Active energy ray curable resin composition, cured product, and laminate

Abstract

The present invention provides an active energy ray curable resin composition that has excellent adhesion to the substrate and excellent transparency and coating hardness in the cured product, and can be used as a hard coat agent in a single layer. [Solution] An active energy ray curable resin composition containing the following monomer component (A) and component (B). Monomer component (A): Containing at least two monomer components, each monomer component having one or two (meth)acrylate groups in one molecule and at least one functional group from among ether groups and hydroxyl groups, and not having aromatic hydrocarbon groups or alicyclic hydrocarbon groups, and the glass transition temperature (Tg) of the polymer when homopolymerized is 150°C or less. Among the monomer components (A), when the monomer component with the highest Tg of the polymer after homopolymerization is designated as monomer component (a1) and the monomer component with the lowest Tg of the polymer after homopolymerization is designated as monomer component (a2), the difference between the Tg of monomer component (a1) and the Tg of monomer component (a2) is 10°C or more. Component (B): A monomer, oligomer, or polymer having two or more (meth)acrylate groups in one molecule (excluding those corresponding to the monomer component (A)).

Description

[Technical Field]

[0001] The present invention relates to an active energy ray curable resin composition, a cured product using the same, and a laminate. [Background technology]

[0002] Flat panel displays (FPDs), such as liquid crystal displays (LCDs), organic light-emitting diodes (OLEDs), and plasma displays (PDPs), are laminates of substrates with various functions. In recent years, there has been a growing demand for lower costs and higher resolution in FPDs. Generally, the outermost surface layer of an FPD is provided with a protective layer that has various functions. One of the functions of the protective layer is anti-glare properties, which reduce reflections from fluorescent lights and other sources.

[0003] One known method for imparting anti-glare functionality to a protective layer is to create a fine, uneven surface to diffusely reflect light. Methods for forming fine irregularities on the surface include applying a UV hard coat agent containing organic or inorganic microparticles (see, for example, Patent Document 1). Examples of substrates for UV hard coats include TAC (triacetylcellulose), PET (polyethylene terephthalate), and PMMA (polymethyl methacrylate) films. Among these, PMMA films have attracted attention in recent years due to the increasing size of FPDs, from the viewpoint of cost and humidity stability.

[0004] However, compared to other base films such as TAC film, PMMA film has the problem of having low adhesion between the base film surface and the hard coat layer, making it difficult to form a hard coat layer with high adhesion to the PMMA film surface.

[0005] A widely used method to improve adhesion between the substrate film surface and the hard coat layer involves applying a primer layer with excellent adhesion to the substrate film surface, followed by coating and curing an active energy ray-curable resin composition. However, while this method of applying a primer layer with excellent adhesion can improve adhesion between the film surface and the hard coat layer, it has the drawback of increasing the number of steps involved in applying and drying the primer layer, leading to reduced yield and increased costs.

[0006] Therefore, research is being conducted on photocurable resin compositions that can form a single-layer cured film with excellent adhesion to the surface of acrylic resin films, particularly acrylic resin films that are difficult to adhere to, such as protective films for polarizing plates incorporated into liquid crystal displays, without the need for a primer layer, and that are resistant to peeling (see, for example, Patent Document 2). The photocurable resin composition described in Patent Document 2 contains a monomer component having a certain permeability to a specific acrylic resin film, a urethane acrylate having a specific weight-average molecular weight and acryloyl group equivalent, and a reaction product having a specific (meth)acryloyl equivalent, a specific hydroxyl value, and a specific weight-average molecular weight obtained by adding a carboxyl group-containing (meth)acrylic compound to an epoxy group-containing vinyl compound polymer. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2012-063504 [Patent Document 2] Japanese Patent Publication No. 2014-173072 [Overview of the project] [Problems that the invention aims to solve]

[0008] However, the photocurable resin composition described in Patent Document 2 contains a monomer component in which, when an acrylic resin film is immersed as a measurement sample at room temperature for 5 minutes, the increase in surface haze of the film after immersion compared to before immersion is 3.0 or more. Therefore, from the viewpoint of transparency of the cured coating film obtained by curing the photocurable resin composition, there is room for improvement, and in particular, there is room for improvement when used as a hard coat agent for transparent films and low-haze AG (Anti-Glare) films used in optical components.

[0009] The present invention was made to solve the above-mentioned problems, and aims to provide an active energy ray curable resin composition, cured product, and laminate that can be used as a hard coat agent in a single layer, having excellent adhesion to the substrate and excellent transparency and coating hardness in the cured product.

[0010] The present inventors conducted diligent studies to solve the above problems and, as a result, discovered that by primarily including at least two monomer components, each monomer component having a specific structure and a specific glass transition temperature (A), and a high-density crosslinked component (B), an active energy ray curable resin composition can be obtained that has excellent adhesion to the substrate and excellent transparency and coating hardness in the cured product, and can be used as a hard coat agent in a single layer, thus completing the present invention.

[0011] In other words, the present invention encompasses the following embodiments. (1) An active energy ray curable resin composition containing the monomer component (A) and component (B) described below. Monomer component (A): Contains at least two monomer components, Each monomer component has one or two (meth)acrylate groups in one molecule, and has at least one functional group from among ether groups and hydroxyl groups, and does not have aromatic hydrocarbon groups or alicyclic hydrocarbon groups, and the glass transition temperature (Tg) of the polymer when homopolymerized is 150°C or less. When, among the monomer components (A), the monomer component with the highest Tg of the polymer when homopolymerized is defined as monomer component (a1), and the monomer component with the lowest Tg of the polymer when homopolymerized is defined as monomer component (a2), the difference between the Tg of the monomer component (a1) and the Tg of the monomer component (a2) is 10 °C or more. Component (B): A monomer, oligomer, or polymer having two or more (meth)acrylate groups in one molecule (however, those corresponding to the monomer component (A) are excluded). (2) The active energy ray-curable resin composition according to (1), wherein the molecular weight of the monomer component (A) is 300 or less. (3) The active energy ray-curable resin composition according to (1) or (2), wherein the monomer component (A) has erosiveness with respect to a PMMA substrate. (4) The active energy ray-curable resin composition according to any one of (1) to (3), wherein the component (B) is a polyfunctional urethane (meth)acrylate. (5) The active energy ray-curable resin composition according to (4), wherein the polyfunctional urethane (meth)acrylate has an isocyanurate skeleton in the molecule. (6) The active energy ray-curable resin composition according to (4), wherein the polyfunctional urethane (meth)acrylate has an isocyanurate skeleton and a cyclic structure in the molecule. (7) The active energy ray-curable resin composition according to any one of (1) to (6), further containing fine particles (C). (8) The active energy ray-curable resin composition according to (7), wherein the fine particles (C) are organic fine particles. (9) The active energy ray-curable resin composition according to (7) or (8), wherein the average particle diameter of the fine particles (C) is in the range of 0.1 μm to 10 μm. (10) A cured product of the active energy ray-curable resin composition according to any one of (1) to (9). (11) A laminate, wherein a cured coating film of the active energy ray-curable resin composition according to any one of (1) to (9) is provided in direct contact with one or both sides of a PMMA substrate.

Advantages of the Invention

[0012] According to the present invention, it is possible to provide an active energy ray curable resin composition, a cured product, and a laminate that can be used as a hard coat agent in a single layer, having excellent adhesion to a substrate and excellent transparency and coating hardness in the cured product. [Brief explanation of the drawing]

[0013] [Figure 1] This figure shows the FT-IR spectrum of a PMMA substrate. [Figure 2] This figure shows the FT-IR spectrum of triethylene glycol diacrylate. [Figure 3] This figure shows the FT-IR spectrum of the PMMA substrate in the area where triethylene glycol diacrylate solution was dropped onto the substrate, followed by washing and drying. [Figure 4] This figure shows the FT-IR spectrum of dimethylol-tricyclodecanediaacrylate. [Figure 5] This figure shows the FT-IR spectrum of the PMMA substrate in the area where a dimethylol-tricyclodecanediaacrylate solution was dropped onto the substrate, followed by washing and drying. [Modes for carrying out the invention]

[0014] The following describes in detail the active energy ray curable resin composition, cured product, and laminate of the present invention. However, the description of the constituent elements described below is an example (representative example) of one embodiment of the present invention and is not limited to these contents.

