Active energy ray-curable resin composition, coating film, and laminate

Abstract

To provide an active energy ray-curable resin composition capable of forming a coating film having high hardness and excellent scratch resistance.SOLUTION: The present invention provides the active energy ray-curable resin composition containing an active energy ray-curable component. The active energy ray-curable component contains an addition reaction product (X) of a monomer (M) containing glycerol diacrylate (A) and an isocyanate compound (C). The monomer (M) further contains glycerol triacrylate (B). The monomer (M) has a hydroxyl value of 5 mg KOH / g or more and 80 mg KOH / g or less. The isocyanate compound (C) is at least one selected from the group consisting of aliphatic isocyanates and derivatives thereof. The addition reaction product (X) is contained in an amount of 15 mass% or less based on the total mass of the active energy ray-curable component.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable resin composition, a coating film, and a laminate. [Background technology]

[0002] Active energy ray-curable resin compositions containing a polymerizable component that is cured by active energy rays such as ultraviolet rays are widely used in coating applications and the like because they can form cured products such as coating films when cured.

[0003] For example, it is known that active energy ray-curable resin compositions are used as coating agents for the purpose of protecting the surfaces of resin films and the like used in electronic devices, optical devices, and the like. Specifically, a process is carried out in which the active energy ray-curable resin composition is applied to the surface of a resin film or the like to form a film, and the film is then irradiated with active energy rays such as ultraviolet rays to cure the film. This process forms a coating film of the active energy ray-curable resin composition on the surface of the resin film or the like. Such a coating film protects the surface of the resin film or the like, making it possible to prevent the resin film from being scratched, for example. From this perspective, various active energy ray-curable resin compositions excellent in performance such as scratch resistance have been studied in order to improve the surface protection performance of resin films and the like.

[0004] For example, Patent Document 1 discloses an active energy ray-curable composition containing a urethane acrylate resin having a specific structure and a photopolymerization initiator, and it is said that such a composition can form a cured coating film that has high hardness and excellent scratch resistance. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2023-161761 Summary of the Invention [Problem to be solved by the invention]

[0006] However, in recent years, with the rapid progress in improving the performance of electronic devices, optical devices, etc., there has been an increasing demand for further performance improvements in the resin films used therein. Accordingly, there has been an increasing demand for coating agents (active energy ray-curable resin compositions), and there has been a demand for active energy ray-curable resin compositions that can form coating films on resin films that are more scratch-resistant than conventional ones.

[0007] The present invention has been made in view of the above, and has an object to provide an active energy ray-curable resin composition capable of forming a coating film having high hardness, excellent scratch resistance, and excellent adhesion to a substrate. Another object of the present invention is to provide a coating film formed using the active energy ray-curable resin composition, and a laminate including the coating film. [Means for solving the problem]

[0008] As a result of extensive research into achieving the above object, the present inventors have found that the above object can be achieved by using an active energy ray-curable component containing a product obtained by the reaction of glycerin diacrylate with an isocyanate compound and glycerin triacrylate in a predetermined ratio, thereby completing the present invention.

[0009] That is, the present invention includes, for example, the subject matter described in the following sections. Item 1 An active energy ray-curable resin composition containing an active energy ray-curable component, The active energy ray-curable component is The composition contains an addition reaction product (X) of a monomer (M) containing glycerin diacrylate (A) and an isocyanate compound (C), The monomer (M) further contains glycerin triacrylate (B), the monomer (M) has a hydroxyl value of 5 mgKOH / g or more and 80 mgKOH / g or less; the isocyanate compound (C) is at least one selected from the group consisting of aliphatic isocyanates and derivatives thereof, The active energy ray-curable resin composition contains the addition reaction product (X) in an amount of 15 mass % or less based on the total mass of the active energy ray-curable components. Section 2 Item 2. The active energy ray-curable resin composition according to Item 1, wherein the derivative of the isocyanate compound (C) is at least one selected from the group consisting of an isocyanurate of an aliphatic polyisocyanate and a biuret of an aliphatic polyisocyanate. Section 3 Item 3. The active energy ray-curable resin composition according to Item 1 or 2, wherein the reaction product contains the addition reaction product (X) and the glycerin triacrylate (B). Section 4 A method for producing an active energy ray-curable resin composition, comprising: The method includes a step of obtaining the active energy ray-curable component using a raw material including a monomer (M) containing glycerin diacrylate (A) and glycerin triacrylate (B) and an isocyanate compound (C), the monomer (M) has a hydroxyl value of 5 mgKOH / g or more and 80 mgKOH / g or less; the isocyanate compound (C) is at least one selected from the group consisting of aliphatic isocyanates and derivatives thereof, the active energy ray-curable component contains an addition reaction product (X) of the glycerin diacrylate (A) and the isocyanate compound (C), and the glycerin triacrylate (B). Section 5 Item 5. The method for producing an active energy ray-curable resin composition according to Item 4, wherein the derivative of the isocyanate compound (C) is at least one selected from the group consisting of an isocyanurate of an aliphatic polyisocyanate and a biuret of an aliphatic polyisocyanate. Section 6 Item 6. The method for producing an active energy ray-curable resin composition according to Item 4 or 5, wherein the addition reaction product (X) is contained in an amount of 15 mass % or less based on the total mass of the active energy ray-curable component. Section 7 Item 4. A coating film comprising a cured product of the active energy ray-curable resin composition according to any one of Items 1 to 3. Section 8 Item 8. A laminate comprising the coating film according to item 7 on a substrate. [Effects of the Invention]

[0010] The active energy ray-curable resin composition of the present invention can form a coating film that has high hardness, excellent scratch resistance, and excellent adhesion to substrates. DETAILED DESCRIPTION OF THE INVENTION

[0011]

[0023] In the present specification, the terms "contain" and "comprise" include the concepts of "contain," "comprise," "consist essentially of," and "consist only of."

