Laminates and articles

Abstract

Provided is a laminate and article having excellent adhesion between a resin substrate containing an acrylic resin and a hard coat layer, and having a hard coat layer with high hardness. [Solution] A laminate (10) comprising a resin substrate (11) and a hard coat layer (12) provided on the resin substrate (11), wherein the resin substrate (11) contains an acrylic resin, and the hard coat layer (12) is made of a cured product of an active energy ray-curable coating composition containing an unsaturated double bond-containing compound, and when the cross section of the hard coat layer (12) cut in the thickness direction is divided into two equal parts perpendicular to the thickness direction and divided into two regions, region (α) 12α on the resin substrate (11) side and region (β) 12β on the outermost surface side, the number of particles contained in region (α) 12α is five times or more the number of particles contained in region (β) 12β, and the particles are derived from the resin substrate (11).

Description

[Technical Field]

[0001] The present invention relates to laminates and articles. [Background technology]

[0002] Acrylic resins such as polymethyl methacrylate, which are produced from acrylic monomers such as methyl methacrylate, are excellent in transparency, weather resistance, colorability, and moldability, and are therefore used in a variety of applications, including display windows for mobile phones and light guide plates for backlights in liquid crystal displays. A hard coat layer may be provided on the surface of a resin molded product made of an acrylic resin in order to impart hardness or the like.

[0003] For example, Patent Document 1 discloses a laminate having a primer layer and a hard coat layer in this order on an acrylic resin substrate, the primer layer being made of a cured product of an active energy ray-curable resin composition containing an acrylic resin and a (meth)acryloyl group-containing compound, and the hard coat layer being made of a cured product of a hard coat agent containing a urethane (meth)acrylate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6641957 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the laminate described in Patent Document 1, the adhesion of the hard coat layer to the substrate is not considered. An object of the present invention is to provide a laminate and an article in which the adhesion between a resin substrate containing an acrylic resin and a hard coat layer is excellent and the hard coat layer has a high hardness. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] A resin substrate and a hard coat layer provided on the resin substrate, the resin substrate contains an acrylic resin, the hard coat layer is made of a cured product of an active energy ray-curable coating composition containing an unsaturated double bond-containing compound, A laminate in which, when the hard coat layer is cut in the thickness direction and the cut surface is divided into two equal parts in a direction perpendicular to the thickness direction, i.e., a region (α) on the resin substrate side and a region (β) on the outermost surface side, the number of particles contained in the region (α) is 5 times or more the number of particles contained in the region (β), and the particles are derived from the resin substrate. [2] The laminate according to [1] above, wherein the resin substrate is in the form of a sheet. [3] The resin substrate is composed of an acetone soluble component and an acetone insoluble component, The content of the acetone insoluble matter (gel content) in the total amount of the resin substrate is 15% or more, The acetone soluble component includes an acrylic resin having a weight-average molecular weight of 300,000 or less and an acrylic resin having a weight-average molecular weight of more than 300,000, The laminate according to [1] or [2] above, wherein the acrylic resin having a weight-average molecular weight of 300,000 or less has a glass transition temperature Tg of 95° C. or less. [4] An article having the laminate according to any one of [1] to [3] on its surface. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a laminate and an article in which the adhesion between the resin substrate containing an acrylic resin and the hard coat layer is excellent and the hardness of the hard coat layer is high. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a cross-sectional view schematically illustrating an example of a laminate of the present invention. [Figure 2]1 shows images of cross sections of the laminates obtained in Examples 1 to 5 cut in the thickness direction, observed with a scanning electron microscope. [Figure 3] This is an image obtained by binarizing the image in Figure 2. [Figure 4] 1 shows images of cross sections cut in the thickness direction of the laminates obtained in Comparative Examples 1 to 4, observed with a scanning electron microscope. [Figure 5] This is an image obtained by binarizing the image in FIG. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in further detail below by presenting preferred embodiments of the invention. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to the contents of the following description as long as it does not go beyond the gist of the invention. In this specification, the term "hard coat layer" refers to a coating film formed using an active energy ray-curable coating composition after curing, and is also referred to as a "cured product." "(Meth)acrylic" is a general term for "acrylic" and "methacrylic." "(Meth)acryloyl" is a general term for "acryloyl" and "methacryloyl". "(Meth)acrylate" is a general term for "acrylate" and "methacrylate." The term "structural unit" refers to a structural unit derived from a monomer, i.e., a structural unit formed by polymerizing a monomer, or a structural unit in which a portion of the structural unit is converted into a different structure by treating the polymer. The term "sheet" conceptually encompasses sheets and films. The symbol "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits. The ranges of the contents, physical properties, and characteristic values ​​disclosed in this specification can be arbitrarily combined to form new ranges of values.

[0010] [Laminate] FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention. The laminate 10 shown in FIG. 1 includes a resin substrate 11 and a hard coat layer 12 provided on the resin substrate 11. In addition, in order to make the features easier to understand, for the sake of convenience, characteristic parts may be shown enlarged in Figure 1, and the dimensional ratios of each component may differ from the actual ones.

[0011] <Resin substrate> The resin base material 11 in the illustrated example is in the form of a sheet with a single layer structure. The thickness of the sheet-like resin substrate 11 is not particularly limited, but is preferably, for example, 5 μm or more and 500 μm or less, and more preferably 20 μm or more and 300 μm or less.

[0012] The resin base material 11 contains an acrylic resin, that is, the resin base material 11 is an acrylic resin base material. From the viewpoint of productivity and handling, the resin substrate 11 preferably contains particles (X-1). In addition to the particles (X-1), the resin substrate 11 preferably further contains, as a resin other than the particles (X-1), at least one of a reactive group-containing resin (X-2) and a thermoplastic resin (X-3) other than the reactive group-containing resin (X-2). The resin substrate 11 may further contain an additive (X-4) as a component other than the particles (X-1), the reactive group-containing resin (X-2) and the thermoplastic resin (X-3), as needed. The resin substrate 11 may be made of only particles (X-1). When the resin substrate 11 is made of only particles (X-1), the acrylic resin contained in the resin substrate 11 is in a particulate form, and is preferably acrylic rubber particles, which will be described later.

[0013] (particle(X-1)) The particles (X-1) are preferably resin particles, more preferably rubber particles. Examples of rubber particles include acrylic rubber particles, silicone rubber particles, butadiene rubber particles, etc. Among these, acrylic rubber particles are preferred from the viewpoints of transparency and weather resistance of the resin substrate 11. The acrylic rubber particles are preferably an acrylic resin in the resin substrate 11 as an acetone-insoluble component, which will be described later. An example of the acrylic rubber particles will be described below.

[0014] The acrylic rubber particles are preferably acrylic rubber particles having a core-shell structure in which a layer containing a hard polymer (x-2) as an outer layer (shell portion) having a structure of one or more layers and obtained by graft polymerization of a monomer having alkyl methacrylate as the main component is formed on a layer containing an elastic copolymer (x-1) as an inner layer (core portion) having a structure of one or more layers and obtained from alkyl (meth)acrylate as the main component. The acrylic rubber particles may also have one or more layers containing an intermediate polymer (x-3) between a layer containing an elastic copolymer (x-1) and a layer containing a hard polymer (x-2).

[0015] The content of the elastic copolymer (x-1) relative to the total mass of the acrylic rubber particles is preferably 10% by mass to 90% by mass, and more preferably 20% by mass to 70% by mass. The content of the rigid polymer (x-2) relative to the total mass of the acrylic rubber particles is preferably 10% by mass to 90% by mass, and more preferably 30% by mass to 70% by mass. The content of the intermediate polymer (x-3) relative to the total mass of the acrylic rubber particles is preferably 0% by mass to 35% by mass, and more preferably 0% by mass to 20% by mass.