[0015] In the following explanation, "(meth)acryloyl" means acryloyl and / or methacryloyl. Also, "(meth)acrylate" means acrylate and / or methacrylate. Furthermore, "(meth)acrylic" means acrylic and / or methacrylic.

[0016] (Composition of ray-curable resin) The active energy ray curable resin composition of the present invention (hereinafter also simply referred to as "the composition") contains the following monomer component (A) and component (B). Monomer component (A): Containing at least two monomer components, each monomer component having one or two (meth)acrylate groups in one molecule and at least one functional group from among ether groups and hydroxyl groups, and not having aromatic hydrocarbon groups or alicyclic hydrocarbon groups, and the glass transition temperature (Tg) of the polymer when homopolymerized is 150°C or less. Among the monomer components (A), when the monomer component with the highest Tg of the polymer after homopolymerization is designated as monomer component (a1) and the monomer component with the lowest Tg of the polymer after homopolymerization is designated as monomer component (a2), the difference between the Tg of monomer component (a1) and the Tg of monomer component (a2) is 10°C or more. Component (B): Monomers, oligomers, or polymers having two or more (meth)acrylate groups in one molecule (excluding those corresponding to the above monomer component (A)).

[0017] To our surprise, the inventors have discovered that the active energy ray curable resin composition having the above configuration exhibits excellent adhesion to substrates, as well as excellent transparency and coating hardness in the cured product, and can be used as a hard coat agent in a single layer.

[0018] The mechanism by which the above effects are achieved by the configuration of the present invention is presumed to be as follows.

[0019] The active energy ray curable resin composition of the present invention is characterized by containing a high-density crosslinking component (B) along with a monomer component (A) that is corrosive to acrylic resin substrates. In the curing process of the active energy ray curable resin composition of the present invention, the monomer component (A) corrodes the acrylic resin substrate, so the cured product formed by the composition of the present invention has excellent substrate adhesion to the acrylic resin substrate.

[0020] Furthermore, monomer component (A) contains two or more monomer components, and each monomer component has a specific different Tg, so that during the curing process, the erosion performance on the acrylic resin substrate differs. Because it contains two or more monomer components that have different erosion performance on the acrylic resin substrate, it is presumed that the cured product formed by the composition of the present invention has a gradient structure of components (hereinafter also referred to as a component gradient structure) formed in the depth direction (from the side not in contact with the substrate to the side in contact with the substrate) near the interface with the acrylic resin substrate.

[0021] Generally, a component gradient structure refers to a multi-component system in which the concentration of a specific component changes in a particular direction. Specifically, the active energy ray curable resin composition of the present invention is presumed to have a component gradient structure in which the surface of the cured product (the side not in contact with the substrate) has a high proportion of monomer component (A) with high Tg and low corrosiveness and component (B) which is a high-density crosslinked molecule, resulting in good surface properties, while the interior of the cured product (the side in contact with the substrate) has a high proportion of monomer component (A) with low Tg and high corrosiveness, resulting in excellent substrate adhesion. Furthermore, it is presumed that having the above component gradient structure results in the cured product as a whole having excellent transparency and coating properties.

[0022] <Monomer component (A)> Monomer component (A) contains at least two monomer components. Each monomer component is corrosive to acrylic resin substrates.

[0023] Acrylic resin substrates are resin substrates mainly composed of methacrylic acid ester resins. Methacrylic acid ester resins are polymers having methacrylic acid ester monomer units as their main component. Methacrylic acid ester resins may be homopolymers of one type of methacrylic acid ester monomer, copolymers of two or more types of methacrylic acid ester monomers, or copolymers of one or more types of methacrylic acid ester monomers with vinyl compounds other than methacrylic acid ester monomers. Examples of methacrylic acid ester monomers include, but are not limited to, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, and hexyl methacrylate. Furthermore, alkyl groups such as propyl groups, butyl groups, pentyl groups, and hexyl groups in methacrylic acid ester monomers may be linear or branched. Examples of vinyl compounds other than methacrylic acid esters include, but are not limited to, acrylic acid esters, styrene, ethylene, butadiene, isoprene, α-methylstyrene, acrylonitrile, acrylic acid, and propylene. Among these, polymethyl methacrylate (PMMA) is preferred as the methacrylic acid ester resin. In other words, the acrylic resin substrate used in the present invention is preferably a PMMA substrate, and the monomer component (A) is corrosive to the PMMA substrate.

[0024] In this specification, "corrosive to PMMA substrates" means that when 1 mL of monomer component solution is dropped onto a 40 μm thick PMMA substrate, left to stand at 80°C for 5 minutes, the PMMA substrate is washed with 50 mL of isopropanol and dried, and then the PMMA substrate in the dropped portion is measured by infrared absorption spectroscopy (IR), absorption of the monomer component is detected in addition to the absorption of the PMMA substrate. Here, detection of absorption means that in the difference spectrum between the spectrum of the PMMA substrate after the erosion test and the spectrum of the PMMA substrate alone, an absorption peak derived from the monomer with a signal-to-noise ratio of 2 or more is confirmed.

[0025] The measurement method for the above-mentioned IR is as follows: The following measurement method is used with FT-IR (instrument name: Fourier Transform Infrared Spectrophotometer FT / IR-6X, JASCO Corporation). First, a diamond prism is used to measure wavenumbers of 400-4000 cm. -1 , disassembled 4cm -1 First, background measurements are performed with a set accumulation count of 16. Next, the surface on which the monomer component solution of the PMMA substrate is dropped is brought into contact with the diamond prism, and sample measurements are performed under the same conditions as the background measurement.

[0026] The monomer component has one or two (meth)acrylate groups in its molecule and at least one functional group from among an ether group (ROR', where R,R' is a hydrocarbon group such as an alkyl group) and a hydroxyl group (-OH). Furthermore, the monomer component does not have aromatic hydrocarbon groups or alicyclic hydrocarbon groups in its molecule. By having the above structural characteristics of the monomer component, compositions with excellent substrate adhesion to PMMA substrates tend to be obtained.

[0027] The monomer component has a glass transition temperature (Tg) of 150°C or lower when homopolymerized. When the polymer's Tg is 150°C or lower, a composition with excellent coating properties tends to be obtained. The Tg of the above polymer is preferably 130°C or lower, more preferably 100°C or lower. On the other hand, the lower limit of the polymer's Tg is not particularly limited, but is usually -80°C or higher.

[0028] The method for measuring the Tg in the above polymer is specifically as follows: The Tg of the polymer is measured using a differential scanning calorimeter (DSC) (device name: DSC7000X, Hitachi High-Technologies Corporation) by placing component (B) in a sealed pan and heating it at a heating rate of -10°C / min in the range of -60°C to (thermal decomposition temperature (°C) -5°C). The Tg of the polymer measured during the second heating cycle is used. Furthermore, when using a commercially available product as monomer component (A), if the Tg value is listed in the catalog of that commercially available product, that value may be used as the Tg of the polymer obtained by homopolymerization.