[0012] 1. Active energy ray-curable resin composition The active energy ray-curable resin composition of the present invention contains an active energy ray-curable component. The active energy ray-curable component contains an addition reaction product (X) of a monomer (M) containing glycerin diacrylate (A) and an isocyanate compound (C). The monomer (M) further contains glycerin triacrylate (B), and the monomer (M) has a hydroxyl value of 5 mgKOH / g or more and 80 mgKOH / g or less. The isocyanate compound (C) is at least one selected from the group consisting of aliphatic isocyanates and derivatives thereof. The addition reaction product (X) is contained in an amount of 15 mass% or less based on the total mass of the active energy ray-curable component.

[0013] In this specification, glycerin diacrylate will be referred to as "glycerin diacrylate (A)", glycerin triacrylate will be referred to as "glycerin triacrylate (B)", and isocyanate compounds will be referred to as "isocyanate compounds (C)".

[0014] In the present specification, hereinafter, "the active energy ray-curable resin composition of the present invention" will be abbreviated simply as "the curable resin composition of the present invention."

[0015] The curable resin composition of the present invention can form a coating film having high hardness and excellent scratch resistance. In particular, the coating film obtained from the curable resin composition of the present invention is excellent in both Martens hardness and pencil hardness.

[0016] Furthermore, a coating film formed using the curable resin composition of the present invention has high adhesion to resin films.

[0017] Therefore, the curable resin composition of the present invention can be suitably used as a coating agent for substrates such as resin films.

[0018] (active energy ray-curable component) The curable resin composition of the present invention contains an active energy ray-curable component as an essential component. The active energy ray-curable component is a component that has the property of being cured by active energy rays, particularly the property of being polymerized by active energy rays. The active energy ray referred to in the present invention is preferably ultraviolet light, but other examples include electron beams, gamma rays, carbon arc lamps, xenon lamps, and metal halide lamps. Hereinafter, the active energy ray-curable component will be simply abbreviated as "curable component."

[0019] As described above, the curable component contains an addition reaction product (X) of a monomer (M) containing glycerin diacrylate (A) and an isocyanate compound (C).

[0020] Monomer (M) further contains glycerin triacrylate (B), and therefore, monomer (M) is a mixture of glycerin diacrylate (A) and glycerin triacrylate (B).

[0021] The hydroxyl value of the monomer (M) is 5 mgKOH / g or more and 80 mgKOH / g or less. When the hydroxyl value of the monomer (M) is in this range, the coating film obtained from the curable resin composition of the present invention has high hardness and excellent scratch resistance. When the hydroxyl value of the monomer (M) is less than 5 mgKOH / g or exceeds 80 mgKOH / g, the hardness of the coating film obtained from the curable resin composition of the present invention decreases, particularly the Martens hardness, and it becomes difficult to form a coating film with the desired scratch resistance.

[0022] The hydroxyl value of the monomer (M) is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, even more preferably 20 mgKOH / g or more, and particularly preferably 25 mgKOH / g or more, and is preferably 70 mgKOH / g or less, more preferably 60 mgKOH / g or less, even more preferably 50 mgKOH / g or less, and particularly preferably 40 mgKOH / g or less.

[0023] Monomer (M) may contain components other than glycerin diacrylate (A) and glycerin triacrylate (B) as long as the hydroxyl value is 5 mgKOH / g or more and 80 mgKOH / g or less. Monomer (M) preferably contains 80 mass% or more of glycerin diacrylate (A) and glycerin triacrylate (B), more preferably 90 mass% or more, and even more preferably 95 mass% or more. Monomer (M) particularly preferably consists of glycerin diacrylate (A) and glycerin triacrylate (B) only.

[0024] In the monomer (M), the content ratio of glycerin diacrylate (A) and glycerin triacrylate (B) can be adjusted so that the hydroxyl value is in the range of 5 mgKOH / g or more and 80 mgKOH / g or less. For example, it is preferable that the content of glycerin triacrylate (B) is 50 mass% or more relative to the total amount of glycerin diacrylate (A) and glycerin triacrylate (B).

[0025] The addition reaction product (X) is a product obtained by an addition reaction between the glycerin diacrylate (A) in the monomer (M) and the isocyanate compound (C). More specifically, the addition reaction product (X) is a polyaddition product obtained by a polyaddition reaction between the glycerin diacrylate (A) and the isocyanate compound (C). Therefore, the addition reaction product (X) is a compound containing units derived from the glycerin diacrylate (A) and units derived from the isocyanate compound (C).

[0026] Since the glycerin triacrylate (B) in the monomer (M) is a compound that does not have a hydroxyl group, it does not undergo an addition reaction with the isocyanate compound (C), and therefore the addition reaction product (X) does not contain units derived from the glycerin triacrylate (B).