[0016] The elastic copolymer (x-1) is preferably a polymer obtained by polymerizing a monomer composition (m2) containing an alkyl (meth)acrylate. The elastic copolymer (x-1) is more preferably a polymer obtained by polymerizing a monomer composition containing an alkyl acrylate. That is, the elastic copolymer (x-1) preferably contains a structural unit derived from an alkyl (meth)acrylate, and more preferably contains a structural unit derived from an alkyl acrylate. The monomer composition (m2) may further contain at least one of a monomer other than alkyl(meth)acrylate and a crosslinkable monomer. For example, the monomer composition (m2) may contain 80% by mass or more and 99.9% by mass or less of an alkyl acrylate having an alkyl group with 1 to 8 carbon atoms and an alkyl methacrylate having an alkyl group with 1 to 4 carbon atoms, 0% by mass or more and 20% by mass or less of a monomer other than alkyl(meth)acrylate, and 0.1% by mass or more and 10% by mass or less of a crosslinkable monomer (the total of these amounts being 100% by mass).

[0017] Examples of alkyl acrylates having an alkyl group having 1 to 8 carbon atoms include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These alkyl acrylates having an alkyl group having 1 to 8 carbon atoms may be used alone or in any combination of two or more kinds in any ratio.

[0018] The alkyl acrylate having an alkyl group having 1 to 8 carbon atoms is used as the main component of the monomer constituting the elastic copolymer (x-1). Specifically, the amount of the alkyl acrylate having an alkyl group having 1 to 8 carbon atoms used is preferably 30% by mass or more and 99.9% by mass or less, and more preferably 50% by mass or more and 95% by mass or less, based on the total monomers constituting the elastic copolymer (x-1). When the amount used is equal to or more than the above lower limit, good moldability is obtained. When the elastic copolymer (x-1) has a structure of two or more layers, the range of the amount used indicates the amount of alkyl acrylate used in the elastic copolymer (x-1) as a whole. For example, when the elastic copolymer (x-1) has a hard core structure, the amount of alkyl acrylate used in the first layer (core) can be less than 30 mass%.

[0019] Examples of alkyl methacrylates having an alkyl group with 1 to 4 carbon atoms include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. These alkyl methacrylates having an alkyl group with 1 to 4 carbon atoms may be used alone or in any combination of two or more kinds in any ratio. The amount of alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms used is preferably 0% by mass or more and 69.9% by mass or less, more preferably 0% by mass or more and 40% by mass or less, based on all monomers constituting the elastic copolymer (x-1).

[0020] Examples of the monomer other than the alkyl (meth)acrylate include other vinyl monomers copolymerizable with the alkyl (meth)acrylate, such as styrene and acrylonitrile. These other vinyl monomers may be used alone or in any combination of two or more kinds in any ratio. The amount of the other vinyl monomer used is preferably 0% by mass or more and 69.9% by mass or less, more preferably 0% by mass or more and 20% by mass or less, based on all the monomers constituting the elastic copolymer (x-1).

[0021] Examples of the crosslinkable monomer include ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, graft crossing agents, etc. Among these, graft crossing agents are preferred in terms of the stability of the production of acrylic rubber particles. These crosslinkable monomers may be used alone or in any combination of two or more kinds in any ratio. The amount of the crosslinkable monomer used is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, based on the total amount of monomers constituting the elastic copolymer (x-1).

[0022] Examples of the grafting agent include allyl esters, methallyl esters, or crotyl esters of α,β-unsaturated carboxylic acids or unsaturated dicarboxylic acids; triallyl cyanurate; triallyl isocyanurate, etc. Among these, allyl esters of acrylic acid, methacrylic acid, maleic acid, fumaric acid, etc. are preferred, and allyl methacrylate is more preferred because of its excellent effect. In such a graft crossing agent, the conjugated unsaturated bond of the ester reacts and chemically bonds much faster than the allyl group, methallyl group, or crotyl group, and therefore most of the allyl group, methallyl group, or crotyl group, which reacts more slowly, works effectively during the polymerization of the next layer polymer, providing a graft bond between two adjacent layers.

[0023] The glass transition temperature (Tg) of the elastic copolymer (x-1) is preferably -100°C or higher and lower than 20°C, more preferably -80°C or higher and lower than 10°C, even more preferably -70°C or higher and lower than 0°C, and particularly preferably -60°C or higher and lower than 0°C. When the glass transition temperature of the elastic copolymer (x-1) is equal to or higher than the lower limit, moldability is improved. When the glass transition temperature of the elastic copolymer (x-1) is equal to or lower than the upper limit, toughness can be imparted to the resin substrate 11.

[0024] The glass transition temperature of the elastic copolymer (x-1) can be calculated by the Fox equation shown in the following formula (1) using the glass transition temperatures of the homopolymers of the components constituting the elastic copolymer (x-1). 1 / (273+Tg)=Σ(wi / (273+Tgi)) ···(1) (In formula (1), "Tg" is the glass transition temperature (°C) of the acrylic resin, "wi" is the mass fraction of monomer i constituting elastic copolymer (x-1), and "Tgi" is the glass transition temperature (°C) of the homopolymer obtained by polymerizing monomer i.)

[0025] Here, the Tg value of the homopolymer is determined from the value given in the POLYMER HANDBOOK THIRD EDITION (WILEY INTERSCIENCE) or the value given in the catalogue of the monomer manufacturer. When the monomer contains a crosslinkable monomer, the Tg is determined for the monomer excluding the crosslinkable monomer.

[0026] The rigid polymer (x-2) is preferably a polymer obtained by polymerizing an alkyl methacrylate, an alkyl acrylate, and, if necessary, a monomer other than the alkyl (meth)acrylate. For example, the rigid polymer (x-2) can be obtained by polymerizing, in the presence of the elastic copolymer (x-1), a monomer component (m3) containing 51 mass% or more of an alkyl methacrylate having an alkyl group with 1 to 4 carbon atoms and 49 mass% or less of a monomer other than the alkyl acrylate or alkyl (meth)acrylate having an alkyl group with 1 to 8 carbon atoms. As the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, the alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, and the monomer other than the alkyl (meth)acrylate, the same monomers as those used in the polymerization of the elastic copolymer (x-1) can be used.

[0027] The glass transition temperature (Tg) of the rigid polymer (x-2) is preferably 60°C or higher and lower than 150°C, more preferably 60°C or higher and lower than 140°C, even more preferably 60°C or higher and lower than 130°C, even more preferably 70°C or higher and lower than 120°C, and particularly preferably 75°C or higher and lower than 110°C. If the glass transition temperature of the rigid polymer (x-2) is equal to or higher than the lower limit, the crack resistance of the resin substrate 11 will be good. If the glass transition temperature of the rigid polymer (x-2) is equal to or lower than the upper limit, the resin substrate 11 can be molded at a low temperature, which suppresses the generation of foreign matter due to thermal degradation of the resin and improves the appearance. The glass transition temperature of the rigid polymer (x-2) can be determined by the method described above.

[0028] The weight average molecular weight (Mw) of the rigid polymer (x-2) is preferably 10,000 or more and 300,000 or less, more preferably 30,000 or more and 250,000 or less, and even more preferably 50,000 or more and 200,000 or less. When the weight average molecular weight of the rigid polymer (x-2) is at least the above lower limit value, the mechanical properties are good. When the weight average molecular weight of the rigid polymer (x-2) is at most the above upper limit value, the melt viscosity during molding is good, and the formation of gelified products due to thermal degradation can be suppressed. On the other hand, the weight average molecular weight is preferably 10,000 or more, more preferably 30,000 or more, and even more preferably 50,000 or more.