[0029] Among monomer components (A), the monomer component with the highest Tg of the polymer after homopolymerization is designated as monomer component (a1), and the monomer component with the lowest Tg of the polymer after homopolymerization is designated as monomer component (a2). The difference between the Tg of monomer component (a1) and the Tg of monomer component (a2) is 10°C or more. If the difference between the Tg of monomer component (a1) and monomer component (a2) is 10°C or more, a composition is likely to be obtained that has excellent substrate adhesion and excellent transparency and coating hardness in the cured product, and can be used as a hard coat agent in a single layer. The difference between the Tg of monomer component (a1) and monomer component (a2) is preferably 15°C or more, more preferably 20°C or more. On the other hand, there is no particular upper limit to the difference between the Tg of monomer component (a1) and monomer component (a2), but it is usually 100°C or less.

[0030] The molecular weight of the monomer component is preferably 300 or less, and more preferably 250 or less. When the molecular weight of the monomer component is below the above upper limit, a composition with excellent substrate adhesion tends to be obtained. The lower limit of the molecular weight of the monomer component is not particularly limited, but is usually 50 or more.

[0031] The monomer component is not limited as long as it satisfies the above conditions, but it is preferably a monomer represented by formula (1) or formula (2) below. [ka] (In formula (1), R 1 R represents a hydrogen atom or a methyl group. 2 (This represents a divalent aliphatic hydrocarbon group that does not have a cyclic structure.)

[0032] [ka] (In formula (2), R3 represents a hydrogen atom or a methyl group, and R 4 represents a divalent aliphatic hydrocarbon group having no cyclic structure, and R 5 represents a monovalent aliphatic hydrocarbon group having no cyclic structure or a (meth)acryloyl group. n represents an integer of 1 to 5.)

[0033] The above monovalent aliphatic hydrocarbon group refers to a group obtained by removing one hydrogen atom bonded to an aliphatic carbon of an aliphatic compound. The above divalent aliphatic hydrocarbon group refers to a group obtained by removing two hydrogen atoms bonded to an aliphatic carbon of an aliphatic compound. Having no cyclic structure means having no aromatic hydrocarbon group and no alicyclic hydrocarbon group.

[0034] In the above formula (1), R 2 and in formula (2), R 4 Examples of the divalent aliphatic hydrocarbon group include an alkylene group which may have a substituent and an alkenylene group which may have a substituent. The alkylene group and the alkenylene group may be either linear or branched.

[0035] In the above formula (2), R 5 Examples of the monovalent aliphatic hydrocarbon group include an alkyl group which may have a substituent and an alkenyl group which may have a substituent. The alkyl group and the alkenyl group may be either linear or branched.

[0036] The number of carbon atoms of the above aliphatic hydrocarbon group is preferably 1 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms.

[0037] The substituent which may have a substituent is not particularly limited as long as it has no cyclic structure, and examples thereof include a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkylidene group, an acyl group, an acyloxy group, an amino group, a silyl group, a carboxy group, a sulfo group, a cyano group, a nitro group, a mercapto group, and an oxo group.

[0038] Examples of halogen atoms used as substituents include fluorine, chlorine, bromine, and iodine atoms. Alkyl groups used as substituents may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. Alkenyl groups used as substituents may be linear or branched. The number of carbon atoms in the alkenyl group is preferably 2 to 10. Alkoxy groups used as substituents may be linear or branched. The number of carbon atoms in the alkoxy group is preferably 1 to 10. An alkylidene group used as a substituent refers to a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms in the alkylidene group is preferably 1 to 10. An acyl group used as a substituent refers to a group represented by the formula:-C(=O)-R (where R is an alkyl group). The alkyl group represented by R may be linear or branched. The number of carbon atoms in the acyl group is preferably 2 to 10. The acyloxy group used as a substituent is a group represented by the formula -OC(=O)-R (wherein R is the same as above). The number of carbon atoms in the acyloxy group is preferably 2 to 10. The above substituent may have further substituents (sometimes called "secondary substituents"). The same substituent as above may be used as the secondary substituent.

[0039] Among the above, R in equation (1) 2 and R 4Preferably, the alkylene group has 1 to 10 carbon atoms. Examples of alkylene groups with 1 to 10 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, s-butylene group, t-butylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, and 4-methyl Examples include n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, n-heptylene group, n-octylene group, n-nonylene group, or n-decanylene group. Among the above, R in equation (1) 2 More preferably, the group is an ethylene group, n-propylene group, n-butylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, or n-decanylene group, with n-butylene group being particularly preferred. Among the above, R in equation (1) 4 More preferably, the group is an ethylene group, an n-propylene group, an n-butylene group, or an n-pentylene group, with an ethylene group being particularly preferred.

[0040] Also, among the above, R in equation (2) 5Preferably, the alkyl group has 1 to 10 carbon atoms. Examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n- Examples include pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, decyl group, etc. Among these, R in formula (2) 5 It is particularly preferable that the group be a methyl group or an ethyl group.

[0041] An example of a monomer component corresponding to formula (1) is 4-hydroxybutyl acrylate.

[0042] Examples of monomer components corresponding to formula (2) include ethyl carbitol acrylate, methoxyethyl acrylate, and triethylene glycol diacrylate.

[0043] The combination of monomer component (a1) and monomer component (a2) is not particularly limited, but it is preferable that one is a compound corresponding to formula (1) and the other is a compound corresponding to formula (2). With this combination, a composition that can be used as a hard coat agent in a single layer tends to be obtained, which has excellent adhesion to the substrate and excellent transparency and coating hardness in the cured product.

[0044] When monomer component (A) contains three monomer components, the combination of monomer component (a1), monomer component (a2), and monomer component (a3) ​​whose Tg of the polymer after homopolymerization is not the maximum or minimum is not particularly limited, and monomer component (a3) ​​may be a compound corresponding to formula (1) or a compound corresponding to formula (2).

[0045] The monomer component (A) can be a commercially available product. Examples of commercially available monomer components include "Miramer M232" manufactured by MIWON Corporation and "Viscoat #190" manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0046] The content of monomer component (A) in the solid content of the active energy ray curable composition is preferably in the range of 10 to 50% by mass, more preferably in the range of 15 to 40% by mass, and particularly preferably in the range of 20 to 35% by mass. When the content of monomer component (A) is within the above range, a composition is likely to be obtained that has excellent adhesion to the substrate and excellent transparency and coating hardness in the cured product, and can be used as a hard coat agent in a single layer. The content of monomer component (A) above is expressed as the percentage (by mass) of the solid content of monomer component (A) relative to the solid content of the composition (i.e., the components that constitute the active energy ray curable composition, excluding components that volatilize at room temperature or by heating as necessary, such as solvents) which is set at 100% by mass. Furthermore, the content of monomer component (A) above refers to the total amount obtained by summing the content of each monomer component that constitutes monomer component (A) (for example, monomer component (a1) and monomer component (a2)).

[0047] The mass ratio of monomer component (a1) to monomer component (a2) (monomer component (a1) / monomer component (a2), solid content ratio) is not particularly limited, but is preferably 90 / 10 to 10 / 90.

[0048] <Ingredient (B)> Component (B) is a monomer, oligomer, or polymer having at least two (meth)acryloyl groups in its molecule. However, component (B) is excluded if it corresponds to the above-mentioned monomer component (A). By containing component (B), the active energy ray curable composition of the present invention improves the crosslinking density after curing, resulting in a cured product with excellent scratch resistance and coating hardness. Component (B) can be used alone or in combination of two or more types.

[0049] Examples of difunctional (meth)acrylates include 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and dipropyl Examples include di(meth)acrylates of dihydric alcohols such as ethylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, di(meth)acrylate of diols obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol, and di(meth)acrylates of diols obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A.

[0050] Examples of (meth)acrylates with three or more functions include poly(meth)acrylates of polyhydric alcohols with three or more functions, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol poly(meth)acrylate; tri(meth)acrylates of triols obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of glycerin; di(meth)acrylates of triols obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane; and poly(meth)acrylates of polyoxyalkylene polyols, such as di(meth)acrylates of diols obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A.