[0027] Specifically, the addition reaction product (X) is a product obtained by reacting a hydroxyl group (OH) present in the molecule of glycerin diacrylate (A) with an isocyanate group (NCO) present in the molecule of the isocyanate compound (C). In particular, since the isocyanate compound (C) has two or more isocyanate groups as described below, the reaction between the glycerin diacrylate (A) and the isocyanate compound (C) proceeds sequentially, resulting in a polyaddition reaction.

[0028] The addition reaction product (X) is produced by the reaction of the hydroxyl group (OH) in the glycerin diacrylate (A) with the isocyanate group (NCO) in the isocyanate compound (C), and therefore contains a urethane bond (OCONH). That is, the addition reaction product (X) contains both a urethane moiety produced by the above-mentioned reaction and an acrylate moiety derived from the glycerin diacrylate (A), and therefore can be called a urethane acrylate compound.

[0029] The isocyanate compound (C) is at least one selected from the group consisting of aliphatic isocyanates and their derivatives. In particular, the isocyanate compound (C) has two or more isocyanate groups in the molecule. It is preferable that the aliphatic isocyanate and its derivatives (aliphatic isocyanate derivatives) do not have an aromatic ring or an alicyclic ring (cyclic hydrocarbon group) in the molecule.

[0030] The aliphatic isocyanate may be, for example, a wide variety of known difunctional or higher aliphatic isocyanates, including aliphatic diisocyanate compounds having 30 or less carbon atoms. Specific examples of the aliphatic isocyanate include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, and 2,2,4-trimethyl-1,6-hexamethylene diisocyanate. In terms of increasing the hardness and improving the scratch resistance of the coating film obtained from the curable resin composition of the present invention, the aliphatic isocyanate is preferably an aliphatic diisocyanate compound having 4 to 30 carbon atoms, and more preferably an aliphatic diisocyanate compound having 4 to 10 carbon atoms.

[0031] Examples of the aliphatic isocyanate derivative (which has the same meaning as a derivative of the isocyanate compound (C)) include trifunctional or higher isocyanate compounds. Among these, the aliphatic isocyanate derivative is preferably at least one selected from the group consisting of isocyanurates of aliphatic polyisocyanates and biuret derivatives of aliphatic polyisocyanates, since this tends to increase the hardness of the coating film obtained from the curable resin composition of the present invention and also improves the scratch resistance.

[0032] Examples of isocyanurates of aliphatic polyisocyanates include compounds in which -R-NCO is bonded to a nitrogen atom derived from isocyanurate, and examples of biuret compounds of aliphatic polyisocyanates include compounds in which -R-NCO is bonded to a nitrogen atom derived from biuret. Here, R can be an alkylene group having 30 or less carbon atoms, preferably an alkylene group having 4 to 30 carbon atoms, and more preferably an alkylene group having 4 to 10 carbon atoms.

[0033] For these reasons, the isocyanate compound (C) can preferably be at least one selected from the group consisting of aliphatic isocyanates, isocyanurates of aliphatic polyisocyanates, and biuret compounds of aliphatic polyisocyanates. The more preferred isocyanate compound (C) is an aliphatic isocyanate, which tends to form a coating film with a higher Martens hardness.

[0034] The isocyanate compound (C) used to obtain the addition reaction product (X) may be one type alone or two or more types.

[0035] The isocyanate compound (C) can be obtained, for example, by production using a known method, or can be obtained from commercial products.

[0036] The reaction method of the glycerin diacrylate (A) and the isocyanate compound (C) is not particularly limited. For example, the addition reaction product (X) can be obtained by the reaction carried out in step 1 described below.

[0037] The molecular weight of the addition reaction product (X) is, for example, preferably 450 or more and 3,000 or less, more preferably 550 or more and 1,200 or less, in terms of molar mass.

[0038] As described above, the curable component contains the addition reaction product (X) of the monomer (M) containing the glycerin diacrylate (A) and the isocyanate compound (C). In other words, the curable component contains the addition reaction product (X) and the glycerin triacrylate (B).

[0039] The curable component may contain other components in addition to the addition reactant (X) and glycerin triacrylate (B). Examples of other components include various compounds having a polymerizable double bond, particularly (meth)acrylic compounds. In this specification, "(meth)acrylic" refers to "acrylic" or "methacrylic."

[0040] The curable component may contain the addition reaction product (X) and glycerin triacrylate (B) in a total amount of 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 99% by mass or more. The curable component may consist solely of the addition reaction product (X) and glycerin triacrylate (B). In this case, this does not exclude the inclusion of glycerin diacrylate (A) and / or isocyanate compound (C) that are inevitably contained in the curable component. The unavoidably contained glycerin diacrylate (A) and / or isocyanate compound (C) are, for example, unreacted products from the reaction to obtain the addition reaction product (X). It is preferable that the curable component does not contain a solvent, as described below.

[0041] (Active energy ray-curable resin composition) Next, the curable resin composition of the present invention will be described. The curable resin composition of the present invention contains the above-mentioned curable component as an essential component. That is, the curable resin composition of the present invention is a mixture containing at least the addition reaction product (X) and glycerin triacrylate (B).