[0029] The weight average molecular weight of the rigid polymer (x-2) can be measured under the following measurement conditions as the molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC). <<GPC Measurement Conditions>> · Column: "TSK-GEL SUPER MULTIPORE HZ-H" · Eluent: Tetrahydrofuran · Flow rate: 0.35 mL / min · Injection volume: 10 μL · Column temperature: 40 °C · Detector: "UV-8020"

[0030] The intermediate polymer (x-3) is preferably a polymer obtained by polymerizing a monomer composition (m4) containing an alkyl acrylate, an alkyl methacrylate, a monomer other than alkyl (meth)acrylate, and a crosslinkable monomer. The intermediate polymer (x-3) is more preferably a polymer obtained by polymerizing a monomer composition (m4) containing an alkyl acrylate having an alkyl group containing 1 to 8 carbon atoms, an alkyl methacrylate having an alkyl group containing 1 to 4 carbon atoms, a monomer other than alkyl (meth)acrylate, and a crosslinkable monomer. For example, the intermediate polymer (x-3) may contain 10% to 90% by mass of an alkyl acrylate having an alkyl group containing 1 to 8 carbon atoms, 90% to 10% by mass of an alkyl methacrylate having an alkyl group containing 1 to 4 carbon atoms, 0% to 20% by mass of a monomer other than alkyl (meth)acrylate, and 0% to 10% by mass of a crosslinkable monomer (the total of these amounts being 100% by mass).

[0031] The monomers used in the intermediate polymer (x-3) may be the same as those used in the polymerization of the elastic copolymer (x-1). Preferably, the alkyl acrylate content (monomer composition ratio) in the intermediate polymer (x-3) is lower than that in the elastic copolymer (x-1) and higher than that in the rigid polymer (x-2).

[0032] The average particle size of the particles (X-1) such as acrylic rubber particles is preferably 0.01 μm or more and 0.5 μm or less, more preferably 0.08 μm or more and 0.3 μm or less. In particular, from the viewpoint of film formability, the average particle size is preferably 0.08 μm or more. In this specification, the term "average particle size" refers to the particle size (median size) corresponding to 50% of the cumulative total in the volume-based particle size distribution measured by dynamic light scattering using a light scattering photometer, i.e., the volume-average particle size.

[0033] The method for producing the acrylic rubber particles is not particularly limited. For example, emulsion polymerization can be used to produce the elastic copolymer (x-1) and the rigid polymer (x-2). Alternatively, they can be produced by emulsion suspension polymerization, in which the emulsion polymerization is converted to a suspension polymerization system during polymerization of the polymer constituting the outermost layer. The polymerization temperature is appropriately selected depending on the type and amount of the polymerization initiator used, but is preferably 40°C or higher and 120°C or lower, and more preferably 60°C or higher and 95°C or lower. Known polymerization initiators can be used as the polymerization initiator. The polymerization initiator can be added to either the aqueous phase or the monomer phase, or both. Examples of emulsifiers that can be used in emulsion polymerization include anionic surfactants, cationic surfactants, and nonionic surfactants, with anionic surfactants being preferred.

[0034] The polymer latex obtained by emulsion polymerization can be filtered, for example, through a filter with a mesh size of 100 μm or less, and then separated and recovered by a method such as acid coagulation, salt coagulation, freeze coagulation, or spray drying. In the acid coagulation method, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, etc., and organic acids such as acetic acid, etc. can be used. In the salt coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate, calcium chloride, etc., and organic salts such as calcium acetate, magnesium acetate, etc., can be used. These may be used alone or in any combination of two or more kinds in any ratio. The separated and recovered polymer is further subjected to washing, dehydration, drying, etc. to obtain acrylic rubber particles.

[0035] (Reactive group-containing resin (X-2)) The reactive group-containing resin (X-2) contains a monomer unit having a reactive group. The reactive group-containing monomer unit is preferably a monomer unit having at least one reactive group selected from the group consisting of a monomer unit having a reactive group with an amino group and a monomer unit having a reactive group with a methylol group (hereinafter also referred to as a monomer unit having a reactive group with an amino group or a methylol group), and more preferably a (meth)acrylic monomer unit having at least one reactive group selected from the group consisting of a (meth)acrylic monomer unit having a reactive group with an amino group and a (meth)acrylic monomer unit having a reactive group with a methylol group. In the resin substrate 11, the reactive group-containing resin (X-2) is preferably an acrylic resin as an acetone-soluble component described below, and more preferably an acrylic resin having a weight-average molecular weight of 300,000 or less. The reactive group-containing resin (X-2) may contain, in addition to the monomer unit having a reactive group, an aromatic vinyl monomer unit such as styrene, and other monomer units. Specifically, the reactive group-containing resin (X-2) may contain 3% by mass or more and 100% by mass or less of monomer units having a reactive group, 0% by mass or more and 3% by mass or less of aromatic vinyl monomer units, and 0% by mass or more and 97% by mass or less of other monomer units, for a total of 100% by mass.

[0036] Examples of groups reactive with amino groups or methylol groups include hydroxy groups, carboxy groups, amino groups, amide groups, acid anhydride groups, imide groups, and epoxy groups. The reactive group-containing resin (X-2) may have one or more of these reactive groups. Furthermore, two or more reactive group-containing resins (X-2) containing different types and / or different ratios of one or more of these reactive groups may be used in combination. The reaction temperature of the reactive group varies depending on the presence or absence of a catalyst and the pH value in the reaction, but is preferably, for example, 50°C or higher and 200°C or lower, more preferably 110°C or higher and 170°C or lower.

[0037] Examples of monomers having a reactive group include monomers having a hydroxy group such as hydroxyalkyl (meth)acrylate; monomers having a carboxy group such as (meth)acrylic acid, (meth)acryloyloxyalkyl carboxylic acid, and (meth)acryloyloxyaromatic carboxylic acid; monomers having an amino group such as aminoalkyl (meth)acrylate; monomers having an amide group such as alkylamidoalkyl (meth)acrylate; acid anhydride monomers such as maleic anhydride; maleimide monomers such as maleimide and alkylmaleimide; and epoxy group-containing monomers such as glycidyl (meth)acrylate. Among these, monomers having a hydroxy group, carboxy group, acid anhydride group, or epoxy group as a reactive group are preferred. Among these, monomers having a hydroxy group, carboxy group, or epoxy group as a reactive group are more preferred because they do not have a hydrolyzable site such as an acid anhydride and can efficiently produce polymers in aqueous polymerization such as emulsion polymerization and suspension polymerization. Furthermore, monomers having a hydroxy group as a reactive group are even more preferred because they prevent crosslinking during melt molding. Furthermore, from the viewpoint of particularly reducing crosslinking during melt molding, a monomer having a secondary hydroxy group as a reactive group is particularly preferred. These monomers having a reactive group may be used alone or in any combination of two or more kinds in any ratio.

[0038] Examples of monomers having a hydroxy group as a reactive group include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-1-methylethyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, and 2-hydroxybutyl acrylate. Among these, 2-hydroxypropyl methacrylate and 2-hydroxypropyl acrylate, which have a secondary hydroxy group, are preferred in order to prevent poor film appearance due to a crosslinking reaction during melt molding. Furthermore, 2-hydroxypropyl methacrylate is more preferred in terms of its good copolymerizability with, for example, methyl methacrylate. These hydroxyl group-containing monomers may be used alone or in any combination of two or more kinds in any ratio.

[0039] Examples of other monomers include acrylic monomers, vinyl cyanide monomers such as acrylonitrile, N-phenylmaleimide, N-cyclohexylmaleimide, etc. Among these, from the viewpoints of compatibility with the particles (X-1) and the thermoplastic resin (X-3) and adhesion to the hard coat layer 12, acrylic monomers are preferred, and methyl methacrylate and n-butyl acrylate are more preferred. These other monomers may be used alone or in any combination of two or more kinds in any ratio.