[0051] Component (B) is not particularly limited as long as it is a monomer, oligomer, or polymer having at least two (meth)acryloyl groups in the molecule, but from the viewpoint of obtaining a composition that can form a cured product with excellent scratch resistance and coating hardness, it is preferable that it is a polyfunctional urethane (meth)acrylate having at least two (meth)acryloyl groups in the molecule.

[0052] Examples of the polyfunctional urethane (meth)acrylates used include reaction products of polyisocyanate and (meth)acrylate having hydroxyl groups; and reaction products of polyisocyanate, (meth)acrylate having hydroxyl groups, and polyol, which have two or more (meth)acryloyl groups.

[0053] Polyisocyanates refer to compounds having two or more isocyanate groups (-N=C=O). Examples of polyisocyanates include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; alicyclic polyisocyanates such as norbornane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, and 2-methyl-1,5-diisocyanatocyclohexane; aromatic polyisocyanates such as toluene diisocyanate, xylene diisocyanate, and diphenylmethane diisocyanate; and their biuret, isocyanurate (nurate), allophanate, and adduct forms.

[0054] Among the polyisocyanates mentioned above, it is preferable to use aliphatic polyisocyanates and / or alicyclic polyisocyanates because they can reduce the discoloration of the cured coating film of the active energy ray curable composition.

[0055] Hydroxylated (meth)acrylates are those having a hydroxyl group and a (meth)acryloyl group, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, hydroxypivalic acid neopentyl glycol mono( Mono(meth)acrylates of dihydric alcohols such as meth)acrylate; trihydric alcohol mono or di(meth)acrylates such as trimethylolpropanedi(meth)acrylate, ethylene oxide (EO)-modified trimethylolpropane(meth)acrylate, propylene oxide (PO)-modified trimethylolpropanedi(meth)acrylate, glycerin di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, or one of the alcoholic hydroxyl groups thereof. Mono and di(meth)acrylates having hydroxyl groups modified with ε-caprolactone; compounds having a monofunctional hydroxyl group and three or more functional (meth)acryloyl groups, such as pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, or polyfunctional compounds having hydroxyl groups obtained by further modifying the said compound with ε-caprolactone. (Meth)acrylates; (meth)acrylates having oxyalkylene chains such as dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate; (meth)acrylates having block-structured oxyalkylene chains such as polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate;Examples include (meth)acrylates having randomly structured oxyalkylene chains, such as poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate and poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate. These hydroxyl group-containing (meth)acrylates may be used individually or in combination of two or more types.

[0056] In particular, from the viewpoint of obtaining even better scratch resistance, it is preferable to use one or more compounds selected from the group consisting of pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol (meth)hexaacrylate, and tripentaerythritol hepta(meth)acrylate, with dipentaerythritol penta(meth)acrylate and dipentaerythritol (meth)hexaacrylate being more preferable.

[0057] Examples of the polyols used include polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyester polyols; and polycarbonate polyols. These polyols may be used individually or in combination of two or more.

[0058] The reaction between polyisocyanates and (meth)acrylates having hydroxyl groups, and the reaction between polyisocyanates, (meth)acrylates having hydroxyl groups, and polyols can be carried out using conventional urethane formation methods. Furthermore, when carrying out the urethane reaction, a urethane catalyst may be used as needed. Examples of urethane catalysts include organometallic compounds such as dibutyltin dilaurate, dibutyltin diacetate, dioctyltin laurate, trimethyltin hydroxide, tetra-n-butyltin, zinc bisacetylacetonate, zirconium tris(acetylacetonate)ethylacetoacetate, zirconium tetraacetylacetonate, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, and tetrabutoxyzirconium; metal salts such as tin octenoate, zinc hexanoate, zinc octenoate, zinc stearate, zirconium 2-ethylhexanoate, cobalt naphthenate, stannous chloride, stannous chloride, and potassium acetate; and triethylamine, triethylenediamine, and benzyldiethylamine. Amine catalysts such as 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene, N,N,N′,N′-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethylmorpholine, diazabicyclononene; bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, and other organic bismuths such as dibutylbismuth dilaurate and dioctylbismuth dilaurate. Examples of bismuth compounds include bismuth-based catalysts such as organic acid bismuth salts including bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth lybisneodecanoate, bismuth disalicylate, and bismuth digallate.

[0059] Furthermore, the reaction between polyisocyanates and (meth)acrylates having hydroxyl groups, and the reaction between polyisocyanates, (meth)acrylates having hydroxyl groups, and polyols can be carried out using organic solvents that do not have functional groups that react with isocyanate groups, such as esters like ethyl acetate and butyl acetate, ketones like methyl ethyl ketone and methyl isobutyl ketone, and aromatics like toluene and xylene.

[0060] A polyfunctional urethane (meth)acrylate suitable as component (B) has an isocyanuryl skeleton in its molecule. The isocyanuryl skeleton is a compound having a six-membered ring of isocyanurate groups obtained by the trimerization reaction of isocyanates. Having an isocyanuryl skeleton in the molecule has a polar structure with hydroxyl groups and the isocyanuryl skeleton, which promotes the aggregation of organic fine particles described later and can further improve anti-glare properties. Furthermore, a polyfunctional urethane (meth)acrylate particularly suitable as component (B) has an isocyanuryl skeleton and a cyclic structure in its molecule. Having a cyclic structure means having an aromatic hydrocarbon group and / or an alicyclic hydrocarbon group. More specifically, the isocyanuryl skeleton is synthesized from a diisocyanate having a cyclic structure. That is, a polyfunctional urethane (meth)acrylate particularly suitable as component (B) has a structure in which an aromatic hydrocarbon group and / or an alicyclic hydrocarbon group are bonded to an isocyanuryl skeleton in its molecule. This tends to lead to the creation of compositions capable of forming cured products with even greater scratch resistance and coating hardness.

[0061] Commercially available polyfunctional urethane (meth)acrylates can be used. Examples of commercially available urethane (meth)acrylates include "EPS-1146" and "UNIDIC® V-4000" from DIC Corporation, "Shiko®" from Nippon Synthetic Chemical Co., Ltd., "Beamset® 500" from Arakawa Chemical Co., Ltd., "EBECRYL®" from Daicel-Scytec Corporation, and "Art Resin®" from Negami Kogyo Co., Ltd.

[0062] The content of component (B) in the solid content of the active energy ray curable composition is preferably in the range of 50 to 90% by mass, more preferably in the range of 55 to 87% by mass, and particularly preferably in the range of 60 to 85% by mass. When the content of component (B) is within the above range, a composition is likely to be obtained that has excellent adhesion to the substrate and excellent transparency and coating hardness in the cured product, and can be used as a hard coat agent in a single layer.

[0063] <Fine particles (C)> The composition of the present invention preferably contains fine particles (C). The fine particles create an uneven surface on the cured coating film formed from the composition of the present invention, thereby providing anti-glare properties.

[0064] As the fine particles, organic fine particles, inorganic fine particles, and organic-inorganic composite fine particles can be used. Among these, organic fine particles are preferable from the viewpoint of transparency. Organic fine particles also have the function of controlling the haze value of the hard coat layer by controlling the difference between their refractive index and the refractive index of the composition.

[0065] Examples of organic fine particles include polymethyl methacrylate fine particles, silicone fine particles, polystyrene fine particles, polycarbonate fine particles, acrylic styrene fine particles, benzoguanamine fine particles, melamine fine particles, polyolefin fine particles, polyester fine particles, polyamide fine particles, polyimide fine particles, and polyfluoroethylene fine particles. These organic fine particles may be used individually or in combination of two or more types. Among these, acrylic styrene fine particles are preferred from the viewpoint of excellent cohesiveness, which allows for the formation of appropriate irregularities on the coating surface and provides even better anti-glare properties.