[0042] In the curable resin composition of the present invention, the addition reaction product (X) is contained in an amount of 15 mass % or less based on the total mass of the curable components. This allows the coating film obtained from the curable resin composition of the present invention to have high hardness and excellent scratch resistance. If the content of the addition reaction product (X) exceeds 15 mass % based on the total mass of the curable components, the hardness of the coating film obtained from the curable resin composition of the present invention decreases, particularly the Martens hardness, and it becomes difficult to obtain the desired scratch resistance.

[0043] In the curable resin composition of the present invention, the addition reaction product (X) is contained in an amount of preferably 1 mass % or more, more preferably 5 mass % or more, even more preferably 7 mass % or more, and particularly preferably 8 mass % or more, based on the total mass of the curable components.

[0044] The curable resin composition of the present invention may contain other components as long as the curable component is an essential component, such as a solvent, a polymerization initiator, a polymerization inhibitor, a photosensitizer, a light stabilizer, a silane coupling agent, an ultraviolet absorber, a catalyst, a leveling agent, an antifoaming agent, a polymerization accelerator, an antioxidant, a flame retardant, an infrared absorber, an antistatic agent, a slip agent, a plasticizer, and a dispersant.

[0045] The solvent may be added, for example, to improve the coatability of the curable resin composition of the present invention. Examples of the solvent include chlorinated hydrocarbons such as chloroform and 1,2-dichloroethane; ether compounds such as diethyl ether and tetrahydrofuran; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; ketone compounds such as acetone and methyl ethyl ketone; ester compounds such as vinyl acetate; alcohols such as methanol, ethanol, isopropyl alcohol, and t-butanol; formamides such as N,N-dimethylformamide and N,N-dimethylacetamide; pyrrolidones such as 2-pyrrolidone and N-methylpyrrolidone; and dimethyl sulfoxide.

[0046] The amount of solvent contained in the curable resin composition of the present invention is not particularly limited. For example, the amount of solvent can be adjusted so that the total concentration of the curable components is 1 to 100 mass %, and in consideration of coatability, the amount is preferably about 5 to 50 mass %.

[0047] The polymerization initiator may be, for example, a wide variety of known polymerization initiators. The polymerization initiator may be either a thermal decomposition polymerization initiator or a photopolymerization initiator, and is preferably a photopolymerization initiator in terms of ease of film formation.

[0048] Examples of the photopolymerization initiator include aromatic ketones such as benzophenone, aromatic compounds such as anthracene and α-chloromethylnaphthalene, and sulfur compounds such as diphenyl sulfide and thiocarbamate. Examples of the polymerization initiator using active energy rays other than visible light, such as ultraviolet light, include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzil dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1- Examples of the phenylpropan-1-one include thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone).

[0049] The content of the polymerization initiator in the curable resin composition of the present invention is not particularly limited, and may be 0.01 to 10 parts by mass, preferably 0.03 to 5 parts by mass, relative to 100 parts by mass of the total amount of the curable components. Alternatively, the content of the polymerization initiator may be 0.1 to 1% by mass relative to the total amount of the addition reaction product (X).

[0050] The curable resin composition of the present invention preferably contains the curable component in an amount of 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on the total mass excluding the solvent.

[0051] (Method for producing active energy ray-curable resin composition) The method for producing the curable resin composition of the present invention is not particularly limited, and for example, a wide variety of known methods for producing active energy ray-curable resin compositions can be adopted. Preferably, the curable resin composition of the present invention can be produced by a production method including the following step 1. Step 1: A step of obtaining the active energy ray-curable component using a raw material containing a monomer (M) including glycerin diacrylate (A) and glycerin triacrylate (B) and an isocyanate compound (C).

[0052] In step 1, a raw material containing a monomer (M) including glycerin diacrylate (A) and glycerin triacrylate (B) and an isocyanate compound (C) is used.

[0053] In step 1, the reaction using the raw materials is specifically an addition reaction (polyaddition) of glycerin diacrylate (A) and an isocyanate compound (C). By carrying out such a reaction, an addition reaction (polyaddition) of glycerin diacrylate (A) and an isocyanate compound (C) occurs, and the addition reaction product (X) is produced.

[0054] The raw material used in step 1 can be prepared by mixing the monomer (M) and the isocyanate compound (C) in a predetermined ratio.

[0055] The hydroxyl value of the monomer (M) contained in the raw material is 5 mgKOH / g or more and 80 mgKOH / g or less. When the hydroxyl value of the monomer (M) is in this range, the curable resin composition obtained by the production method of the present invention can form a coating film that has high hardness and excellent scratch resistance.

[0056] When the hydroxyl value of the monomer (M) contained in the raw material is less than 5 mgKOH / g or exceeds 80 mgKOH / g, the coating film of the curable resin composition obtained by the production method of the present invention will have reduced hardness, particularly reduced Martens hardness, and it will also be difficult to form a coating film with the desired scratch resistance.

[0057] The hydroxyl value of the monomer (M) is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, even more preferably 20 mgKOH / g or more, and particularly preferably 25 mgKOH / g or more, and is preferably 70 mgKOH / g or less, more preferably 60 mgKOH / g or less, even more preferably 50 mgKOH / g or less, and particularly preferably 40 mgKOH / g or less.

