisocyanate monomers and polyisocyanate derivatives having at least two isocyanate groups.

[0021] (Polyisocyanate (A1)) Examples of the polyisocyanate monomer contained in the polyisocyanate (A1) (hereinafter sometimes referred to as "component (A1)") include polyisocyanates such as aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

[0022] ·Aromatic polyisocyanate Examples of the aromatic polyisocyanate include bifunctional aromatic diisocyanates such as tolylene diisocyanate (2,4-, or 2,6-tolylene diisocyanate, or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate, or a mixture thereof), 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate, or a mixture thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), and 4,4'-diphenyl ether diisocyanate. Component (A) may contain one of these aromatic polyisocyanates alone or a combination of two or more thereof.

[0023] ·Aromatic aliphatic polyisocyanate Examples of the aromatic aliphatic polyisocyanate include bifunctional aromatic aliphatic diisocyanates such as xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate, or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate, or a mixture thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene. Component (A) may contain one of these aromatic aliphatic polyisocyanates alone or in combination of two or more thereof.

[0024] ·Aliphatic polyisocyanate Examples of the aliphatic polyisocyanate include bifunctional aliphatic diisocyanates such as trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (also known as hexamethylene diisocyanate) (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatemethyl caproate. Component (A) may contain one of these aliphatic polyisocyanates alone or in combination of two or more thereof.

[0025] ·Cycloaliphatic polyisocyanate Examples of alicyclic polyisocyanates include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate) (IPDI), hydrogenated xylylene diisocyanate (also known as bis(isocyanatomethyl)cyclohexane) (1,3- or 1,4-hydrogenated xylylene diisocyanate, or a mixture thereof) (H6XDI), hydrogenated diphenylmethane diisocyanate (also known as bis(isocyanatocyclohexyl)methane, methylene bis(cyclohexyl isocyanate)) (the trans-trans, trans-cis, cis-cis isomers of 4,4’-, 2,4’-, or 2,2’-methylene bis(cyclohexyl isocyanate), or a mixture thereof) (H 12 MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers, or a mixture thereof) (NBDI), and other bifunctional alicyclic diisocyanates. Component (A) may contain one of these alicyclic polyisocyanates alone or in combination of two or more.

[0026] In one embodiment, component (A1) may contain one of the aforementioned polyisocyanate monomers alone or in combination of two or more.

[0027] ·Polyisocyanate derivative Examples of the polyisocyanate derivative include multimers of the aforementioned polyisocyanate monomers (e.g., dimers, trimers (e.g., isocyanurate-modified products, iminooxadiazinedione-modified products), pentamers, heptamers, etc.), allophanate-modified products (e.g., allophanate-modified products produced by the reaction of the aforementioned polyisocyanate monomers with known monohydric alcohols and / or known dihydric alcohols), polyol-modified products (e.g., polyol-modified products (alcohol adducts, etc.) produced by the reaction of the aforementioned polyisocyanate monomers with known polyhydric alcohols having three or more hydroxyl groups), biuret-modified products (e.g., biuret-modified products produced by the reaction of the aforementioned polyisocyanate monomers with water or amines), urea-modified products (e.g., urea-modified products produced by the reaction of the aforementioned polyisocyanate monomers with diamines), oxadiazinetrione-modified products (e.g., oxadiazinetriones produced by the reaction of the aforementioned polyisocyanate monomers with carbon dioxide gas), carbodiimide-modified products (e.g., carbodiimide-modified products produced by the decarboxylation condensation reaction of the aforementioned polyisocyanate monomers), uretdione-modified products, uretonimine-modified products, and the like.

[0028] In one embodiment, component (A1) may contain one of the aforementioned polyisocyanate derivatives alone, or two or more thereof may be used in combination. From the viewpoint of easily adjusting the isocyanate functionality (a) to be greater than 2, component (A1) preferably contains a polyisocyanate derivative. Further, it may contain multimers of aliphatic diisocyanates.

[0029] When component (A) contains component (A1), it is preferable to use a polyisocyanate having the aforementioned isocyanate group concentration, number average molecular weight (Mn), and NCO equivalent. In a more preferred embodiment, component (A) can contain component (A1) having an isocyanate group concentration of 20 to 30% by mass and an NCO equivalent of 100 to 200 g / mol. Further, the ratio of component (A1) to the total mass of component (A) is preferably 10 to 100% by mass, more preferably 50 to 100% by mass.

[0030] Component (A) can further contain at least one (meth)acryloyl group. That is, component (A) can contain one or more components selected from component (A1) and (meth)acryloyl group-containing polyisocyanate (A2) containing at least two isocyanate groups and at least one (meth)acryloyl group. Note that the "(meth)acryloyl group" can include both acryloyl group and methacryloyl group.

[0031] ((meth)acryloyl group-containing polyisocyanate (A2)) The number of (meth)acryloyl groups in (meth)acryloyl group-containing polyisocyanate (A2) (hereinafter, may also be referred to as "component (A2)") may be 1 to 10, may be 2 to 8, or may be 2 to 4. Also, the number of isocyanate groups in component (A2) is 2 or more, and its upper limit is not particularly limited. In one embodiment, component (A2) may be an isocyanate group-containing urethane (meth)acrylate having at least one urethane bond, at least one (meth)acryloyl group, and at least two isocyanate groups in the molecule.

[0032] When component (A) contains component (A2), it is preferable to use (meth)acryloyl group-containing polyisocyanate having the aforementioned isocyanate group concentration, number average molecular weight (Mn), and NCO equivalent. In a more preferable embodiment, component (A) may contain component (A2) having an isocyanate group concentration of 10 to 15% by mass and an NCO equivalent of more than 200 and 350 or less g / moL. The ratio of component (A2) to the total mass of component (A) may be 0 to 90% by mass, or may be 0 to 50% by mass. In one embodiment, the ratio of component (A2) in component (A) may be 100% by mass.