[0040] The content of the monomer unit having a reactive group is preferably 3% by mass or more and 100% by mass or less, more preferably 3% by mass or more and 80% by mass or less, and even more preferably 10% by mass or more and 30% by mass or less, based on the total mass of all structural units constituting the reactive group-containing resin (X-2). The content of the aromatic vinyl monomer unit is preferably 0% by mass or more and 3% by mass or less, more preferably 0% by mass or more and 1% by mass or less, and even more preferably 0% by mass or more and 0.1% by mass or less, relative to the total mass of all structural units constituting the reactive group-containing resin (X-2), and may be 0% by mass. The content of the other monomers is preferably 0% by mass or more and 96% by mass or less, more preferably 20% by mass or more and 96% by mass or less, and may be 0% by mass, relative to the total mass of all structural units constituting the reactive group-containing resin (X-2). In particular, when methyl methacrylate and n-butyl acrylate are used in combination as the other monomers, when the total of methyl methacrylate and n-butyl acrylate is taken as 100% by mass, it is preferable that methyl methacrylate is 70% by mass or more and 100% by mass or less, and n-butyl acrylate is 0% by mass or more and 30% by mass or less, and more preferably 80% by mass or more and 100% by mass or less, and n-butyl acrylate is 0% by mass or more and 20% by mass or less.

[0041] The reactive group-containing resin (X-2) can be produced by various polymerization methods such as suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization, etc. However, when a monomer having an acid anhydride or an imide structure is used as a monomer having a reactive group, hydrolysis occurs during polymerization, and therefore the resin cannot be produced by aqueous polymerization such as suspension polymerization or emulsion polymerization. During the polymerization, a chain transfer agent, other polymerization aids, etc. may be used. Mercaptans are preferred as the chain transfer agent.

[0042] The weight-average molecular weight (Mw) of the reactive group-containing resin (X-2) is preferably 300,000 or less, more preferably 10,000 to 300,000, even more preferably 30,000 to 250,000, and particularly preferably 50,000 to 200,000, from the viewpoint of providing adequate elongation during molding of the resin substrate 11 and achieving good film-forming properties. When the weight-average molecular weight of the reactive group-containing resin (X-2) is equal to or greater than the above-mentioned lower limit, the mechanical properties of the laminate 10 are good. When the weight-average molecular weight of the reactive group-containing resin (X-2) is equal to or less than the above-mentioned upper limit, the melt viscosity during film formation is good, and the formation of gelled matter due to thermal degradation can be suppressed. The weight average molecular weight of the reactive group-containing resin (X-2) can be determined by the method described above.

[0043] The glass transition temperature (Tg) of the reactive group-containing resin (X-2) is preferably 60°C or higher and 95°C or lower, more preferably 65°C or higher and 90°C or lower, and even more preferably 70°C or higher and 85°C or lower. When the glass transition temperature of the reactive group-containing resin (X-2) is equal to or higher than the above lower limit, the heat resistance, water resistance, and blocking resistance of the laminate 10 are improved. When the glass transition temperature of the reactive group-containing resin (X-2) is equal to or lower than the above upper limit, the resin substrate 11 can be molded at a low temperature, which suppresses the generation of foreign matter due to thermal degradation of the resin and improves the appearance. The glass transition temperature of the reactive group-containing resin (X-2) can be determined by the method described above.

[0044] (Thermoplastic resin (X-3)) The thermoplastic resin (X-3) is preferably an acrylic resin, more preferably a polymer obtained by polymerizing a monomer component (m5) containing alkyl methacrylate. In the resin substrate 11, the thermoplastic resin (X-3) is preferably an acrylic resin as an acetone-soluble component described below, more preferably an acrylic resin having a weight-average molecular weight of 300,000 or less. The thermoplastic resin (X-3) is particularly preferably a polymer obtained by polymerizing a monomer component (m5) containing alkyl methacrylate, alkyl acrylate, and, if necessary, a monomer other than alkyl (meth)acrylate. For example, the thermoplastic resin (X-3) may be a polymer obtained by polymerizing 50% by mass to 99.9% by mass of alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, 0.1% by mass to 50% by mass of alkyl acrylate, and 0% by mass to 49.9% by mass of a monomer other than alkyl (meth)acrylate, for a total of 100% by mass.

[0045] Examples of alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. Among these, methyl methacrylate is preferred. Examples of alkyl acrylates include methyl acrylate, ethyl acrylate, and butyl acrylate. Examples of monomers other than alkyl (meth)acrylates include aromatic vinyl monomers such as styrene; cyanide vinyl monomers such as acrylonitrile; unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; N-phenylmaleimide; and N-cyclohexylmaleimide. Each of these monomers may be used alone or in any combination of two or more kinds in any ratio.

[0046] The method for producing the thermoplastic resin (X-3) is not particularly limited, and various polymerization methods such as suspension polymerization, emulsion polymerization, and bulk polymerization can be used. During polymerization, a chain transfer agent, other polymerization aids, etc. may be used. The chain transfer agent is not particularly limited, but mercaptans are preferred.

[0047] The weight average molecular weight (Mw) of the thermoplastic resin (X-3) is preferably 10,000 or more, more preferably 10,000 to 300,000, from the viewpoint of providing adequate elongation during molding of the resin substrate 11 and favorable film formability. The weight average molecular weight of the thermoplastic resin (X-3) can be determined by the method described above.

[0048] The glass transition temperature (Tg) of the thermoplastic resin (X-3) is preferably 60°C or higher and 95°C or lower, more preferably 65°C or higher and 90°C or lower, and even more preferably 70°C or higher and 85°C or lower. When the glass transition temperature of the thermoplastic resin (X-3) is equal to or higher than the lower limit, the crack resistance of the resin substrate 11 is good. When the glass transition temperature of the thermoplastic resin (X-2) is equal to or lower than the upper limit, the resin substrate 11 can be molded at a low temperature, which suppresses the generation of foreign matter due to thermal degradation of the resin and improves the appearance. The glass transition temperature of the thermoplastic resin (X-3) can be determined by the method described above.

[0049] (Additive (X-4)) Examples of the additive (X-4) include processing aids, ultraviolet absorbers, light stabilizers, antioxidants, lubricants, plasticizers, impact resistance improvers, foaming agents, fillers, and colorants. These additives (X-4) may be used alone or in any combination of two or more kinds in any ratio.

[0050] For example, in the production of the resin substrate 11, the resin substrate 11 preferably contains a processing aid as the additive (X-4) in order to cause appropriate elongation when the resin is melted and improve film formability. The processing aid may be any resin other than particles (X-1), reactive group-containing resin (X-2) having reactive groups other than hydroxyl groups, and thermoplastic resin (X-3), preferably a thermoplastic resin, more preferably a polymer obtained by polymerizing a monomer mainly composed of alkyl methacrylate, and even more preferably a polymer obtained by polymerizing a total of 100% by mass of 50% to 100% by mass of methyl methacrylate and 0% to 50% by mass of a monomer other than methyl methacrylate. In the resin substrate 11, the processing aid is preferably an acrylic resin as an acetone-soluble component, as described below, more preferably an acrylic resin having a weight-average molecular weight of more than 300,000. The processing aid may be a polymer that is basically the same as the thermoplastic resin (X-3) described above, but differs from the thermoplastic resin (X-3) only in the weight average molecular weight, as described below.

[0051] The weight-average molecular weight of the processing aid is preferably greater than 300,000, more preferably greater than 300,000 and not greater than 5,000,000, even more preferably 500,000 to 4,500,000, and particularly preferably 1,000,000 to 4,000,000. If the weight-average molecular weight of the processing aid is equal to or greater than the lower limit, appropriate elongation occurs when the resin is melted during production of the resin substrate 11, resulting in good film-forming properties. If the weight-average molecular weight of the processing aid is equal to or less than the upper limit, the formation of gelled matter due to thermal degradation can be suppressed. The weight average molecular weight of the processing aid can be determined by the method described above.

[0052] Furthermore, for example, in order to impart weather resistance to protect the resin base material 11, the resin base material 11 may contain an ultraviolet absorber as an additive (X-4). The molecular weight of the ultraviolet absorber is preferably at least 300, more preferably at least 400. When the molecular weight is at least 300, bleeding out of the ultraviolet absorber in the multilayer film is reduced. As the ultraviolet absorber, a benzotriazole-based ultraviolet absorber having a molecular weight of 400 or more and a triazine-based ultraviolet absorber having a molecular weight of 400 or more are preferred. In terms of maintaining ultraviolet shielding ability for a long period of time, a triazine-based ultraviolet absorber having a molecular weight of 400 or more is more preferred.