[0058] Monomer (M) may contain components other than glycerin diacrylate (A) and glycerin triacrylate (B) as long as the hydroxyl value is 5 mgKOH / g or more and 80 mgKOH / g or less. Monomer (M) preferably contains 80 mass% or more of glycerin diacrylate (A) and glycerin triacrylate (B), more preferably 90 mass% or more, and even more preferably 95 mass% or more. Monomer (M) particularly preferably consists of glycerin diacrylate (A) and glycerin triacrylate (B) only.

[0059] In the monomer (M), the content ratio of glycerin diacrylate (A) and glycerin triacrylate (B) can be adjusted so that the hydroxyl value is in the range of 5 mgKOH / g or more and 80 mgKOH / g or less. For example, it is preferable that the content of glycerin triacrylate (B) is 50 mass% or more relative to the total amount of glycerin diacrylate (A) and glycerin triacrylate (B).

[0060] The monomer (M) containing glycerin diacrylate (A) and glycerin triacrylate (B) can be obtained from commercial products, such as M-930 from the Aronix (registered trademark) series manufactured by Toagosei Co., Ltd.

[0061] The isocyanate compound (C) contained in the raw material is at least one selected from the group consisting of aliphatic isocyanates and their derivatives. As described above, the derivative of the isocyanate compound (C) is at least one selected from the group consisting of isocyanurates of aliphatic polyisocyanates and biuret forms of aliphatic polyisocyanates.

[0062] The isocyanate compound (C) contained in the raw material is preferably at least one selected from the group consisting of aliphatic isocyanates, isocyanurates of aliphatic polyisocyanates, and biuret compounds of aliphatic polyisocyanates. The isocyanate compound (C) is more preferably an aliphatic isocyanate, in which case the curable resin composition obtained by the production method of the present disclosure is likely to form a coating film with a higher Martens hardness. The isocyanate compound (C) contained in the raw material can be one type alone or two or more types.

[0063] The addition reaction (polyaddition) of glycerin diacrylate (A) and isocyanate compound (C) performed in step 1 can be carried out using, for example, a wide variety of known polyaddition reactions. For example, a wide variety of reaction conditions for reacting a known alcohol compound with an isocyanate compound can be used in the present invention.

[0064] For example, an addition reaction product (X) can be obtained by reacting glycerin diacrylate (A) in a monomer (M) with an isocyanate compound (C) in the presence of a catalyst. Note that since the glycerin triacrylate (B) in the monomer (M) does not have a hydroxyl group, the glycerin triacrylate (B) does not react with the isocyanate compound (C). Therefore, the glycerin triacrylate (B) remains even after the polyaddition reaction.

[0065] The catalyst may be, for example, an organic tin compound, and specific examples include tin octoate, dibutyltin dilaurate, dioctyltin dineodecanoate, dioctyltin dilaurate, manganese, cobalt, lead, bismuth stannate, lead stannate, zirconium octoate, zinc octoate, dibutyltin-bis-o-phenylphenylene, dibutyltin-S,S-dibutyldithiocarbonate, triphenylantimony dichloride, dibutyltin maleate, dibutyltin diacetate, dibutyltin dilaurate mercaptide, triethylenediamine, bismuth stearate, lead stearate, and dimethyltin dichloride. The amount of catalyst used can usually be adjusted within a range of 0.001 to 5 parts by weight per 100 parts by weight of the total of glycerin diacrylate (A) and isocyanate compound (C).

[0066] The reaction for obtaining the addition product (X) can be carried out in the presence of a polymerization inhibitor. As the polymerization inhibitor, a wide variety of known polymerization inhibitors such as hydroquinone monomethyl ether can be used.

[0067] The reaction temperature for obtaining the addition reaction product (X) is not particularly limited and can be, for example, about 30 to 100°C, preferably 50 to 80°C. The reaction time is also not particularly limited and can be set within an appropriate range depending on the reaction temperature. For example, the reaction can be continued until the amount of free isocyanate is 10% by mass or less, preferably 5% by mass or less, and more preferably 0.1% by mass or less, based on the amount of isocyanate compound (C) used.

[0068] The raw materials used in step 1 may contain other components in addition to glycerin diacrylate (A), glycerin triacrylate (B), and the isocyanate compound (C). Examples of other components include the above-mentioned catalyst, polymerization inhibitor, and polymerizable monomers that are added as needed.

[0069] By carrying out a reaction (polyaddition reaction) using the above raw materials, the reaction between glycerin diacrylate (A) and the isocyanate compound (C) proceeds, producing an addition reaction product (X). As mentioned above, glycerin triacrylate (B) does not have a hydroxyl group and therefore remains unreacted. Therefore, by the reaction using the above raw materials, a curable component containing the addition reaction product (X) and glycerin triacrylate (B) is obtained.

[0070] The molecular weight of the addition reaction product (X) is, for example, preferably 450 or more and 3,000 or less, more preferably 550 or more and 1,200 or less, in terms of molar mass.

[0071] The curable component obtained in step 1 may be mixed with a solvent, a photopolymerization initiator, etc. as needed to obtain the curable resin composition of the present invention.

[0072] The curable component (active energy ray-curable component) obtained in step 1 contains 15 mass % or less of the addition reaction product (X) based on the total mass of the curable component. This allows the curable resin composition obtained by the production method of the present invention to form a coating film that has high hardness and excellent scratch resistance. If the content of the addition reaction product (X) exceeds 15 mass % based on the total mass of the curable component, the hardness of the coating film decreases, particularly the Martens hardness, and it becomes difficult to obtain the desired scratch resistance.