[0033] As the component (A2), commercially available products may be used. For example, products such as "EBECRYL (registered trademark) 4141", "EBECRYL 4250", and "EBECRYL 4510" manufactured by Daicel Ornex Co., Ltd. can be adopted. Further, the component (A2) may be used alone or in combination of two or more kinds.

[0034] In one embodiment, from the viewpoint that the thermosetting property of the curable composition is likely to be good, the component (A) preferably contains the component (A1).

[0035] From the viewpoint that an environmentally friendly curable composition is likely to be obtained, the component (A1) and the component (A2) may contain components derived from biomass.

[0036] Examples of the biomass-derived component (A1) (hereinafter, the biomass-derived component (A1) is referred to as "component (A11)") include polyisocyanates obtained from plant-derived raw materials. In one embodiment, as the component (A11), those having a biomass content of 40% or more are preferable, and those having a biomass content of 50% or more are more preferable. Examples of the component (A11) having such a biomass content include those obtained by converting a plant-derived dicarboxylic acid into an acid amide and reducing it to convert it into a terminal amino group, and then reacting it with phosgene to convert the amino group into an isocyanate group. Preferably, an aliphatic polyisocyanate having 5 to 18 carbon atoms can be used. Specifically, aliphatic diisocyanates obtained from plant-derived raw materials such as 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,7-heptamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, dimer acid diisocyanate, octamethylene diisocyanate, and decamethylene diisocyanate can be mentioned. These may be used alone or in combination of two or more kinds.

[0037] In one embodiment, component (A11) may be obtained by converting the amino group in the amino acid, which is a plant-derived raw material, into an isocyanate group using the amino acid as a raw material. For example, the above-mentioned pentamethylene diisocyanate derived from biomass may be obtained using lysine as a raw material.

[0038] In one embodiment, component (A11) may contain derivatives such as multimers, biuret-modified products, allophanate-modified products, oxadiazinetrione-modified products, and polyol-modified products of aliphatic polyisocyanates obtained from the above-mentioned plant-derived raw materials. Among these, it is preferable to contain multimers of aliphatic polyisocyanates.

[0039] Examples of the multimers of aliphatic polyisocyanates obtained from plant-derived raw materials include dimers such as uretdione, uretoimine, and carbodiimide, and trimers or higher such as isocyanurate and iminooxadiazidione. It is more preferable to contain isocyanurate. In a more preferable embodiment, component (A11) can contain 1,5-pentamethylene diisocyanate and / or its derivative (more preferably isocyanurate) obtained from plant-derived raw materials.

[0040] In other preferable embodiments, component (A11) may be an aliphatic polyisocyanate and / or its derivative obtained from the above-mentioned plant-derived raw materials, having a biomass content of 50% or more and having an isocyanate group concentration and an NCO equivalent similar to those of the above-mentioned component (A1). Commercially available products can also be used as such component (A11). For example, products such as "Stabio (registered trademark) D-370N" and "Stabio D-376N" manufactured by Mitsui Chemicals, Inc. can be adopted.

[0041] Component (A) can contain component (A11) in a proportion similar to that of the above-mentioned component (A1).

[0042] Component (A2) can also contain a biomass-derived component (A2) (hereinafter, the biomass-derived component (A2) is referred to as "component (A21)"). The biomass content of component (A21) can be at any ratio.

[0043] Component (A) can contain component (A21) at the same ratio as the aforementioned component (A2).

[0044] (Polyol component (B)) The curable component contains a polyol component (B) having at least two hydroxyl groups (hereinafter, may also be referred to as "component (B)"). Here, the "polyol component (B)" contains a polyol having at least two hydroxyl groups (for example, polyol (B1) and / or (meth)acryloyl group-containing polyol (B2) described later, etc.) in an amount of 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more based on the total mass of component (B).

[0045] In one embodiment, the number of hydroxyl groups of component (B) (hereinafter, referred to as "number of hydroxyl groups (b)") may be 2 or more and less than 4 from the viewpoint that the balance between photocuring and thermosetting is more likely to be good. When component (B) contains polyol (B1) and (meth)acryloyl group-containing polyol (B2) described later, the number of hydroxyl groups (b) is the total value of the number of hydroxyl groups of polyol (B1) and (B2).

[0046] In one embodiment, the hydroxyl value of component (B) may be 10 to 2,000 KOHmg / g, or may be 100 to 2,000 KOHmg / g. Also, the number average molecular weight (Mn) of component (B) may be 30 to 10,000, may be 50 to 5,000, or may be 90 to 1,600. Also, in one embodiment, the average hydroxyl equivalent weight of component (B) may be 30 to 5,000 g / mol, may be 30 to 1,000 g / mol, or may be 30 to 600 g / mol. When the number average molecular weight, hydroxyl value, and / or average hydroxyl equivalent weight of component (B) are within the above ranges, the curability tends to be good. In this specification, the "hydroxyl value" can adopt the method described in the JIS standard. The number average molecular weight (Mn) of component (B) can be measured using GPC with the solvent: THF, column temperature: 40°C, and standard substance: standard polystyrene. Also, the "average hydroxyl equivalent weight" (hereinafter sometimes referred to as "OH equivalent weight") may adopt the value measured in accordance with the JIS standard, or may adopt the value calculated from the following formula (4). (Molecular weight of KOH (56.1) × 100) / (Hydroxyl value (KOH mg / g)) × 100 ···(4)

[0047] Component (B) can contain a known or commonly used polyol (B1) having at least two hydroxyl groups in the molecule.