[0053] In order to further improve weather resistance, a radical scavenger such as a hindered amine light stabilizer may be used in combination with the ultraviolet absorber. Furthermore, as the radical scavenger such as a hindered amine light stabilizer, a high molecular weight hindered amine stabilizer can also be used from the viewpoint of bleed-out resistance. The molecular weight of the hindered amine stabilizer is preferably 1,000 or more, more preferably 2,000 or more.

[0054] (Content) When the total content of particles (X-1) and reactive group-containing resin (X-2) is taken as 100% by mass, the content of particles (X-1) is preferably 16% by mass to 99.9% by mass and the content of reactive group-containing resin (X-2) is preferably 0.1% by mass to 84% by mass, more preferably 17% by mass to 99% by mass and the content of reactive group-containing resin (X-2) is 1% by mass to 83% by mass, and even more preferably 18% by mass to 98% by mass and the content of particles (X-1) is 2% by mass to 82% by mass.

[0055] The content of the thermoplastic resin (X-3) is preferably 0 parts by mass or more and 50 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, even more preferably 1 part by mass or more and 5 parts by mass or less, and particularly preferably 1.5 parts by mass or more and 4 parts by mass or less, relative to 100 parts by mass of the total content of the particles (X-1) and the reactive group-containing resin (X-2).

[0056] With respect to 100 parts by mass of the total content of the particles (X-1) and the reactive group-containing resin (X-2), the content of the additive (X-4) is preferably from 0 to 50 parts by mass, more preferably from 0.1 to 20 parts by mass, even more preferably from 0.1 to 10 parts by mass, particularly preferably from 1 to 5 parts by mass, and most preferably from 2 to 4 parts by mass. From the viewpoint of ensuring melt tension during film formation, the content of the processing aid is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.3 parts by mass or more and 15 parts by mass or less, and even more preferably 0.5 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total content of the particles (X-1) and the reactive group-containing resin (X-2). From the viewpoint of weather resistance, the content of the ultraviolet absorber is preferably 0 to 20 parts by mass relative to 100 parts by mass of the total content of the particles (X-1) and the reactive group-containing resin (X-2). From the viewpoint of bleed-out resistance, the content of the light stabilizer is preferably 0 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the total content of the particles (X-1) and the reactive group-containing resin (X-2).

[0057] (Acetone soluble and acetone insoluble) The resin base material 11 is preferably composed of an acetone soluble component and an acetone insoluble component. The acetone-insoluble matter in the resin substrate 11 includes the above-mentioned particles (X-1), and acrylic rubber particles are particularly preferred. The acetone-soluble components in the resin substrate 11 include the reactive group-containing resin (X-2), the thermoplastic resin (X-3), and the processing aids described above.

[0058] The content of acetone-insoluble matter (gel content) in the total amount of the resin substrate 11 is preferably 15% or more, more preferably 15% to 75% or less, even more preferably 16% to 70% or less, particularly preferably 17% to 65% or less, and most preferably 18% to 60% or less. If the gel content is equal to or greater than the above-mentioned lower limit, adhesion to the hard coat layer 12 is further improved. In addition, the toughness of the resin substrate 11 is improved, and the handleability of the laminate 10 is improved. If the gel content is equal to or less than the above-mentioned upper limit, the generation of foreign matter due to thermal degradation of the resin is appropriately suppressed, and the appearance of the resin substrate 11 is improved. There are several possible methods for adjusting the gel fraction to fall within the above range, and for example, it can be adjusted by adjusting the content of particles (X-1) in the resin substrate 11.

[0059] The gel content is determined as follows. 50 mL of acetone was added to 0.5 g of resin substrate and stirred at 65°C for 4 hours. The mixture was then centrifuged at 4°C and 14,000 rpm for 30 minutes. After removing the supernatant, 50 mL of acetone was added again and centrifuged again under the same conditions. After removing the supernatant, the precipitated gel was vacuum dried for 8 hours, the mass was measured, and the gel content was calculated using the following formula (2). Gel content (%) = (mass of gel part (g) / 0.5) × 100 (2)

[0060] The acetone-soluble components in the resin substrate 11 include an acrylic resin having a weight-average molecular weight of 300,000 or less and an acrylic resin having a weight-average molecular weight of more than 300,000. By including an acrylic resin having a weight-average molecular weight of more than 300,000, the melt tension becomes good, and film-forming properties become better. Among the acetone-soluble components in the resin substrate 11, examples of acrylic resins having a weight-average molecular weight of 300,000 or less include the reactive group-containing resin (X-2) and thermoplastic resin (X-3) described above, while examples of acrylic resins having a weight-average molecular weight of more than 300,000 include the processing aid described above. The weight average molecular weight of the acetone soluble matter can be determined by the method described above.

[0061] The glass transition temperature (Tg) of the acrylic resin having a weight-average molecular weight of 300,000 or less is 95° C. or less, preferably 60° C. or more and 95° C. or less, more preferably 65° C. or more and 90° C. or less, and even more preferably 70° C. or more and 85° C. or less. When the glass transition temperature of the acrylic resin having a weight-average molecular weight of 300,000 or less is the above upper limit or less, the adhesion to the hard coat layer 12 is further improved. There are several possible methods for adjusting the glass transition temperature to fall within the above range. For example, a method in which a monomer having a low glass transition temperature is copolymerized as a monomer constituting an acrylic resin having a weight-average molecular weight of 300,000 or less is preferred from the viewpoint of suppressing bleed-out. The glass transition temperature of an acrylic resin having a weight-average molecular weight of 300,000 or less can be determined by the method described above.

[0062] (Method of manufacturing resin substrate) The resin substrate 11 can be obtained, for example, by forming the acrylic resin composition (X) containing the above-described particles (X-1) into a sheet. The acrylic resin composition (X) preferably further contains the reactive group-containing resin (X-2) described above in addition to the particles (X-1). The acrylic resin composition (X) may further contain at least one of the thermoplastic resin (X-3) and the additive (X-4) described above, if necessary, and preferably contains a processing aid in particular. The acrylic resin composition (X) may consist of only the particles (X-1). The content of each component in the acrylic resin composition (X) is the same as the content of each component in the resin substrate 11.

[0063] The acrylic resin composition (X) can be molded by any known method, such as compression molding, transfer molding, injection molding, blow molding, vacuum molding, extrusion molding, lamination molding, and calendar molding.

[0064] <Hard coat layer> The hard coat layer 12 in the illustrated example is provided on one surface of the resin substrate 11 in contact with the resin substrate 11 . The hard coat layer 12 is made of a cured product of an active energy ray-curable coating composition containing an unsaturated double bond-containing compound. The active energy ray-curable coating composition will be described later. The thickness of the hard coat layer 12 is not particularly limited, but is preferably, for example, 5 μm or more and 100 μm or less, and more preferably 10 μm or more and 60 μm or less.