[0073] The addition reaction product (X) is preferably contained in an amount of 1% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 8% by mass or more, based on the total mass of the curable component.

[0074] (paint film) A coating film can be formed by using the curable resin composition of the present invention or the curable resin composition obtained by the production method of the present invention. Specifically, a coating liquid is prepared by adding a solvent, a polymerization initiator, etc. to the curable resin composition as needed, and this coating liquid is applied to a substrate to form a coating film, which is then cured to form a coating film on the substrate. That is, the coating film contains a cured product of the curable resin composition of the present invention.

[0075] The substrate is not particularly limited, and examples thereof include various known resin films. The type of film is also not particularly limited, and examples thereof include a wide variety of resin films, such as polyethylene terephthalate film, polyethylene film, and acrylic film.

[0076] The method for applying the coating liquid obtained from the curable resin composition of the present invention onto a substrate is not particularly limited, and a wide variety of known application methods can be used. For example, application can be performed using known coating devices, such as a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a microgravure coater, a rod blade coater, a lip coater, a die coater, and a curtain coater.

[0077] The method for curing the coating formed on the substrate is not particularly limited, and examples thereof include a method of irradiating the coating with active energy rays. The active energy rays are preferably ultraviolet rays, and other examples include electron beams, gamma rays, carbon arc lamps, xenon lamps, and metal halide lamps. The method and conditions for irradiating the active energy rays are also not limited and can be the same as known methods. Examples of ultraviolet radiation sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and ultraviolet lamps such as LEDs.

[0078] The thickness of the coating film is not particularly limited, and can be set within an appropriate range depending on the intended use.

[0079] The coating film obtained from the curable resin composition of the present invention contains a cured product of the active energy ray-curable resin composition, and therefore has high hardness and excellent scratch resistance, particularly excellent in both Martens hardness and pencil hardness. The coating film obtained from the curable resin composition of the present invention has high not only pencil hardness but also Martens hardness, which makes it possible to achieve scratch resistance that is superior to conventional coatings. Furthermore, the coating film formed using the curable resin composition of the present invention also has high adhesion to resin films.

[0080] Therefore, the curable resin composition of the present invention is suitable for use as a coating agent for forming a coating film on a substrate such as a resin film.

[0081] The coating film can be used to form various laminates, and examples thereof include a laminate having the coating film on a substrate. By providing the coating film, such a laminate is likely to prevent scratches on the surface of the substrate.

[0082] In specifying the inventions included in the present disclosure, the components (properties, structures, functions, etc.) described in the embodiments of the present disclosure may be combined in any manner. In other words, the present disclosure includes all subject matter consisting of all combinations of the components that can be combined as described in this specification. [Example]

[0083] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0084] Example 1 A raw material was prepared according to the formulation of Example 1 shown in Table 1. Specifically, the raw material used in step 1 was prepared by blending in a flask 3.6 parts by mass of hexamethylene diisocyanate (hereinafter referred to as HDI) as the isocyanate compound (C), 0.05 parts by mass of hydroquinone monomethyl ether as a polymerization inhibitor, 0.03 parts by mass of dioctyltin dineodecanoate as a catalyst, and 96.4 parts by mass of monomer M ("Aronix (registered trademark) M-930" manufactured by Toagosei Co., Ltd.) having a hydroxyl value of 30 mgKOH / g and consisting of glycerin diacrylate (A) and glycerin triacrylate (B).

[0085] Next, the raw materials in the flask were heated to 70°C to carry out a reaction. The reaction was carried out until the amount of free isocyanate was 0.1 mass% or less relative to the amount of isocyanate compound (C) charged. This reaction yielded a composition containing an active energy ray-curable component containing urethane acrylate (addition reaction product (X)), which was a reaction product of glycerin diacrylate (A) and the isocyanate compound (C) in the monomer M, and glycerin triacrylate (B) (Step 1).

[0086] Example 2 As shown in Table 1, a composition containing an active energy ray-curable component was obtained in the same manner as in Example 1, except that the isocyanate compound (C) was changed from HDI to 1,5-pentamethylene diisocyanate (hereinafter, PDI) to prepare the raw materials.

[0087] Example 3 As shown in Table 1, a composition containing an active energy ray-curable component was obtained in the same manner as in Example 1, except that the isocyanate compound (C) was changed to 7.2 parts by mass of HDI nurate ("Coronate HXR" manufactured by Tosoh Corporation), an HDI derivative, instead of HDI, and the amount of monomer M used was changed to 92.8 parts by mass to prepare the raw material.

[0088] Example 4 As shown in Table 1, a composition containing an active energy ray-curable component was obtained in the same manner as in Example 1, except that the isocyanate compound (C) was changed to 6.8 parts by mass of PDI nurate ("STABIO (registered trademark) D-376N" manufactured by Mitsui Chemicals) which is a PDI derivative, instead of HDI, and the amount of monomer M used was changed to 93.2 parts by mass to prepare the raw material.

[0089] Example 5 As shown in Table 1, a composition containing an active energy ray-curable component was obtained in the same manner as in Example 1, except that the isocyanate compound (C) was changed to 6.4 parts by mass of HDI biuret (Duranate 24A-100 manufactured by Asahi Kasei Corporation), an HDI derivative, instead of HDI, and the amount of monomer M used was changed to 93.6 parts by mass to prepare the raw material.