[0048] (Polyol (B1)) The polyol (B1) (hereinafter sometimes referred to as "component (B1)") is not particularly limited. For example, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 1,3 - butanediol, 1,4 - butanediol, 1,6 - hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, polyoxy - C2 - 4 alkylene glycol (such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, etc.), polyester diol, polyether diol, polycarbonate diol, bisphenol A and its alkylene oxide adduct, bisphenol F and its alkylene oxide adduct, hydrogenated bisphenol A and its alkylene oxide adduct, hydrogenated bisphenol F and its alkylene oxide adduct, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, isosorbide, xylene glycol and other diols; glycerin, 1,1,1 - tris(hydroxymethyl)propane, D - sorbitol, xylitol, D - mannitol, D - mannite, diglycerin, polyglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, epoxy polyol, natural oil polyol, silicone polyol, fluorine polyol, polyolefin polyol and other polyols having at least three hydroxyl groups in the molecule can be mentioned. Further, as the component (B1), a polyoxyalkylene polyol obtained by adding an alkylene oxide using the above - mentioned polyol as an initiator may be used. The component (B1) can be used alone or in combination of two or more thereof.

[0049] When the component (B) contains the component (B1), it is preferable to use a polyol having the above - mentioned hydroxyl value, number average molecular weight (Mn), and OH equivalent. In a more preferred embodiment, component (B) can contain component (B1) having a hydroxyl value of 10 to 2,000 KOH mg / g and an OH equivalent of 30 to 5,000 g / mol. Further, the ratio of component (B1) to the total mass of component (B) is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and even more preferably 50 to 100% by mass.

[0050] Component (B) can further contain at least one (meth)acryloyl group. That is, component (B) can contain one or more components selected from component (B1) and (meth)acryloyl group-containing polyol (B2) containing at least two hydroxyl groups and at least one (meth)acryloyl group.

[0051] ((meth)acryloyl group-containing polyol (B2)) The number of (meth)acryloyl groups in the (meth)acryloyl group-containing polyol (hereinafter, may also be referred to as "component (B2)") may be 1 to 10, may be 2 to 8, or may be 2 to 4. Further, the number of hydroxyl groups in component (B2) may be 2 to 10, may be 2 to 8, or may be 2 to 4. In one embodiment, component (B2) may be a hydroxyl group-containing urethane (meth)acrylate having at least one urethane bond, at least one (meth)acryloyl group, and at least two hydroxyl groups in the molecule.

[0052] Examples of component (B2) include trimethylolpropane (meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and the like. These may be used alone or in combination of two or more.

[0053] When component (B) contains component (B2), it is preferable to use the (meth)acryloyl group-containing polyol having the above-mentioned hydroxyl value, number average molecular weight (Mn), and OH equivalent. In a more preferred embodiment, component (B) can contain one or more component (B2) having a hydroxyl value of 150 to 350 KOHmg / g and an OH equivalent of 100 to 600 g / moL. Further, the ratio of component (B2) to the total mass of component (B) can adopt any value in the range of 10 to 100% by mass.

[0054] In one embodiment, from the viewpoint of facilitating the balance between photocuring and thermosetting, component (B) preferably contains component (B2).

[0055] From the viewpoint of easily obtaining an environmentally friendly curable composition, component (B1) and component (B2) may contain components derived from biomass.

[0056] As the biomass-derived component (B1) (hereinafter, the biomass-derived component (B1) is referred to as "component (B11)"), for example, a polyol compound obtained from a plant-derived raw material, preferably having a biomass degree of 20% or more, more preferably 40% or more, and even more preferably 50% or more. The biomass degree of component (B11) may be 100%. Examples of such polyol compounds include isosorbide, vegetable oil-based polyols, plant-derived glycerin, bioethylene glycol, bio-1,3-propanediol, biobutylene glycol, and the like. These may be used alone or in combination of two or more.

[0057] Examples of vegetable oil-based polyols include castor oil-based polyols, soybean oil-based polyols, palm oil-based polyols, palm kernel oil-based polyols, coconut oil-based polyols, cashew nut oil-based polyols, olive oil-based polyols, cottonseed oil-based polyols, safflower oil-based polyols, sesame oil-based polyols, sunflower oil-based polyols, linseed oil-based polyols, etc. The number of hydroxyl groups in a molecule of polyols derived from vegetable oils is usually 2 to 3. Examples of castor oil-based polyols include castor oil, reaction products of castor oil and polyols, esterification reaction products of castor oil fatty acids and polyols, etc. Examples of polyols to be reacted with castor oil or castor oil fatty acids include dihydric polyols such as ethylene glycol, diethylene glycol, and propylene glycol, or polyhydric polyols having three or more valences such as glycerin, trimethylolpropane, hexanetriol, and sorbitol. Examples of soybean oil-based polyols include polyols derived from soybean oil, such as reaction products of soybean oil and polyols, esterification reaction products of soybean oil fatty acids and polyols, etc. As the polyol to be reacted with soybean oil or soybean oil fatty acids, the same ones as in the case of castor oil described above can be used. The same applies to palm oil-based polyols, cashew oil-based polyols, etc., as in the case of soybean oil-based polyols.

[0058] Component (B) can contain component (B11) in a proportion similar to that of the aforementioned component (B1).

[0059] In one embodiment, as the aforementioned component (B2), it can also contain a biomass-derived component (B2) (hereinafter, the biomass-derived component (B2) is referred to as "component (B21)").