[0065] The hard coat layer 12 contains particles. When the hard coat layer 12 is cut in the thickness direction, the cross section is divided into two equal parts in the direction perpendicular to the thickness direction of the hard coat layer 12, that is, the region (α) 12α on the resin substrate 11 side and the remaining region, i.e., the region (β) 12β on the outermost surface side, and the number of particles contained in the region (α) 12α (hereinafter referred to as the "particle number (α n) is the number of particles contained in the region (β) 12β (hereinafter referred to as the "number of particles (β n ) is 5 times or more, preferably 5 times or more and 100 times or less, more preferably 7 times or more and 70 times or less, and even more preferably 8 times or more and 50 times or less. In other words, the number of particles (α n ) / number of particles(β n The ratio (R) of the number of particles obtained by (a) is 5 or more, preferably 5 or more and 100 or less, more preferably 7 or more and 70 or less, and even more preferably 8 or more and 50 or less. When the particle number ratio (R) is equal to or greater than the lower limit, the resin substrate 11 and the hard coat layer 12 partially form a mixed phase, improving the adhesion between the resin substrate 11 and the hard coat layer 12. In addition, the hardness of the hard coat layer 12 increases. When the particle number ratio (R) is equal to or less than the upper limit, a decrease in crosslink density due to excess particles can be suppressed, and good durability can be maintained. Here, the "outermost surface" refers to the surface opposite to the surface on the resin substrate 11 side, that is, the exposed surface, of the pair of opposing surfaces of the hard coat layer 12.

[0066] When the resin substrate 11 contains the above-mentioned particles (X-1), the particles (not shown) contained in the region (α) 12α and the region (β) 12β are particles (X-1) derived from the resin substrate 11. That is, the hard coat layer 12 contains particles (X-1) derived from the resin substrate 11. The hard coat layer 12 is obtained by applying an active energy ray-curable coating composition to the surface of the resin substrate 11 to form a coating film, drying the coating film as needed, and then curing the coating film. The fact that the particles contained in the region (α) 12α and the region (β) 12β are particles (X-1) derived from the resin substrate 11 means that the surface of the resin substrate 11 that comes into contact with the active energy ray-curable coating composition is appropriately dissolved by the active energy ray-curable coating composition, and the particles (X-1) contained in the resin substrate 11 migrate to the coating film. By curing the coating film in a state where the particles (X-1) contained in the resin substrate 11 have migrated to the coating film, a hard coat layer 12 containing particles (X-1) derived from the resin substrate 11 is obtained. If the particle number ratio (R) is equal to or greater than the lower limit, it means that the particles (X-1) derived from the resin substrate 11 that have migrated to the coating film are sufficiently unevenly distributed closer to the resin substrate 11 side (region (α) 12α) than to the outermost surface side (region (β) 12β), and the coating film is cured in a state where the resin substrate 11 and the coating film are sufficiently compatible with each other to form the hard coat layer 12. Therefore, the adhesion between the resin substrate 11 and the hard coat layer 12 is further improved. On the other hand, if the particles (X-1) derived from the resin substrate 11 are excessively distributed in the region (α) 12α rather than in the region (β) 12β, the hardness tends to decrease due to a decrease in the crosslink density of the surface and the softness of the particles. If the ratio (R) of the number of particles is equal to or greater than the above lower limit, the crosslink density due to the excess particles can be suppressed, and good durability can be maintained.

[0067] The particle number ratio (R) can be controlled by adjusting the formulation of the active energy ray-curable coating composition and the drying temperature when drying the coating film formed on the resin substrate 11. For example, if the active energy ray-curable coating composition contains the component (A) described below, the resin substrate 11 dissolves when it comes into contact with the active energy ray-curable coating composition, and the particles (X-1) contained in the resin substrate 11 tend to migrate more easily to the coating film. Furthermore, the higher the drying temperature for the coating film, the more easily the particles (X-1) contained in the resin substrate 11 tend to migrate to the coating film. In addition, when the particles contained in the hard coat layer 12 include particles (X-1) derived from the resin substrate 11, the average particle diameter of the particles contained in the hard coat layer 12 is the same as the average particle diameter of the particles (X-1) contained in the resin substrate 11.

[0068] In the present invention, the ratio (R) of the number of particles is a value determined as follows. A cross section (cross section in the thickness direction) of the hard coat layer 12 is observed at a magnification of 2000 times or more using a scanning electron microscope, and the observed image is binarized using image processing software such as ImageJ. The cross section is divided into two equal parts perpendicular to the thickness direction of the hard coat layer 12, and divided into two regions: a region (α) 12α on the resin substrate 11 side and a region (β) 12β on the outermost surface side. From the binarized image, the number of particles (particle diameter 0.05 μm or more) observed in the region (α) 12α is counted, and a 1 μm section of the region (α) 12α is obtained. 2 Similarly, the number of particles (particle diameter 0.05 μm or more) observed in the region (β) 12β is counted and converted into the number of particles per 1 μm of the region (β) 12β. 2 The particle number ratio (R) is calculated using the following formula (3). Ratio of particle number (R) = 1 μm of area (α) 2 Number of particles per 1 μm of area (β) 2 Number of particles per particle (3)

[0069] (Active energy ray curable coating composition) An example of an active energy ray-curable coating composition (hereinafter also simply referred to as "coating composition") for forming the hard coat layer 12 will be described. The coating composition contains an unsaturated double bond-containing compound. Examples of the unsaturated double bond-containing compound include the following components (A) and (B). The coating composition preferably contains components (A) and (B). In addition to the unsaturated double bond-containing compound, the coating composition preferably further contains the following components (C) and (D). In addition to components (A), (B), (C), and (D), the coating composition may further contain components other than components (A), (B), (C), and (D) (hereinafter also referred to as "optional components") as necessary, provided that the effects of the present invention are not impaired.

[0070] <<Component (A)>> Component (A) has one or two (meth)acryloyl groups and a dispersion term (δD) of the Hansen solubility parameter of 15.5 MPa. 1 / 2 Over 16.9MPa 1 / 2 or less, and the polarization term (δP) is 4.7 MPa 1 / 2 Over 13.2MPa 1 / 2 The hydrogen bond term (δH) is 4.9 MPa or less. 1 / 2 Over 13.4MPa 1 / 2 The compound (A) is an unsaturated double bond-containing compound (hereinafter also referred to as "compound (A)") shown below. That is, component (A) is a monofunctional or difunctional unsaturated monomer ((meth)acrylate monomer) having a specific Hansen solubility parameter. Since the coating composition contains component (A), when the coating composition is applied to a resin substrate 11 to form a coating film, the surface of the resin substrate 11 that comes into contact with the coating composition is appropriately dissolved by component (A), and the substrate components migrate to the coating film, improving compatibility between the resin substrate 11 and the coating film. The coating film is then cured by irradiation with active energy rays, forming a hard coat layer 12 that has excellent adhesion to the resin substrate 11.

[0071] The dispersion term (δD) of the Hansen solubility parameter of compound (A) is 15.5 MPa. 1 / 2 Over 16.9MPa 1 / 2 or less, 15.5 MPa 1 / 2 Over 16.8MPa 1 / 2 Preferably less than 16.0 MPa 1 / 2 Over 16.7MPa 1 / 2 The following is more preferred: The polarization term (δP) of the Hansen solubility parameter of compound (A) is 4.7 MPa. 1 / 2 Over 13.2MPa 1 / 2 is less than 5.1 MPa 1 / 2 Over 13.2MPa 1 / 2 Preferably less than 6.0 MPa 1 / 2 Over 8.0MPa 1 / 2 The following is more preferred: The hydrogen bond term (δH) of the Hansen solubility parameter of compound (A) is 4.9 MPa. 1 / 2 Over 13.4MPa 1 / 2less than 5.5MPa 1 / 2 Over 13.4MPa 1 / 2 Preferably less than 6.3 MPa 1 / 2 Over 12.0MPa 1 / 2 The following is more preferred:

[0072] The Hansen solubility parameters are the solubility parameters introduced by Hildebrand, divided into three components: dispersion term (δD), polarization term (δP), and hydrogen bonding term (δH), and expressed in three-dimensional space. The dispersion term (δD) indicates the effect of van der Waals dispersion forces. The polarization term (also called the polar term) (δP) indicates the effect of dipole-dipole forces. The hydrogen bonding term (δH) indicates the effect of hydrogen bonding forces.