[0066] Furthermore, the organic fine particles may be cross-linked organic fine particles (organic cross-linked fine particles). The method of cross-linking is not particularly limited, and organic cross-linked fine particles can be obtained by adding commonly used cross-linking agents as needed and adjusting the degree of cross-linking to an appropriate range.

[0067] Examples of inorganic fine particles include silica particles such as spherical silica and amorphous silica, metal oxide particles such as titanium dioxide, zinc oxide, zircon, zirconia, and alumina, calcium carbonate particles, and barium sulfate particles. These inorganic fine particles may be used individually or in combination of two or more types.

[0068] If inorganic fine particles are included, a dispersion aid may be included. Examples of dispersion aids include isopropyl acid phosphate, triisodecyl phosphite, ethylene oxide-modified phosphate dimethacrylate and other phosphate ester compounds. These dispersion aids can be used alone or in combination of two or more. Examples of commercially available dispersion aids include "Kayama PM-21" and "Kayama PM-2" manufactured by Nippon Kayaku Co., Ltd., and "Light Ester P-2M" manufactured by Kyoeisha Chemical Co., Ltd.

[0069] The shape of the fine particles is not particularly limited, but may be, for example, bead-like or roughly spherical, or amorphous such as powder, but roughly spherical is preferred. More preferably, the particles are roughly spherical with an aspect ratio of 1.5 or less, and most preferably perfectly spherical.

[0070] The average particle size of the fine particles is not particularly limited, but is preferably in the range of 0.1 μm to 10 μm. Here, the average particle size (μm) is the 50% volume diameter (median diameter) obtained by measurement using the laser diffraction-scattering method based on Mie theory. If the average particle size of the fine particles is larger than the above numerical range, the image clarity of the display will decrease, and if it is smaller than the above numerical range, sufficient anti-glare will not be obtained, and glare will increase. The particle size distribution of the fine particles is not particularly limited, but it is preferable that they be monodisperse fine particles with uniform particle size. Furthermore, when using commercially available fine particles, if the average particle size is listed in the catalog value of the commercially available product, that value may be used as the average particle size of the fine particles.

[0071] The fine particles are not particularly limited, but it is preferable that they have a refractive index such that the refractive index difference between them and the cured products of monomer component (A) and component (B) is, for example, 0 to 0.20.

[0072] The content of fine particles in the solid content of the active energy ray curable composition (solid content) is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 15% by mass, and particularly preferably in the range of 1 to 10% by mass.

[0073] <Photopolymerization initiator> The composition of the present invention preferably contains a photopolymerization initiator. The type of photopolymerization initiator used in the composition of the present invention is not particularly limited, and conventionally known photopolymerization initiators can be used.

[0074] Examples of photopolymerization initiators include various benzophenones such as benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bisdimethylaminobenzophenone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, Michlar's ketone, and 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone;

[0075] Xanthones, thioxanthones, 2-methylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and other xanthones and thioxanthones; various acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether;

[0076] α-diketones such as benzyl and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; various benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate;

[0077] 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one,3,3′-carbonyl-bis(7-diethylamino)coumarin,1-hydroxycyclohexylphenyl ketone,2,2′-dimethoxy-1,2-diphenylethane-1-one,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one,2-H Droxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2 -Methylpropan-1-one, 4-benzoyl-4′-methyldimethyl sulfide, 2,2′-diethoxyacetophenone, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, o-benzoylmethyl benzoate, bis(4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α,α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2-(o-chlorophenyl)-4,5-di Examples include phenylimidazolyl dimer, 2,4-bis-trichloromethyl-6-[di-(ethoxycarbonylmethyl)amino]phenyl-S-triazine, 2,4-bis-trichloromethyl-6-(4-ethoxy)phenyl-S-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-ethoxy)phenyl-S-triazine anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, and β-chloranthraquinone. These photopolymerization initiators can be used alone or in combination of two or more.

[0078] Furthermore, among the above photopolymerization initiators, it is preferable to use one or more mixed systems selected from the group consisting of 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, as these exhibit activity to a wider range of wavelengths of light and can improve the curability of the cured coating film of the above active energy ray curable composition.

[0079] Commercially available photopolymerization initiators include, for example, IGM's "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", and "Omnirad Examples include "-500", "Omnirad-81", "KayaCure-DETX", "KayaCure-MBP", "KayaCure-DMBI", "KayaCure-EPA", and "KayaCure-OA" from Nippon Kayaku Co., Ltd., "VyCure-10" and "VyCure-55" from Stoufa Chemical, "Trigonal P1" from Akzo, "Sandoz-1000" from Sandoz, "Deep" and "Quantacure-PDO" from Apjohn, "Quantacure-ITX" and "Quantacure-EPD" from Wardbrenkinsop, and "Runtecure(registered trademark)-1104" from Runtec.

[0080] The amount of photopolymerization initiator added is preferably an amount that can fully exhibit its function as a photopolymerization initiator, and is within a range that does not cause crystal precipitation or deterioration of the coating film properties. Specifically, it is preferably in the range of 0.05 to 20 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass, per 100 parts by mass of the active energy ray curing composition.

[0081] Furthermore, since the active energy ray curable composition can improve the curability of the cured coating film, it may also contain a photosensitizer.

[0082] Examples of photosensitizers include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, and sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothironium-p-toluenesulfonate.

[0083] <Other resin components with active energy ray curability> The active energy ray-curable resin composition of the present invention may also contain other active energy ray-curable resin components other than monomer components (A) and (B), as long as they do not impair the effects of the present invention. Preferably, the total content of monomer components (A) and (B) is 50% by mass or more in the solid content of the active energy ray-curable resin composition.

[0084] (Other optional additives) The active energy ray curable resin composition of the present invention may further contain organic solvents, ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, silane coupling agents, phosphate ester compounds, rheology control agents, defoaming agents, antifogging agents, colorants, and the like as additives.

[0085] Examples of organic solvents include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; and glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate. These organic solvents can be used individually or in combination of two or more. These organic solvents are mainly used to adjust the viscosity of the composition, and it is generally preferable to adjust the non-volatile content to be in the range of 10 to 80% by mass.

[0086] Examples of UV absorbers include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthen carboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthen carboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These UV absorbers can be used individually or in combination of two or more.

[0087] Examples of antioxidants include hindered phenol antioxidants, hindered amine antioxidants, organosulfur antioxidants, and phosphate ester antioxidants. These antioxidants can be used individually or in combination of two or more.

[0088] Examples of silicon-based additives include polyorganosiloxanes having alkyl or phenyl groups, such as dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethylpolysiloxane copolymer, and amino-modified dimethylpolysiloxane copolymer; polydimethylsiloxane having polyether-modified acrylic groups; and polydimethylsiloxane having polyester-modified acrylic groups. These silicon-based additives can be used individually or in combination of two or more types.

[0089] Examples of fluorine-based additives include the "Megaface" series manufactured by DIC Corporation. These fluorine-based additives can be used individually or in combination of two or more types.

[0090] Examples of silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Vinyl-based silane coupling agents such as aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, special aminosilanes, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatetopropyltriethoxysilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane;

[0091] Epoxy-based silane coupling agents such as diethoxy(glycidyloxypropyl)methylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane;

[0092] Styrene-based silane coupling agents such as p-styryltrimethoxysilane;

[0093] (Meth)acryloxy-based silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane;

[0094] Amino-based silane coupling agents such as N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane;

[0095] Ureidopropyltriethoxysilane and other ureidopropyl silane coupling agents;

[0096] Chloropropyl silane coupling agents such as 3-chloropropyltrimethoxysilane;

[0097] Mercaptopropyl silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoquinsilane;

[0098] Sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide;

[0099] Examples include isocyanate-based silane coupling agents such as 3-isocyanate-propyltriethoxysilane. These silane coupling agents can be used individually or in combination of two or more.