[0060] As the component (B21), those with a biomass content of 10% or more are preferred, those with 20% or more are more preferred, and those with 30% or more are even more preferred. In one embodiment, from the viewpoint of obtaining a curable composition excellent in the balance between photocuring and thermocuring, a polyol-modified (meth)acrylate having 2 to 4 hydroxyl groups and 1 to 4 (meth)acryloyl groups is preferred. As such a polyol-modified (meth)acrylate, sorbitol-modified (meth)acrylate (number of hydroxyl groups: 4, number of (meth)acryloyl groups: 2), epoxidized soybean oil-modified (meth)acrylate (number of hydroxyl groups: 3.5, number of (meth)acryloyl groups: 3.5) are particularly preferred. Commercially available products may be used as such a polyol-modified (meth)acrylate. For example, products such as "ARONIX (registered trademark) M-926" manufactured by Toagosei Co., Ltd., and "EBECRYL 5848" manufactured by Daicel Allnex Co., Ltd. can be adopted. As described above, the component (B) also includes a compound that generates a hydroxyl group in the molecule by ring-opening.

[0061] ((Meth)acrylate component (C)) The curable component contained in the curable composition according to this embodiment can include a (meth)acrylate component (C) (hereinafter, may also be referred to as "component (C)") containing at least one (meth)acryloyl group. Here, the "(meth)acrylate component (C)" contains a (meth)acrylate having at least one (meth)acryloyl group (for example, a monofunctional or higher (meth)acrylate (C1) and / or a hydroxyl group-containing (meth)acrylate (C2) described later, etc.) in an amount of 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more based on the total mass of the component (C).

[0062] The curable composition according to this embodiment contains a curable component containing an isocyanate group, a hydroxyl group, and a (meth)acryloyl group. Among these, the (meth)acryloyl group may be contained in one or more components selected from component (A) and component (B), may be separately blended as component (C), or may be both. Thus, by containing three different functional groups, the curable composition according to this embodiment can be made into a dual-cure material capable of using both photocuring and thermocuring. Furthermore, by arbitrarily adjusting the number of isocyanate groups, hydroxyl groups, and (meth)acryloyl groups in the curable component, the composition after photocuring can be thermally cured at a lower temperature than before.

[0063] In one embodiment, the number of (meth)acryloyl groups in component (C) (hereinafter referred to as “(meth)acryloyl number (c)”) may be 1 to 20, may be 1 to 10, or may be 1 to 6. If the (meth)acryloyl group number (c) is within the above range, it becomes easier to balance photocuring and thermocuring, and the amount of energy during production is likely to decrease. When component (C) contains a monofunctional or higher (meth)acrylate (C1) and a hydroxyl group-containing (meth)acrylate (C2) described later, the (meth)acryloyl number (c) is the total value of the (meth)acryloyl numbers of (meth)acrylate (C1) and (C2).

[0064] Component (C) can contain a monofunctional or higher (meth)acrylate (C1) (hereinafter sometimes referred to as “component (C1)”) containing at least one (meth)acryloyl group in the molecule.

[0065] (Monofunctional or higher (meth)acrylate (C1)) Examples of the monofunctional (meth)acrylate in the component (C1) include aliphatic (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, butoxyethyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate; and alicyclic (meth)acrylates such as cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate. These may be used alone or in combination of two or more.

[0066] Examples of the bifunctional (meth)acrylate include aliphatic (meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, glycerin di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, and ethoxylated 2-methyl-1,3-propanediol di(meth)acrylate; alicyclic (meth)acrylates such as cyclohexane dimethanol (meth)acrylate, ethoxylated cyclohexane dimethanol (meth)acrylate, propoxylated cyclohexane dimethanol (meth)acrylate, ethoxylated propoxylated cyclohexane dimethanol (meth)acrylate, tricyclodecane dimethanol (meth)acrylate, ethoxylated tricyclodecane dimethanol (meth)acrylate, propoxylated tricyclodecane dimethanol (meth)acrylate, ethoxylated propoxylated tricyclodecane dimethanol (meth)acrylate, ethoxylated hydrogenated bisphenol A di(meth)acrylate, propoxylated hydrogenated bisphenol A di(meth)acrylate, and ethoxylated propoxylated hydrogenated bisphenol A di(meth)acrylate. These may be used alone or in combination of two or more.

[0067] Examples of the (meth)acrylate having three or more functional groups include aliphatic (meth)acrylates such as trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated propoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated propoxylated pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. These may be used alone or in combination of two or more. Among these, from the viewpoint of the strength of the coating film, it is preferable to contain a (meth)acrylate having two or more functional groups, and it may contain a trifunctional (meth)acrylate or a tetrafunctional (meth)acrylate.

[0068] (Hydroxyl group-containing (meth)acrylate (C2)) In one embodiment, component (C) can contain a hydroxyl group-containing (meth)acrylate (C2) (hereinafter, may also be referred to as "component (C2)") containing at least one (meth)acryloyl group and a hydroxyl group. Here, the number of hydroxyl groups contained in component (C2) is more than 0 and less than 2. The (meth)acrylate having two or more hydroxyl groups is contained in the aforementioned component (B2).

[0069] In one embodiment, the number of (meth)acryloyl groups in component (C2) is not particularly limited and may be 1 to 20, may be 1 to 10, or may be 1 to 6.

[0070] Examples of the component (C2) containing one (meth)acryloyl group and one hydroxyl group in the molecule include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and hydroxy (meth)acrylate compounds such as (poly)alkylene glycol mono (meth)acrylates such as (poly)ethylene glycol mono (meth)acrylate and (poly)propylene glycol mono (meth)acrylate. These may be used alone or in combination of two or more.

[0071] Examples of the component (C2) containing two or more (meth)acryloyl groups and more than 0 and less than 1 hydroxyl group include glycerin-modified (meth)acrylate (number of hydroxyl groups: 0.5, number of (meth)acryloyl groups: 2.5), pentaerythritol triacrylate, and the like. These may be used alone or in combination of two or more.