[0073] The Hansen solubility parameter values ​​(HSP values) of various compounds are described, for example, in "Hansen Solubility Parameters: A Users Handbook" by Charles M. Hansen (CRC Press, 2007). Furthermore, by using computer software (Hansen Solubility Parameters in Practice (h)), the HSP value can be easily estimated from the chemical structure of compounds for which literature values ​​are unknown. In the present invention, for compounds registered in the database of computer software (Hansen Solubility Parameters in Practice (HSPiP) Ver. 5.3.02), the registered HSP values ​​are used. For compounds not in the database, the HSP values ​​estimated by HSPiP Ver. 5.3.02 are used.

[0074] The compound (A) is not particularly limited as long as it is a monomer having the dispersion term (δD), polarization term (δP), and hydrogen bond term (δH) of the Hansen solubility parameter within the above ranges and having one or two (meth)acryloyl groups in the molecule. For example, straight-chain or branched alkyl group-containing (meth)acrylates such as ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, and i-butyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyethyl ... Examples of the hydroxyl group-containing (meth)acrylate include hydroxyhexyl (meth)acrylate, 2-(2-hydroxyethoxy)ethyl acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; oxyethylene group-containing (meth)acrylates such as 2-methoxyethyl (meth)acrylate and ethoxydiethylene glycol (meth)acrylate; heterocycle-containing (meth)acrylates such as glycidyl (meth)acrylate and tetrahydrofurfuryl (meth)acrylate; and bifunctional (meth)acrylates such as ethylene glycol di(meth)acrylate and diethylene glycol di(meth)acrylate. These compounds (A) may be used alone or in any combination of two or more kinds in any ratio. When two or more compounds (A) are used in combination, the dispersion term (δD), polarization term (δP), and hydrogen bond term (δH) of the Hansen solubility parameters of all the compounds (A) are within the above ranges.

[0075] The content of component (A) is preferably 0.1% by mass or more and 10% by mass or less, more preferably 2% by mass or more and 8% by mass or less, and even more preferably 3% by mass or more and 7% by mass or less, based on the total mass of the coating composition. If the content of component (A) is equal to or greater than the above-mentioned lower limit, when the coating composition is applied to the resin substrate 11, the resin substrate 11 is sufficiently dissolved and the substrate components are sufficiently transferred to the coating film, thereby further improving the adhesion of the hard coat layer 12 to the resin substrate 11. If the content of component (A) is equal to or less than the above-mentioned upper limit, excessive dissolution of the resin substrate 11 can be prevented and a decrease in the crosslink density of the hard coat layer 12 can be prevented, thereby maintaining good hardness.

[0076] <<(B) Component>> Component (B) is a bifunctional or higher functional unsaturated double bond-containing compound (hereinafter also referred to as "compound (B)") other than component (A). That is, component (B) is a bifunctional or higher functional unsaturated monomer. When the coating composition contains component (B), the hardness of the hard coat layer 12 is improved.

[0077] Examples of the compound (B) include polyfunctional (meth)acrylates having two or more (meth)acryloyl groups. Examples of bifunctional (meth)acrylates having two (meth)acryloyl groups include 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7- Heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,11-undecanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, 1,14-Tetradecanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, dioxane glycol di(meth)acrylate, tricyclodecane dimethano Examples of suitable diol di(meth)acrylates include bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, bisphenoxyfluoreneethanol di(meth)acrylate, bis(2-acryloyloxyethyl)-2-hydroxyethyl isocyanurate, isocyanuric acid EO-modified di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, polycarbonate diol di(meth)acrylate, polyester diol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, and polyurethane di(meth)acrylate.

[0078] Examples of trifunctional (meth)acrylates having three (meth)acryloyl groups include isocyanuric acid EO-modified tri(meth)acrylate, polyester tri(meth)acrylate, glycerin tri(meth)acrylate, glycerin EO-modified tri(meth)acrylate, glycerin PO-modified tri(meth)acrylate, glycerin caprolactone-modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, EO-modified pentaerythritol tri(meth)acrylate, PO-modified pentaerythritol tri(meth)acrylate, and caprolactone-modified pentaerythritol tri(meth)acrylate.

[0079] Examples of tetrafunctional (meth)acrylates having four (meth)acryloyl groups include dipentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate, PO-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate.

[0080] Examples of pentafunctional (meth)acrylates having five (meth)acryloyl groups include dipentaerythritol penta(meth)acrylate, EO-modified dipentaerythritol penta(meth)acrylate, PO-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, and ditrimethylolpropane penta(meth)acrylate.

[0081] Examples of hexafunctional (meth)acrylates having six (meth)acryloyl groups include dipentaerythritol hexa(meth)acrylate, EO-modified dipentaerythritol hexa(meth)acrylate, PO-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and ditrimethylolpropane hexa(meth)acrylate.

[0082] Among these, from the viewpoint of increasing the crosslink density of the hard coat layer 12 and further improving the hardness, (meth)acrylates having a heterocyclic skeleton and (meth)acrylates having five or more functionalities are preferred, and among these, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, dioxane glycol di(meth)acrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly more preferred. These compounds (B) may be used alone or in any combination of two or more kinds in any ratio. In addition, "EO" means ethylene oxide and "PO" means propylene oxide.

[0083] The content of component (B) is preferably 60% by mass or more and 95% by mass or less, more preferably 65% ​​by mass or more and 90% by mass or less, and even more preferably 68% by mass or more and 83% by mass or less, based on the total mass of the coating composition. If the content of component (B) is equal to or greater than the above-mentioned lower limit, the hardness of the hard coat layer 12 is further increased. If the content of component (B) is equal to or less than the above-mentioned upper limit, warping of the coating film due to cure shrinkage and the resulting poor adhesion can be suppressed.

[0084] <<(C) component>> Component (C) is an acrylic resin. When the coating composition contains the component (C), cure shrinkage during curing of the coating composition can be suppressed, and the adhesion of the hard coat layer 12 to the resin substrate 11 can be improved.

[0085] An acrylic resin is a polymer containing at least one structural unit derived from a (meth)acrylic monomer, and may contain a structural unit derived from a monomer other than the (meth)acrylic monomer, as necessary. That is, examples of the acrylic resin include a homopolymer or copolymer of a (meth)acrylic monomer, and a copolymer of a (meth)acrylic monomer and another monomer. These acrylic resins may be used alone or in any combination of two or more kinds in any ratio.