[0100] Examples of phosphate ester compounds include those having a (meth)acryloyl group in their molecular structure. Commercially available examples include "Kayama PM-2" and "Kayama PM-21" from Nippon Kayaku Co., Ltd., "Light Ester P-1M," "Light Ester P-2M," and "Light Acrylate P-1A(N)" from Kyoeisha Chemical Co., Ltd., "SIPOMER PAM 100," "SIPOMER PAM 200," "SIPOMER PAM 300," and "SIPOMER PAM 4000" from SOLVAY, "Viscote #3PA" and "Viscote #3PMA" from Osaka Organic Chemical Industry Co., Ltd., and "New Frontier S-23A" from Daiichi Kogyo Seiyaku Co., Ltd.; and "SIPOMER PAM 5000" from SOLVAY, which is a phosphate ester compound having an allyl ether group in its molecular structure.

[0101] (cured product) The cured product of the present invention can be obtained by irradiating the active energy ray-curable resin composition of the present invention with active energy rays. Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. When ultraviolet rays are used as the active energy rays, the irradiation may be carried out under an inert gas atmosphere such as nitrogen gas, or under an air atmosphere, in order to efficiently carry out the curing reaction by ultraviolet rays.

[0102] For practical and economic reasons, ultraviolet lamps are commonly used as sources of ultraviolet light. Specifically, these include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

[0103] The integrated light intensity of active energy rays is not particularly limited, but is between 0.1 and 50 kJ / m 2 Preferably, it is 0.3 to 20 kJ / m³. 2 It is more preferable that the cumulative light intensity is within the above range, as this can prevent or suppress the occurrence of uncured areas.

[0104] The irradiation with active energy rays may be performed in one stage or in two or more stages.

[0105] <Slope structure> As described above, the cured product of the present invention has a component gradient structure. The cured product of the present invention has a good surface property because the component gradient structure is formed such that the surface of the cured product (the side not in contact with the substrate) has a high proportion of monomer component (A) with high Tg and low corrosiveness and component (B) which is a high-density crosslinked organism. In addition, the interior of the cured product (the side in contact with the substrate) has a high proportion of monomer component (A) with low Tg and high corrosiveness, resulting in excellent substrate adhesion and, as a whole, excellent coating properties.

[0106] Furthermore, as described above, the cured product of the present invention exhibits a change in the concentration of a specific component in a specific direction, and therefore also exhibits a change in hardness in that specific direction. For this reason, the cured product of the present invention can be said to have a hardness gradient structure (hereinafter also referred to as a hardness gradient structure) in which the hardness changes in a specific direction (depth direction). Because monomer component (A) is corrosive to the substrate, the hardness of the cured product of the present invention gradually decreases from the surface of the cured product (the side not in contact with the substrate) toward the side in contact with the substrate.

[0107] The fact that the cured product of the present invention has the above-mentioned component gradient structure and / or hardness gradient structure can be confirmed by performing cross-sectional analysis using, for example, scanning electron microscopy (SEM)-energy dispersive X-ray spectrometer (EDS), microslurry jet erosion (MSE), Fourier transform infrared spectroscopy (FT-IR), micro-Raman spectrophotometer, nanoindentation device, etc.

[0108] Therefore, by performing the above cross-sectional analysis and observing the cross-section, if the above-mentioned inclined structure is observed, the conventional cured product and the cured product of the present invention can be clearly distinguished.

[0109] (Laminated structure) The laminate of the present invention has a cured coating film of the active energy ray curable resin composition of the present invention on one or both sides of a substrate, and can be obtained by coating the substrate with the active energy ray curable resin composition and curing it by irradiation with active energy rays.

[0110] Examples of substrates include cyclic olefin substrates and acrylic resin substrates. Since the active energy ray-curable resin composition of the present invention yields a cured coating film with excellent adhesion to acrylic resins, an acrylic resin substrate is preferred as the substrate. As mentioned above, a PMMA substrate is more preferable for the acrylic resin substrate. The substrate may also be in film form.

[0111] PMMA film is a substrate formed by molding PMMA resin onto a film. The active energy ray curable resin composition of the present invention exhibits excellent adhesion to PMMA resin, therefore, an untreated PMMA film may be used as the substrate. However, in order to further improve substrate adhesion, a PMMA film may be treated by sandblasting, solvent treatment, electrical treatment (corona discharge treatment, atmospheric pressure plasma treatment), chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet / electron beam irradiation treatment, oxidation treatment, etc.

[0112] The thickness of the substrate is preferably 90 μm or less, more preferably 85 μm or less, and particularly preferably 80 μm or less. On the other hand, the thickness of the substrate is preferably 10 μm or more, more preferably 15 μm or more, and particularly preferably 20 μm or more. By keeping the thickness of the substrate within the above range, curling is more easily suppressed even when a hard coat layer is provided on one side of the acrylic resin film.

[0113] Methods for forming the cured coating film that constitutes the laminate include, for example, painting methods, transfer methods, and sheet bonding methods.

[0114] Painting methods involve either spray-coating the product with paint, or applying a topcoat to the molded product using printing equipment such as curtain coaters, roll coaters, or gravure coaters, and then curing it by irradiating it with active energy rays.

[0115] The transfer method involves applying the above-mentioned active energy ray curable resin composition onto a release-type substrate sheet to obtain a transfer material, adhering the transfer material to the surface of a molded product, peeling off the substrate sheet to transfer the top coat to the surface of the molded product, and then irradiating it with active energy rays to cure it; or, after adhering the transfer material to the surface of a molded product, irradiating it with active energy rays to cure it, and then peeling off the substrate sheet to transfer the top coat to the surface of the molded product.

[0116] The sheet bonding method is a method of forming a protective layer on the surface of a molded product by bonding a protective sheet having a coating made of a curable composition on a base sheet, or a protective sheet having a coating made of a curable composition and a decorative layer on a base sheet, to a molded product.

[0117] Sheet bonding methods include, specifically, a method in which a base sheet of a protective layer-forming sheet, which has been prepared in advance, is bonded to the molded product, and then the resin layer is cross-linked and cured by heat curing to form a B-stage (post-bonding method), and a method in which a protective layer-forming sheet is sandwiched in a molding die, resin is injected and filled into the cavity to obtain a resin molded product, and at the same time the surface of the product is bonded to the protective layer-forming sheet, and then the resin layer is cross-linked and cured by heat curing (simultaneous molding bonding method).

[0118] If the active energy ray-curable composition contains an organic solvent, it is preferable to heat it at 40 to 120°C for several tens of seconds to several minutes after application to volatilize the organic solvent, and then cure the active energy ray-curable composition by irradiating it with active energy rays.

[0119] As described above, the active energy ray curable resin composition of the present invention has excellent substrate adhesion, particularly to PMMA substrates. For this reason, it is preferable that the laminate of the present invention does not have a primer layer between the PMMA substrate and the cured coating film, and that the cured coating film is directly in contact with the PMMA substrate as a single layer. This makes it possible to omit the process of coating and drying the primer layer in the laminate of the present invention, and further reduce the cost of manufacturing.

[0120] Furthermore, the laminate of the present invention may have other layer configurations besides the cured coating film made of the active energy ray curable resin composition. The method for forming these various layer configurations is not particularly limited; for example, they may be formed by directly applying the resin raw material, or by bonding pre-formed sheets together with an adhesive. [Examples]

[0121] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. Unless otherwise specified, "parts," "%," etc., in the examples refer to mass-based measurements.