[0072] In one embodiment, from the viewpoint of improving thermosetting properties, the component (C) preferably contains the component (C2). More preferably, it contains a hydroxyl group-containing (meth)acrylate containing two or more (meth)acryloyl groups and more than 0 and less than 1 hydroxyl group.

[0073] From the viewpoint of easily obtaining an environmentally friendly curable composition, the component (C2) may contain a biomass-derived component (hereinafter, the biomass-derived component (C2) is referred to as "component (C21)"). The component (C21) may contain the aforementioned component (B11) as a raw material. The biomass content of the component (C21) is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more. Commercially available products may be used as such a component (C21). For example, "Aronix M-920" (plant-derived raw material glycerin-modified (meth)acrylate) manufactured by Toagosei Co., Ltd. can be adopted.

[0074] (Other components) In one embodiment, the curable component may contain components other than the aforementioned components (A) to (C) (other components). Examples of other components include isocyanate components other than component (A), hydroxyl group components other than component (B), and the like.

[0075] Examples of isocyanate components other than component (A) include isocyanate monomers and / or isocyanate derivatives having a number of isocyanate groups in the molecule of more than 0 and less than 2; (meth)acryloyl group-containing isocyanates other than component (A2) (the number of isocyanate groups in the molecule is more than 0 and less than 2), and the like. These may be used alone or in combination of two or more.

[0076] Examples of hydroxyl group components other than component (B) include monohydric alcohols such as methanol and ethanol. These may be used alone or in combination of two or more.

[0077] In one embodiment, the isocyanate index (average isocyanate group equivalent weight / average hydroxyl group equivalent weight) of the curable component is preferably from 0.01 to 2.0, more preferably from 0.1 to 1.5, and even more preferably from 0.2 to 1.2. In a particularly preferred embodiment, the isocyanate index may be 1.0. By setting the isocyanate index within the above range, a curable composition excellent in the balance between photocuring and thermocuring is likely to be obtained. The isocyanate index refers to a value calculated based on all isocyanate groups and all hydroxyl groups contained in the curable component. When the curable component contains an isocyanate component other than the aforementioned component (A) and a hydroxyl group-containing component other than component (B) and component (C2), it is preferable to contain these components within a range that satisfies the aforementioned isocyanate index.

[0078] In one embodiment, the ratio of the biomass-derived component to the total mass of the curable component is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more. Further, from the viewpoint of making the curable composition more environmentally friendly, the ratio of the biomass component in the total mass of the curable component may be 100%.

[0079] <Photoinitiator> The curable composition according to the first embodiment further contains a photoinitiator. Examples of the photoinitiator include benzophenone, acetophenone benzyl, benzyldimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyldisulfite, methyl orthobenzoylbenzoate, ethyl 4-dimethylaminobenzoate (e.g., manufactured by Nippon Kayaku Co., Ltd., trade name "KAYACURE (registered trademark) EPA", etc.), 2,4-diethylthioxanthone (e.g., manufactured by Nippon Kayaku Co., Ltd., trade name "KAYACURE DETX", etc.), 2-methyl-1-[4-(methyl)phenyl]-2-morpholinopropanone-1 (e.g., manufactured by Ciba Geigy Ltd., trade name "Irgacure (registered trademark) 907", etc.), 1-hydroxycyclohexyl phenyl ketone (e.g., manufactured by IGM, trade name "Omn184", etc.), 2-amino-2-benzoyl-1-phenylalkane compounds such as 2-dimethylamino-2-(4-morpholino)benzoyl-1-phenylpropane, tetra(t-butylperoxycarbonyl)benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, aminobenzene derivatives such as 4,4'-bis(diethylamino)benzophenone, imidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole (e.g., manufactured by Hodogaya Chemical Co., Ltd., trade name "B-CIM", etc.), halomethylated triazine compounds such as 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-triazine, and halomethyloxadiazole compounds such as 2-trichloromethyl-5-(2-benzofuran-2-yl-ethenyl)-1,3,4-oxadiazole. These may be used alone or in combination of two or more. Further, a photosensitizer may be added as necessary.

[0080] The content of the photoinitiator in the curable composition is preferably 0.5 to 12% by mass, more preferably 0.5 to 10% by mass, and even more preferably 0.5 to 8% by mass with respect to the total mass of the curable composition. When the content of the photoinitiator is within the above range, the curable composition according to the present embodiment can be appropriately cured by ultraviolet rays or the like described later.

[0081] (Other additives) The curable composition according to the present embodiment may contain components other than the curable components and photoinitiators (other additives). The other additives are not particularly limited, and any additives that can be blended in a photocurable composition and / or a thermosetting composition can be blended. For example, radical polymerization initiators other than photoinitiators, ultraviolet absorbers, reaction accelerators, light stabilizers, surface modifiers, etc. may be blended.

[0082] ·Ultraviolet absorber As the ultraviolet absorber, known or commonly used ones can be used and are not particularly limited. For example, cyanoacrylate-based, dihydroxybenzophenone-based, benzotriazole-based, triazine-based, and benzophenone-based ultraviolet absorbers can be mentioned.

[0083] Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3-diphenylacrylate and ethyl-2-cyano-3,3-diphenylacrylate. Examples of the dihydroxybenzophenone-based ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, (2,4-dihydroxyphenyl)-phenylmethane, hydroxymethoxybenzophenone sulfonic acid, 2-(2H-benzotriazol-2-yl)-4-methyl, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl), and 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl. Examples of benzotriazole-based ultraviolet absorbers include 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], and the like. Examples of triazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanolyloxy)ethoxy]phenol, 2-(4-((2-hydroxy-3-dodecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(4-((2-hydroxy-3-tridecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(4-((2-hydroxy-3-(2’ethyl)hexyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bisbutyloxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy, and the like. Examples of benzophenone-based ultraviolet absorbers include [2-hydroxy-4-(octyloxy)phenyl]phenylmethanone. The ultraviolet absorber may be used alone or in combination of two or more.