[0090] (Comparative Example 1) A raw material was prepared according to the formulation of Comparative Example 1 shown in Table 1. Specifically, the raw material used in step 1 was prepared by blending 12.1 parts by mass of HDI as the isocyanate compound (C), 0.05 parts by mass of hydroquinone monomethyl ether as a polymerization inhibitor, 0.03 parts by mass of dioctyltin dineodecanoate as a catalyst, and 87.9 parts by mass of a monomer consisting of glycerin diacrylate (A) and glycerin triacrylate (B) in a flask. The monomer consisting of glycerin diacrylate (A) and glycerin triacrylate (B) was a mixed monomer 1 having 111 mg KOH / g of hydroxyl groups, prepared by mixing 54.1 parts by mass of the monomer M and 33.8 parts by mass of monomer m (Toagosei Co., Ltd. "Aronix (registered trademark) M-920", hydroxyl group 240 mg KOH / g).

[0091] Next, the raw materials in the flask were heated to 70°C to carry out a reaction. The reaction was carried out until the amount of free isocyanate was 0.1 mass% or less relative to the amount of isocyanate compound (C) charged. This reaction yielded a composition containing an active energy ray-curable component containing urethane acrylate (addition reaction product (X)), which was a reaction product of glycerin diacrylate (A) and the isocyanate compound (C) in the mixed monomer, and glycerin triacrylate (B).

[0092] (Comparative Example 2) A composition containing an active energy ray-curable component was obtained in the same manner as in Comparative Example 1, except that 75.4 parts by mass of Toagosei's "Aronix (registered trademark) M-920" (hydroxyl value 240 mgKOH / g) was used instead of mixed monomer 1, and the amount of HDI was changed to 24.6 parts by mass to prepare the raw materials.

[0093] (Comparative Example 3) A composition containing an active energy ray-curable component was obtained in the same manner as in Comparative Example 1, except that 94.9 parts by mass of Toagosei's "Aronix (registered trademark) M-930" (hydroxyl value 30 mgKOH / g) was used instead of mixed monomer 1, and that 5.1 parts by mass of isophorone diisocyanate (IPDI), an alicyclic isocyanate, was used instead of HDI as the isocyanate compound (C).

[0094] Comparative Example 4 A composition containing an active energy ray-curable component was obtained in the same manner as in Comparative Example 1, except that 95.6 parts by mass of Toagosei's "Aronix (registered trademark) M-930" (hydroxyl value 30 mgKOH / g) was used instead of mixed monomer 1, and that 4.4 parts by mass of xylene diisocyanate (XDI), an aromatic isocyanate, was used instead of HDI as the isocyanate compound (C).

[0095] (Evaluation method) Coating films were prepared using the compositions obtained in each of the Examples and Comparative Examples by the following method, and the resulting coating films were evaluated for Martens hardness, scratch resistance, pencil hardness, and adhesion to substrates.

[0096] [Preparation of coating film] Methyl ethyl ketone was added to the composition obtained in each Example and Comparative Example to prepare a solution with a solids concentration of 40% by mass. To this solution, 3% by mass of "Omnirad 184" manufactured by IGM Resins BV was added as a polymerization initiator relative to the active energy ray-curable component to obtain a coating solution. This coating solution was applied to a 100 μm-thick PET film ("Cosmoshine A4360" manufactured by Toyobo Co., Ltd.) to a film thickness of approximately 3 μm in a dried state, and then dried in an oven at 80°C for 1 minute to form a film on the PET film. Subsequently, a high-pressure mercury lamp (80 W / cm × 1 lamp) was used under a nitrogen atmosphere, with an integrated illuminance of 600 mJ / cm. 2 The coating was cured by irradiating the coating with light at a temperature of 1000 W at ...

[0097] [Martens hardness HM] The Martens hardness of the coating film was evaluated by measuring the microhardness through an indentation test using an Elionix microhardness tester (product number: ENT-1100a). The indentation test was performed with an indentation load of 0.3 mN. The indentation test was performed in accordance with the indentation test method in accordance with ISO 14577-1, and the Martens hardness HM of the coating film was measured and evaluated according to the following criteria. ≪Judgment criteria≫ A: Martens hardness HM is 360N / mm 2 As a result, the material has an extremely high Martens hardness. B: Martens hardness HM is 340 to 360 N / mm 2 and has a high Martens hardness. C: Martens hardness HM is 320-340N / mm 2 and the Martens hardness is low. D: Martens hardness HM is 320N / mm 2The Martens hardness is extremely low.

[0098] [Scratch resistance] The coating film formed on the surface of the laminate was subjected to a load of 250 g / cm using #0000 steel wool. 2 After the test, the surface of the laminate was visually inspected and the scratch resistance was evaluated according to the following criteria. ≪Judgment criteria≫ A: The number of scratches is 2 or less, and the surface has excellent scratch resistance. B: The number of scratches is 3 or more and 4 or less, and the scratch resistance is poor. C: The number of scratches is 5 or more, and the scratch resistance is extremely poor.

[0099] [Pencil hardness] The pencil hardness of the coating film on the surface of the laminate was measured in accordance with JIS K5600-5-4:1999.