[0122] [Raw materials] The raw materials used in the examples and comparative examples are as follows:

[0123] (Monomer component (A)) <a1>4-Hydroxybutyl acrylate (Trade name: 4-HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg of polymer after homopolymerization: -32℃, Molecular weight: 144) <a2>Ethyl carbitol acrylate (product name: Viscoat #190, manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg of polymer after homopolymerization: -67℃, molecular weight: 188) <a3>Methoxyethyl acrylate (trade name: 2-MTA, manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg of polymer after homopolymerization: -50℃, molecular weight: 130) <a4>Triethylene glycol diacrylate (trade name: Miramer M232, manufactured by Miwon Specialty Chemical, Tg of polymer after homopolymerization: 46°C, molecular weight: 258)

[0124] (Monomers not included in monomer component (A), used for comparison) <ra1>Trimethylolpropane triacrylate (Trade name: Miramer M300, manufactured by Miwon Specialty Chemical, Tg of polymer after homopolymerization: 62°C, Molecular weight: 296) <ra2>Trimethylolpropane triacrylate (Trade name: Miramer M450, manufactured by Miwon Specialty Chemical, Tg of polymer after homopolymerization: 65°C, Molecular weight: 352) <ra3>1,9-Nonanediol diacrylate (Trade name: Light Acrylate 1.9ND-A, manufactured by Kyoeisha Chemical Co., Ltd., Tg of polymer after homopolymerization: 68°C, Molecular weight: 268) <ra4>Dimethylol-tricyclodecanediaacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., Tg of polymer after homopolymerization: 140°C, molecular weight: 304)

[0125] Table 1 below shows a list of the above raw materials. [Table 1]

[0126] (Component (B)) The polyfunctional urethane (meth)acrylate (B1) was synthesized by the method shown in Synthesis Example 1 below. (Synthesis Example 1: Synthesis of polyfunctional urethane (meth)acrylate resin (B1)) In a reactor equipped with a stirrer, condenser, dropping funnel and gas inlet tube, 84.3 parts of Vestat T1890 / 100 (manufactured by Evonik Japan Co., Ltd.: isocyanurate-type polyisocyanate of isophorone diisocyanate, isocyanate group content = 17.3%), 1.6 parts of 2,6-di-tert-butyl-4-methylphenol (BHT), 0.2 parts of dibutyltin dilaurate and 34 parts of butyl acetate were charged, and the system temperature was raised while stirring until it reached 80°C. Then, Arronix M-403 (manufactured by Toagosei Co., Ltd.: After charging 450 parts of dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate (weight ratio = 40 / 60~50 / 50, hydroxyl value = approximately 48 mg KOH / g), the mixture was held for 5 hours to obtain polyfunctional urethane (meth)acrylate (B1), which is a mixture containing polyfunctional urethane (meth)acrylate (non-volatile content: 94%). Polyfunctional urethane (meth)acrylate (B1) was analyzed by FT-IR and it was confirmed that the isocyanate group peak had disappeared.

[0127] (Fine particles (C)) <c1>Acrylic-styrene copolymer crosslinked organic microparticles (product name: Acrybase DLB-301, manufactured by Fujikura Chemical Co., Ltd.) <c2>Acrylic-styrene copolymer crosslinked organic microparticles (product name: Acrybase DLB-303, manufactured by Fujikura Chemical Co., Ltd.)

[0128] (Photopolymerization initiator (D)) <d1>1-Hydroxycyclohexyl-phenyl ketone (Trade name: Omnirad 184, manufactured by IGM Resins)

[0129] (base material) <s1>PMMA base material

[0130] Table 2 below shows a list of the above raw materials. [Table 2]

[0131] (Evaluation of the erosive properties of monomer component (A)) The corrosive properties of monomer component (A) on the PMMA substrate were evaluated as follows.

[0132] (Erosion evaluation test 1: Evaluation of the erosion properties of monomer components) A 40 μm thick PMMA substrate was dropped with 1 mL of triethylene glycol diacrylate (trade name: Miramer M232, manufactured by Miwon Specialty Chemical, Tg of polymer after homopolymerization: 46°C) solution, and allowed to stand at 80°C for 5 minutes. The PMMA substrate was then washed with 50 mL of isopropanol, dried, and the amount of PMMA substrate in the dropped portion was measured by IR.

[0133] In evaluating erosive properties, if absorption of triethylene glycol diacrylate was detected in addition to absorption of the PMMA substrate, it was considered to have erosive properties; if no absorption of triethylene glycol diacrylate was detected, it was considered to have no erosive properties.

[0134] IR was performed under the following measurement conditions. Measurements were taken using an FT-IR (instrument name: Fourier Transform Infrared Spectrophotometer FT / IR-6X, JASCO Corporation) in the following manner. First, a diamond prism was used to measure wavenumbers of 400-4000 cm⁻¹. -1 , disassembled 4cm -1 Background measurements were performed with a set accumulation count of 16. Next, the surface on which the monomer component solution of the PMMA substrate was dropped was brought into contact with the diamond prism, and sample measurements were performed under the same conditions as the background measurements.

[0135] Figure 1 shows the FT-IR spectrum of a PMMA substrate. Figure 2 shows the FT-IR spectrum of triethylene glycol diacrylate. Figure 3 shows the FT-IR spectrum of the PMMA substrate in the area where triethylene glycol diacrylate solution was dropped onto the PMMA substrate, followed by washing and drying.

[0136] As is clear from Figures 1 and 2, the 800 cm³ characteristic of triethylene glycol diacrylate -1 and 1200cm -1 Erosion was evaluated by identifying nearby absorption peaks. As is clear from Figure 3, when a triethylene glycol diacrylate solution is dropped onto a PMMA substrate, and after washing and drying, the FT-IR spectrum of the PMMA substrate in the dropped area shows a characteristic 800 cm⁻¹ of triethylene glycol diacrylate. -1 and 1200cm -1 An absorption peak was detected in the vicinity. Therefore, it was confirmed that triethylene glycol diacrylate is corrosive to PMMA substrates.

[0137] (Erosion evaluation tests 2-4: Erosion evaluation of monomer component (A)) Instead of triethylene glycol diacrylate, 4-hydroxybutyl acrylate (trade name: 4-HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg of polymer after homopolymerization: -32°C), ethyl carbitol acrylate (trade name: Viscoat #190, manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg of polymer after homopolymerization: -67°C), and methoxyethyl acrylate (trade name: 2-MTA, manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg of polymer after homopolymerization: -50°C) were used, and erosion evaluation tests 2 to 4 were conducted using the same method as in erosion evaluation test 1. As a result, it was confirmed that 4-hydroxybutyl acrylate, ethyl carbitol acrylate, and methoxyethyl acrylate all exhibit erosive properties towards the PMMA substrate.

[0138] (Erosion test 5: Evaluation of the erosion of a comparative monomer not included in monomer component (A)) Instead of triethylene glycol diacrylate, dimethylol-tricyclodecane diacrylate (trade name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., Tg of polymer after homopolymerization: 140°C) was used, and an erosion test was conducted using the same method as in erosion test 1.

[0139] Figure 4 shows the FT-IR spectrum of dimethylol-tricyclodecanediaacrylate. Figure 5 shows the FT-IR spectrum of the PMMA substrate in the area where a dimethylol-tricyclodecanediaacrylate solution was dropped onto the PMMA substrate, followed by washing and drying.

[0140] As is clear from Figures 1 and 4, FT-IR detected 800 cm³, which is characteristic of dimethylol-tricyclodecanediaacrylate. -1 and 1400cm -1 Erosion was evaluated by identifying nearby absorption peaks. As is clear from Figure 5, when a dimethylol-tricyclodecanediaacrylate solution was dropped onto a PMMA substrate, and after washing and drying, the FT-IR spectrum of the PMMA substrate in the dropped area showed a characteristic 800 cm⁻¹ of dimethylol-tricyclodecanediaacrylate. -1 and 1400cm -1 No nearby absorption peaks were detected. Therefore, dimethylol-tricyclodecanediaacrylate was evaluated as not corrosive to PMMA substrates.