[0084] ·Light stabilizer As the light stabilizer, known or commonly used ones can be used, and there is no particular limitation. For example, 2,2,6,6-tetraalkyl-4-piperidyl esters (such as 2,2,6,6-tetramethyl-4-piperidyl esters), 4-alkoxy-2,2,6,6-tetraalkylpiperidines [for example, 4-(C1-10 alkoxy)-2,2,6,6-piperidine such as 4-methoxy-2,2,6,6-tetramethylpiperidine; 4-(C6-10 aryloxy)-2,2,6,6-piperidine such as 4-phenoxy-2,2,6,6-tetramethylpiperidine; 4-(C6-10 aryl)-(C1-4 alkyl)-2,2,6,6-tetramethylpiperidine such as 4-benzyloxy-2,2,6,6-tetramethylpiperidine, etc.], bis(2,2,6,6-tetraalkyl-4-piperidyloxy)alkanes [for example, bis(2,2,6,6-tetramethyl-4-piperidyloxy)(C2-6 alkane) such as 1,2-bis(2,2,6,6-tetramethyl-4-piperidyloxy)ethane, etc.], tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate; bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate; the reaction product of tetramethyl 1,2,3,4-butanetetracarboxylate with 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β’,β’-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diol, etc. are mentioned. In addition, the light stabilizer may be used alone or in combination of two or more.

[0085] ·Reaction accelerator As the reaction accelerator, known or commonly used ones can be used and are not particularly limited. For example, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or its salts (e.g., phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) or its salts (e.g., phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylcyclohexylamine, etc.; imidazoles such as 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, etc.; phosphate esters; phosphines such as triphenylphosphine, tris(dimethoxy)phosphine, etc.; phosphonium compounds such as tetraphenylphosphonium tetra(p-tolyl)borate; organometallic salts such as zinc octylate, tin octylate, zinc stearate, etc.; metal chelates such as aluminum acetylacetone complex, etc. The reaction accelerator may be used alone or in combination of two or more.

[0086] <Method for producing curable composition> The curable composition according to the first embodiment can be produced by mixing the above-mentioned curable component, a photopolymerization initiator, and, if necessary, the above-mentioned other additives. As the mixing means, known or commonly used means, for example, various mixers such as a dissolver, a homogenizer, a kneader, a roll, a bead mill, a self-revolving and revolving stirring device, etc. can be used. Conditions such as the temperature and rotation speed during mixing are not particularly limited and can be set as appropriate.

[0087] The curable composition according to the first embodiment can be cured with less thermal energy than before by using photopolymerization and thermal curing in combination. Such a curable composition can be suitably used, for example, as an impregnating resin, an adhesive layer composition, and a top coat layer composition for decorative boards and decorative papers. Of course, the use of the curable composition is not limited to these for decorative boards and decorative papers.

[0088] [Cured product] The second embodiment in the present disclosure is a cured product of the curable composition according to the first embodiment. The curable composition according to the first embodiment can be made into a cured product by the combined use of light irradiation and heating. Note that the cured product according to the second embodiment includes both those obtained by irradiating the aforementioned curable composition with ultraviolet rays or active energy rays described later to promote the curing reaction and those obtained by thermosetting after photocuring to be completely cured. In addition, a "semi-cured product" in a state where the curable composition is irradiated with light or heated until it loses fluidity is also included in the cured product of the present embodiment.

[0089] The cured product according to the present embodiment can be obtained as a cured coating film, for example, by applying the curable composition according to the first embodiment to an object such as a substrate and then performing photocuring and / or thermosetting.

[0090] The method for applying the curable composition is not particularly limited, and a conventionally known method can be adopted. For example, coating methods, casting methods, etc. can be mentioned.

[0091] (Photocuring) Photocuring is preferably performed by irradiating active energy rays such as ultraviolet rays or electron beams. As the light source for ultraviolet irradiation, for example, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, etc. are used. The irradiation time of ultraviolet rays can be arbitrarily adjusted between several seconds and several tens of seconds depending on the type of light source, the distance between the light source and the coating surface, and other conditions. On the other hand, in the case of electron beam irradiation, for example, an electron beam having an energy in the range of 50 to 1000 KeV is used, and an irradiation dose of 2 to 5 Mrad is preferably used. Usually, an irradiation source with a lamp output of about 80 to 300 W / cm is used.

[0092] (Thermosetting) After photo-curing, it is preferably further thermally cured. The temperature during thermal curing is not particularly limited as long as it can cure the curable composition, but from the viewpoint of reducing thermal energy during production, room temperature is preferable, and from the viewpoint of working speed, heating is preferable.

[0093] The thickness of the cured coating film is not particularly limited and can be arbitrarily adjusted according to the application. For example, it may be adjusted in the range of 0.5 to 1,000 μm, preferably 2 to 500 μm.

[0094] The object (coated object) to which the curable composition is applied is not particularly limited. For example, plastic articles such as polyethylene terephthalate (PET), polycarbonate, polymethacrylate, and vinyl chloride resin, those obtained by vapor-depositing metal on the plastic surface of the above articles, and various articles such as glass, wood, metal plates, and paper can be mentioned. The coated surface may be subjected to a release treatment.