[0100] [Adhesion to substrate] The surface of the coating film formed on the surface of the laminate was cut with a cutter knife to create 100 2 mm x 2 mm grids. Cellophane adhesive tape was then applied to the grids and then rapidly peeled off three times. The number of grids that remained unpeeled was counted and the adhesion to the substrate (PET film) was evaluated according to the following criteria. ≪Judgment criteria≫ A: The number of remaining grids was 80 or more, and the adhesion to the substrate was extremely excellent. B: The number of remaining grids was 50 or more and less than 80, and the adhesion to the substrate was excellent. C: The number of remaining grids was less than 50, and the adhesion to the substrate was poor.

[0101] Table 1 shows the preparation conditions for the compositions obtained in each Example and Comparative Example, particularly the blending conditions for obtaining the active energy ray-curable component. Note that blank spaces in Table 1 mean that the raw material was not used, and the types of ingredients are indicated using the abbreviations shown in each Example and Comparative Example.

[0102] Table 1 also shows the content ratio of the addition reaction product (X) (urethane acrylate) relative to the total mass of the active energy ray-curable components (in Table 1, this is expressed as "content ratio (mass %) of the addition reaction product (X) relative to the entire resin"). The content ratio of the addition reaction product (X) (urethane acrylate) relative to the total mass of the active energy ray-curable components was calculated using the following formula (1). Mass ratio of the addition reactant (X) = Mass of the addition reactant (X) / {Mass of the addition reactant (X) + Mass of the unreacted glycerin diacrylate (A) + Mass of the glycerin triacrylate (B)} × 100 (1) Here, the hydroxyl values ​​of glycerin diacrylate (A) and glycerin triacrylate (B) in monomer M can be calculated based on their hydroxyl values ​​and the hydroxyl value of monomer M. From this calculation, the masses of glycerin diacrylate (A) and glycerin triacrylate (B) can be calculated. Furthermore, the mass of glycerin diacrylate (A) that reacts with isocyanate (C) can be calculated by multiplying the molar mass of isocyanate (C) by the number of functional groups in isocyanate (C) by the molar mass of glycerin diacrylate (A). The mass of the addition reactant (X) can be calculated by multiplying the mass of isocyanate (C) by the mass of glycerin diacrylate (A) that reacts with isocyanate (C). The mass of unreacted glycerin diacrylate (A) can be calculated by multiplying the mass of glycerin diacrylate (A) by the mass of glycerin diacrylate (A) that reacts with isocyanate (C). Based on the above calculation results, the content ratio of the addition reaction product (X) (urethane acrylate) relative to the total mass of the active energy ray-curable components can be derived from the above formula (1).

[0103] Furthermore, Table 1 shows the evaluation results (Martens hardness, scratch resistance, pencil hardness, and adhesion to substrate) of the coating films obtained from the compositions of each Example and Comparative Example.

[0104] It can be seen from Table 1 that the coating films obtained using the compositions prepared in each Example have high hardness, excellent scratch resistance, and also high adhesion to the substrate.

[0105] [Table 1]

Claims

1. An active energy ray-curable resin composition containing an active energy ray-curable component, The active energy ray-curable component is The composition contains an addition reaction product (X) of a monomer (M) containing glycerin diacrylate (A) and an isocyanate compound (C), The monomer (M) further contains glycerin triacrylate (B), the monomer (M) has a hydroxyl value of 5 mgKOH / g or more and 80 mgKOH / g or less; the isocyanate compound (C) is at least one selected from the group consisting of aliphatic isocyanates and derivatives thereof, The active energy ray-curable resin composition contains the addition reaction product (X) in an amount of 15 mass % or less based on the total mass of the active energy ray-curable components.

2. 2. The active energy ray-curable resin composition according to claim 1, wherein the derivative of the isocyanate compound (C) is at least one selected from the group consisting of an isocyanurate of an aliphatic polyisocyanate and a biuret of an aliphatic polyisocyanate.

3. 2. The active energy ray-curable resin composition according to claim 1, wherein the active energy ray-curable component contains the addition reaction product (X) and the glycerin triacrylate (B).

4. A method for producing an active energy ray-curable resin composition, comprising: The method includes a step of obtaining an active energy ray-curable component using a raw material including a monomer (M) containing glycerin diacrylate (A) and glycerin triacrylate (B) and an isocyanate compound (C), the monomer (M) has a hydroxyl value of 5 mgKOH / g or more and 80 mgKOH / g or less; the isocyanate compound (C) is at least one selected from the group consisting of aliphatic isocyanates and derivatives thereof, the active energy ray-curable component contains an addition reaction product (X) of the glycerin diacrylate (A) and the isocyanate compound (C), and the glycerin triacrylate (B).

5. 5. The method for producing an active energy ray-curable resin composition according to claim 4, wherein the derivative of the isocyanate compound (C) is at least one selected from the group consisting of an isocyanurate of an aliphatic polyisocyanate and a biuret of an aliphatic polyisocyanate.

6. The method for producing an active energy ray-curable resin composition according to claim 4 or 5, wherein the addition reaction product (X) is contained in an amount of 15 mass % or less based on the total mass of the active energy ray-curable component.

7. A coating film comprising a cured product of the active energy ray-curable resin composition according to any one of claims 1 to 3.

8. A laminate comprising the coating film according to claim 7 on a substrate.

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