[0141] The active energy ray-curable resin composition was prepared as follows. (Example 1: Preparation of Active Energy Ray Curable Resin Composition (1)) 6.3 parts by mass of 4-hydroxybutyl acrylate (product name: 4-HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg of polymer after homopolymerization: -32℃), 18.8 parts by mass of ethyl carbitol acrylate (product name: Viscoat #190, manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg of polymer after homopolymerization: -67℃), 75 parts by mass of polyfunctional urethane (meth)acrylate (B1), 2.5 parts by mass of acrylic-styrene copolymer crosslinked organic fine particles (product name: Acrybase DLB-301, manufactured by Fujikura Chemical Co., Ltd., refractive index: 1.55, D50 average particle size: 0.98 μm), and 5.0 parts by mass of 1-hydroxycyclohexyl-phenyl ketone (product name: Omnirad 184, manufactured by IGM Resins) were mixed and adjusted with n-butyl acetate and isopropanol to obtain an active energy ray curable resin composition (1).

[0142] (Examples 2-7: Preparation of active energy ray curable resin compositions (2)-(7)) Active energy ray curable resin compositions (2) to (7) were obtained using the same method as in Example 1 with the compositions and formulations shown in Table 3.

[0143] [Table 3]

[0144] (Comparative Examples 1-8: Preparation of Active Energy Ray Curable Resin Compositions (R1)-(R8)) Active energy ray curable resin compositions (R1) to (R8) were obtained using the same method as in Example 1 with the compositions and formulations shown in Table 4.

[0145] [Table 4]

[0146] Note that all values ​​for parts by mass in Tables 3 and 4 represent solid content.

[0147] The laminate was prepared as follows: (Examples 8-14: Fabrication of laminates (L1)-(L7)) The active energy ray-curable resin compositions (1) to (7) obtained in Examples 1 to 7 were each applied to a PMMA substrate, an acrylic resin substrate with a thickness of 40 μm, using a bar coater and solvent-dried at 70°C for 30 seconds. Then, under a nitrogen atmosphere, ultraviolet light at 200 mJ / cm² was applied using a high-pressure mercury lamp. 2 Irradiation was performed to obtain laminates (L1) to (11) having a cured coating film with a thickness of 4 μm on a PMMA substrate.

[0148] (Comparative Examples 9-16: Fabrication of laminates (L8)-(L15)) Using the active energy ray curable resin compositions (R1) to (R8) obtained in Comparative Examples 1 to 8, laminates (L8) to (L15) were obtained in the same manner as the preparation of laminates (L1) to (L7) in Examples 8 to 14.

[0149] The laminates (L1) to (L15) obtained in the above examples and comparative examples were used for the following evaluations.

[0150] [Methods for evaluating transparency] The haze value of the laminate was measured using a haze meter (manufactured by Suga Test Instruments Co., Ltd., model number HZ-V3) in accordance with JIS K7136.

[0151] [Method for evaluating transparency clarity] The laminate was measured at five points with optical comb widths of 0.125, 0.25, 0.5, 1.0, and 2.0 mm using an image quality measuring instrument (Suga Test Instruments Co., Ltd. "ICM-IT") in accordance with JIS K7374.

[0152] [Method for evaluating the appearance of the coating film] The cured coating film of the laminate was visually inspected and evaluated according to the following criteria. 5 (Excellent): The coating is free from unevenness, defects, and abnormalities, and the light from the fluorescent lamp is evenly scattered. 4 (Good): Some unevenness, defects, or abnormalities are present in the coating, but the light from the fluorescent lamp is scattered uniformly. 3 (Acceptable): The paint film has some unevenness, defects, or abnormalities, causing the light from the fluorescent lamp to scatter unevenly in some areas. 2 (Not practical): The coating has unevenness, defects, or abnormalities, causing the light from the fluorescent lamp to scatter unevenly. 1 (Not practical): The paint film shows significant unevenness, defects, or other abnormalities, and there is no light scattering from the fluorescent lamp.

[0153] [Method for evaluating scratch resistance] A disc-shaped indenter with a diameter of 1.0 cm was wrapped in 0.5 g of steel wool ("Bonstar #0000" manufactured by Nippon Steel Wool Co., Ltd.), and an abrasion test was conducted by applying a load of 500 g to the indenter and moving it back and forth 10 times across the surface of the laminated coating. Visual evaluation was performed according to the following criteria. 5 (Best): No blemishes 4 (Good): 1 to 5 linear scratches 3 (acceptable): 6-19 linear scratches 2 (Not practical): More than 20 linear scratches 1 (Not usable): Band-like scratches

[0154] [Method for evaluating substrate adhesion (initial stage)] Cuts were made on the surface of the cured coating of the laminate using a utility knife to create 100 grid patterns of 1 mm x 1 mm. Cellophane adhesive tape was then applied over these grid patterns and rapidly peeled off twice. The number of grid patterns that remained without peeling was counted and evaluated according to the following criteria. 5 (Best): The number of remaining grid squares was 100. 4 (Good): The number of remaining grid squares was between 95 and 99. 3 (Acceptable): The number of remaining grid squares was between 65 and 94. 2 (Not practical): The number of remaining grid squares was 64 or less. 1 (Not usable): Peeling was observed outside the grid lines.

[0155] Tables 5 and 6 show the evaluation results.

[0156] [Table 5]

[0157] [Table 6]

[0158] Examples 8-14 shown in Table 5 are examples of laminates using the active energy ray curable composition of the present invention. These laminates were found to have high transparency, excellent adhesion to PMMA substrates, and excellent scratch resistance and coating hardness. On the other hand, Comparative Examples 9-16 shown in Table 6 were not laminates that satisfied all of the requirements of transparency, substrate adhesion, scratch resistance, and coating hardness.

Claims

1. An active energy ray curable resin composition containing the following monomer component (A) and component (B). Monomer component (A): Contains at least two monomer components, Each monomer component has one or two (meth)acrylate groups in one molecule, and has at least one functional group from among ether groups and hydroxyl groups, and does not have aromatic hydrocarbon groups or alicyclic hydrocarbon groups, and the glass transition temperature (Tg) of the polymer when homopolymerized is 150°C or less. Among the monomer components (A), when the monomer component with the highest Tg of the polymer when homopolymerized is designated as monomer component (a1) and the monomer component with the lowest Tg of the polymer when homopolymerized is designated as monomer component (a2), the difference between the Tg of monomer component (a1) and the Tg of monomer component (a2) is 10°C or more. Component (B): A monomer, oligomer, or polymer having two or more (meth)acrylate groups in one molecule (excluding those corresponding to monomer component (A)).

2. The active energy ray curable resin composition according to claim 1, wherein the molecular weight of the monomer component (A) is 300 or less.

3. The active energy ray curable resin composition according to claim 1, wherein the monomer component (A) is corrosive to the PMMA substrate.

4. The active energy ray curable resin composition according to claim 1, wherein the component (B) is a polyfunctional urethane (meth)acrylate.

5. The active energy ray curable resin composition according to claim 4, wherein the polyfunctional urethane (meth)acrylate has an isocyanurate skeleton in its molecule.

6. The active energy ray curable resin composition according to claim 4, wherein the polyfunctional urethane (meth)acrylate has an isocyanurate skeleton and a cyclic structure in its molecule.

7. The active energy ray curable resin composition according to claim 1, further containing fine particles (C).

8. The active energy ray curable resin composition according to claim 7, wherein the fine particles (C) are organic fine particles.

9. The active energy ray curable resin composition according to claim 7, wherein the average particle size of the fine particles (C) is in the range of 0.1 μm to 10 μm.

10. A cured product of an active energy ray curable resin composition according to any one of claims 1 to 9.

11. A laminate comprising a cured coating film of the active energy ray curable resin composition according to any one of claims 1 to 9, provided in direct contact with one or both sides of a PMMA substrate.

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