[0095] [Laminate] The third embodiment of the present disclosure is a laminate including one or more layers selected from the curable composition according to the first embodiment and the cured product according to the second embodiment. Such a laminate is not particularly limited, but is preferably decorative paper or a decorative board. Hereinafter, as an aspect of the laminate, details of decorative paper and decorative boards will be described.

[0096] [Decorative paper] When the laminate according to the third embodiment is decorative paper, the decorative paper is obtained by impregnating a porous base paper with the curable composition according to the first embodiment and then curing it. Note that a pattern layer for enhancing the design property or a top coat layer for enhancing the smoothness may be provided on the surface of the decorative paper. That is, the decorative paper according to the present embodiment may be a multilayer body having a layer containing the curable composition and / or the cured product according to the present embodiment.

[0097] As the porous base paper, a fibrous sheet-like material such as paper with good water absorption that can be impregnated with the curable composition can be used. For example, tissue paper, titanium paper, high-quality paper, bleached or unbleached kraft paper, etc. can be used. Among these, it is preferable to adopt titanium paper, which is excellent in both printability and resin impregnation suitability.

[0098] <Decorative board> By further attaching the decorative paper obtained above to the base material, a decorative board can be obtained.

[0099] FIG. 1 is a cross-sectional view showing an example of a decorative board 100 including a decorative paper 10 containing the curable composition and / or cured product according to the present embodiment as an impregnating resin, and a base material 20. The decorative paper 10 in the decorative board 100 of FIG. 1 includes a porous base paper 1, a top coat layer 2, and an adhesive layer 3. The porous base paper 1 is impregnated with the curable composition and / or cured product according to the present embodiment. Further, in the decorative paper 10 of FIG. 1, the top coat layer 2 and the adhesive layer 3 are also composed of the curable composition and / or cured product according to the present embodiment. Such a decorative board 100 is obtained, for example, by applying the curable composition according to the present embodiment to one surface of the base material 20 by an arbitrary method, then laminating the porous base paper 1, and impregnating the porous base paper 1 with the curable composition. Thereby, the adhesive layer 3 can also be laminated on one surface (the surface on the base material 20 side) of the porous base paper 1. Then, the curable composition according to the present embodiment is further applied onto the other surface of the porous base paper 1 to laminate the top coat layer 2. After covering the surface of the top coat layer 2 with a resin film (such as a PET film), ultraviolet rays or active energy rays are irradiated from the resin film side to cure the top coat layer 2. Then, the resin film is peeled off and further thermally cured to cure the impregnating resin and the adhesive layer 3. Thereby, the decorative paper 10 and the base material 20 can be integrated to obtain the decorative board 100.

[0100] As the base material 20, a plate-like base material is preferable, and for example, an inorganic base material, a wood base material, an organic base material, etc. can be adopted. Examples of the inorganic base material include cement boards, volcanic glass multi-layer boards, calcium silicate boards, magnesium silicate boards, magnesium oxide boards, and the like. Examples of the wood base material include plywood, insulation boards, MDF (Medium Density Fiberboard), hard boards, particle boards, oriented strand boards, and the like. Examples of the organic base material include plastic boards such as thermosetting resins or thermoplastic resins. Specifically, for example, phenolic resin boards, polycarbonate boards, acrylic resin boards, rigid vinyl chloride boards, flexible vinyl chloride boards, polypropylene resin boards, polystyrene resin boards, polyethylene terephthalate (PET) resin boards, and the like can be mentioned. Among these, from the viewpoint of easily obtaining a decorative board excellent in non-combustibility and having excellent strength, an inorganic base material is preferable.

[0101] The thickness of the base material 20 is not particularly limited, but from the viewpoints of the strength of the base material and ease of handling, 20 μm to 25 mm is preferable.

[0102] As described above, since the impregnating resin can be cured by using both photocuring and thermocuring in the decorative paper and the decorative board including the curable composition according to the present embodiment, it can be manufactured with less thermal energy than in the past.

Examples

[0103] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.

[0104] [Materials] The materials used in the examples and comparative examples are as follows. The details of each component are described in Table 1. <Component (A)> · Component (A11-1): Biomass-derived 1,5-pentamethylene diisocyanate derivative (manufactured by Mitsui Chemicals, Inc., product name "Stabio D-370N"). · Component (A11-2): Biomass-derived 1,5-pentamethylene diisocyanate derivative (manufactured by Mitsui Chemicals, Inc., product name "Stabio D-376N"). · Component (A2-1): Isocyanate group-containing acrylate (manufactured by Daicel Allnex Co., Ltd., product name "EBECRYL 4141"). <Component (B)> · Component (B11-1): Plant-derived glycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., product name "R-PG"). · Component (B21-1): Sorbitol-modified acrylate (manufactured by Toagosei Co., Ltd., product name "Aronix M-926"). · Component (B21-2): Soybean oil-modified epoxy acrylate (manufactured by Daicel Allnex Co., Ltd., product name "EBECRYL 5848"). <Component (C)> · Component (C21-1): Glycerin-modified acrylate (manufactured by Toagosei Co., Ltd., product name "Aronix M-920"). <Photoinitiator> · 1-Hydroxycyclohexyl phenyl ketone (manufactured by IGM, product name "Omn184"). <Reaction accelerator> · 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU).

[0105]

Table 1

[0106] [Examples 1 to 3 and Comparative Examples 1 to 4] Using the above materials, each component was mixed at the composition and content ratio shown in Table 2 to obtain a curable composition. For the obtained curable composition, curability and adhesion were evaluated under the following conditions. The results are shown in Table 2.

[0107] <Curability and adhesion evaluation> On the surface of a base PET film (thickness 100 μm), the curable composition was applied at 100 g / m 2It was coated. Then, a porous base paper (impregnated titanium base paper, manufactured by KJ Special Paper Co., Ltd.) was laminated, and the curable composition was impregnated into the porous base paper to obtain a paper layer. On the paper layer, the curable composition was further coated at 100 g / m 2 After coating, the outermost surface was covered with a protective PET film (thickness: 100 μm), and a laminate was obtained by laminating in the order of a base PET film / adhesive layer (curable composition) / paper layer / top coat layer (curable composition) / protective PET film. (Photo-curing evaluation) The obtained laminate was irradiated with ultraviolet rays from the protective PET film side (light source: high-pressure mercury lamp, irradiation conditions: 2 kw, 4 m, 2 passes. Integrated light quantity: 800 mJ / cm 2 ) to cause photo-curing. Then, the protective PET film was peeled off, and the curability of the top coat layer was evaluated according to the following Evaluation Criteria 1. Also, the paper layer was peeled off, and the curability of the paper layer and the curability of the adhesive layer were evaluated according to Evaluation Criteria 2. (Evaluation Criteria 1) A: There is no tack when touching the top coat layer with a finger. B: There is tack when touching the top coat layer with a finger. (Evaluation Criteria 2) A: The base PET film and the paper layer were adhered (the paper layer and the adhesive layer were cured). B: The base PET film and the paper layer were not adhered (the paper layer and the adhesive layer were not cured). (Photo-curing and heat-curing evaluation) After the obtained laminate was photo-cured under the same conditions as above, it was put into an oven at 80 °C, and the time until all layers were cured was measured. After the heat-curing was completed, the protective PET film was peeled off, and the curability of the top coat layer was evaluated according to the above Evaluation Criteria 1. Also, the paper layer was peeled off, and the curability of the paper layer and the curability of the adhesive layer were evaluated according to the above Evaluation Criteria 2. Furthermore, the curability in photo-curing and heat-curing was evaluated according to the following Evaluation Criteria 3. (Evaluation Criteria 3) Pass: All of the top coat layer, the paper layer, and the adhesive layer were cured, and the time required for heat-curing was less than 30 minutes. Non - compliance: Any one of the top - coat layer, paper layer, or adhesive layer was not cured, or although all layers were cured, the time required for thermosetting was 30 minutes or more. (Adhesion evaluation) After the above - mentioned photocuring and thermosetting, the peelability when peeling the paper layer from the base PET film was evaluated in five grades. Regarding "0 evaluation" as the uncured state and "5 evaluation" as the most adherent (difficult to peel), the peelability between the paper layer and the base PET film was evaluated as 0, 1, 2, 3, 4, 5, and a value of 4 or more was considered as passing.

[0108] [Table 2]

[0109] As shown in Table 2, in Examples 1 to 4 that satisfied the composition of the curable composition according to the first embodiment, all of the top - coat layer, paper layer, and adhesive layer were cured by photocuring and thermosetting. Furthermore, the time required for thermosetting was also less than 30 minutes. On the other hand, for the curable compositions of Comparative Examples 1 to 3 that did not contain component (B), although the top - coat layer was cured by photocuring, the paper layer and the adhesive layer did not cure even after heating for 60 minutes or more. Also, for the curable composition of Comparative Example 4 that did not contain a (meth)acryloyl group, although the paper layer and the adhesive layer were cured by photocuring and thermosetting, the top - coat layer did not cure. It is considered that in order to completely cure the curable composition of Comparative Example 4, it is necessary to perform a hot press or thermosetting under higher - temperature conditions. From the above results, it was found that the curable composition according to the first embodiment can be cured with less thermal energy than before. Furthermore, as shown in Examples 1 to 4, by adopting a biomass - derived material, a curable composition with less petroleum - derived components and environmentally - considerate can be obtained. Such a curable composition and / or cured product can be suitably used as an impregnating resin for decorative paper and decorative boards. Also, it can be suitably used as a curable composition for the adhesive layer and the top - coat layer. [Explanation of symbols]

[0110] 1: Porous base paper 2: Top - coat layer 3: Next layer 10: Cosmetic paper 20: Substrate 100: Cosmetic board

Claims

1. Contains a curable component and a photopolymerization initiator, The curable component is a polyisocyanate component (A) containing at least two isocyanate groups; and a polyol component (B) containing at least two hydroxyl groups, The curable composition further comprises one or more components selected from the component (A) and the component (B), which further comprises at least one (meth)acryloyl group, and / or further comprises a (meth)acrylate component (C) comprising at least one (meth)acryloyl group.

2. The curable composition according to claim 1 , wherein one or more components selected from component (A) and component (B) further comprise at least one (meth)acryloyl group.

3. the curable component comprises component (C), The curable composition according to claim 1 or 2, wherein the component (C) comprises a hydroxyl group-containing (meth)acrylate (C2) containing at least one (meth)acryloyl group and a hydroxyl group.

4. The curable composition according to claim 1 or 2, wherein the component (B) comprises a (meth)acryloyl group-containing polyol (B2) having at least one (meth)acryloyl group and at least two hydroxyl groups.

5. The curable composition according to claim 1 or 2, wherein a ratio of the biomass-derived component to a total mass of the curable component is 10 mass% or more.

6. The curable composition according to claim 1 or 2, wherein the average hydroxyl equivalent of the component (B) is 30 to 5,000.

7. The curable composition according to claim 1 or 2, wherein the curable component has an isocyanate index (average isocyanate group equivalent / average hydroxyl group equivalent) of 0.01 to 2.

0.

8. A cured product of the curable composition according to claim 1.

9. A laminate comprising at least one layer selected from the curable composition according to claim 1 and the cured product according to claim 8.

10. The laminate according to claim 9, which is a resin-impregnated decorative paper or a resin-impregnated decorative board.

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