[0086] Examples of the (meth)acrylic monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, i-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. alkyl (meth)acrylates having a straight or branched hydrocarbon skeleton, such as acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, and 4-t-butylcyclohexyl (meth)acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, and dicyclopentani alkyl (meth)acrylates having an alicyclic skeleton such as alkyl (meth)acrylate; (meth)acrylates having a glycidyl group such as glycidyl (meth)acrylate and hydroxybutyl (meth)acrylate glycidyl ether; (meth)acrylates having an aromatic ring such as phenoxy (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, nonylphenol EO adduct (meth)acrylate, and o-biphenyloxyethyl (meth)acrylate; (meth)acrylate salts such as ammonium (meth)acrylate, sodium (meth)acrylate, and potassium (meth)acrylate; (meth)acrylates having a cyclic ether such as tetrahydrofurfuryl (meth)acrylate; (meth)acrylates having an amino group such as N-dimethylaminoethyl (meth)acrylate and N-diethylaminoethyl (meth)acrylate;(Meth)acrylamide, (meth)acrylamide diacetone acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, (meth)acryloylmorpholine and other (meth)acrylamide derivatives; 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxyethyl acid phosphate monoethanolamine salt, diphenyl ((meth)acryloyloxyethyl) phosphate, (meth)acryloyloxypropyl acid phosphate, 3-chloro-2-acid phosphooxypropyl (meth)acrylate, acid phosphooxypolyoxyethylene glycol mono(meth)acrylate, acid phosphooxypolyoxypropylene glycol (meth)acrylate and other monomers having a phosphate group; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 1,2-dihydroxyethyl (meth)acrylate, 1,2-dihydroxypropyl (meth)acrylate, 1,2-dihydroxybutyl (meth)acrylate, 1,2-dihydroxy-5-ethylhexyl (meth)acrylate, 1,1-dihydroxyethyl (meth)acrylate, 1,1-dihydroxypropyl (meth)acrylate ) acrylate, 1,1-dihydroxybutyl (meth)acrylate, 1,2,3-trihydroxypropyl (meth)acrylate, 1,2,3-trihydroxybutyl (meth)acrylate, 1,1,2-trihydroxypropyl (meth)acrylate, 1,1,2-trihydroxybutyl (meth)acrylate, and other (meth)acrylates having a hydroxy group; hydroxy(meth)acrylates having an aromatic ring, such as 2-hydroxy-3-phenoxypropyl (meth)acrylate;Hydroxypolyethyleneoxide mono(meth)acrylate, hydroxypolypropyleneoxide mono(meth)acrylate, hydroxy(polyethyleneoxide-polypropyleneoxide) mono(meth)acrylate, hydroxy(polyethyleneoxide-propyleneoxide) mono(meth)acrylate, hydroxy(polyethyleneoxide-polytetramethyleneoxide) mono(meth)acrylate, hydroxy(polyethyleneoxide-tetramethyleneoxide) mono(meth)acrylate, hydroxy(polypropyleneoxide-polytetramethyleneoxide) mono(meth)acrylate, hydroxy(polypropyleneoxide-polytetramethylene Examples of the hydroxyl group-containing polyalkylene oxide include 1,2-dihydroxypropylene oxide (meth)acrylate, 1,2-dihydroxypolyethyloxide (meth)acrylate, 1,2-dihydroxypolypropylene oxide (meth)acrylate, and polyhydroxyalkyl (meth)acrylates; hydroxypolyalkylene oxide (meth)acrylates such as 1,2,3-trihydroxypropylene glycol (meth)acrylate and 1,1,2-trihydroxypropylene glycol (meth)acrylate; and (meth)acrylates having a carboxy group such as acrylic acid, methacrylic acid, mono(2-(meth)acryloyloxyethyl)succinate, and ω-carboxy-polycaprolactone mono(meth)acrylate. Among these, from the viewpoint of further improving adhesion to the resin substrate 11, it is preferable to contain at least one of alkyl (meth)acrylates having a linear or branched hydrocarbon skeleton and alkyl (meth)acrylates having an alicyclic skeleton, more preferably to contain at least one of methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate, and even more preferably to contain both methyl (meth)acrylate and n-butyl (meth)acrylate; These (meth)acrylic monomers may be used alone or in any combination of two or more kinds in any ratio.

[0087] With respect to the total mass of all structural units constituting the acrylic resin, the content of structural units derived from (meth)acrylic monomers is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass.

[0088] The other monomer is not particularly limited as long as it is copolymerizable with the (meth)acrylic monomer, and examples thereof include aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, and chlorostyrene; cyanide vinyl monomers such as acrylonitrile, methacrylonitrile, α-cyanoacrylate, dicyanovinylidene, and fumaronitrile; monomers having a carboxy group such as crotonic acid, isocrotonic acid, cinnamic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and glutaconic acid; sulfonic acid group-containing monomers such as vinyl sulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid; polyfunctional monomers such as divinylbenzene, divinylnaphthalene, and divinyl ether; vinyl monomers such as vinyl acetate and vinyl propionate; and conjugated diene monomers such as 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, and chloroprene. These other monomers may be used alone or in any combination of two or more kinds in any ratio.

[0089] The weight-average molecular weight (Mw) of the acrylic resin is preferably 5,000 or more, more preferably 5,000 to 20,000, even more preferably 7,000 to 15,000, and particularly preferably 9,000 to 12,000. If the weight-average molecular weight of the acrylic resin is equal to or greater than the lower limit, the hardness of the hard coat layer 12 is further increased. If the weight-average molecular weight of the acrylic resin is equal to or less than the upper limit, an increase in the viscosity of the coating composition can be suppressed, improving handleability. The weight average molecular weight of the acrylic resin can be determined by the method described above.

[0090] The glass transition temperature (Tg) of the acrylic resin is preferably 40°C or higher, more preferably 40°C or higher and 200°C or lower, even more preferably 80°C or higher and 160°C or lower, and particularly preferably 100°C or higher and 130°C or lower. If the glass transition temperature of the acrylic resin (B) is equal to or higher than the lower limit, the hardness of the hard coat layer 12 is further increased. If the glass transition temperature of the acrylic resin (B) is equal to or lower than the upper limit, the handleability of the film after molding is improved. The glass transition temperature of the acrylic resin can be determined by the method described above.

[0091] The acrylic resin can be obtained by polymerizing a monomer component (m1) containing a (meth)acrylic monomer in the presence of a polymerization initiator using a known polymerization method such as solution polymerization, suspension polymerization, bulk polymerization, or emulsion polymerization. Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; and azo compounds such as 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). In order to adjust the weight-average molecular weight of the acrylic resin, a chain transfer agent may be used when polymerizing the monomer components. Examples of the chain transfer agent include known mercaptan compounds, α-methylstyrene dimers, and known terpinolene compounds. These polymerization initiators and chain transfer agents may each be used alone or in any combination of two or more kinds in any ratio.

[0092] Commercially available acrylic resins may be used, such as those available from Mitsubishi Chemical Corporation under the trade name "Dianal" series, DIC Corporation under the trade name "Acrydic" series, and Taisei Fine Chemical Co., Ltd. under the trade name "Acrit."

[0093] The content of component (C) is preferably 1% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 28% by mass or less, and even more preferably 10% by mass or more and 25% by mass or less, relative to the total mass of the coating composition. When the content of component (C) is equal to or greater than the above-mentioned lower limit, cure shrinkage during curing of the coating composition can be suppressed, and adhesion of the hard coat layer 12 to the resin substrate 11 can be further improved. When the content of component (C) is equal to or less than the above-mentioned upper limit, crosslink density of the hard coat layer 12 can be well maintained, and chemical resistance can be improved.

[0094] <<(D) component>> The component (D) is a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it generates radicals by the action of light, and examples thereof include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 1-(4-isopropylenephenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and benzophenone. , benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4',4''-diethylisophthalophenone Examples of suitable acylphosphine compounds include methylphenyl glyoxylate, 9,10-phenanthrenequinone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. These photopolymerization initiators may be used alone or in any combination of two or more kinds in any ratio.

[0095] Commercially available photopolymerization initiators may be used. Examples of commercially available photopolymerization initiators include those available from IGM Group BV under the trade names "Omnirad 184 (1-hydroxycyclohexyl phenyl ketone)," "Omnirad 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one)," "Omnirad 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one)," "Omnirad TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, IGM Resins)," "Omnirad 651 (2,2-dimethoxy-2-phenylacetophenone)," and "Omnirad 127 (2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one)."

[0096] The content of component (D) is preferably 2% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, and even more preferably 4% by mass or more and 10% by mass or less, based on the total mass of the coating composition. If the content of component (D) is equal to or greater than the above-mentioned lower limit, the reaction rate during curing of the coating composition increases. As a result, the crosslink density and glass transition temperature of the hard coat layer 12 increase, and sufficient hardness is obtained. However, if the content of component (D) is too high, component (D) may act as a plasticizer, which may reduce the hardness of the hard coat layer 12. If the content of component (D) is equal to or less than the above-mentioned upper limit, the hardness of the hard coat layer 12 can be maintained at a good level.

[0097] <<Optional ingredients>> Examples of optional components include solvents, curing-accelerating catalysts, ultraviolet absorbers, light stabilizers, antioxidants, anti-yellowing agents, bluing agents, pigments, leveling agents, defoamers, thickeners, anti-settling agents, antistatic agents, and anti-fogging agents. These optional components may be used alone or in any combination of two or more kinds in any ratio.

[0098] The solvent is preferably one that has excellent compatibility with components (A), (B), and (C), and examples thereof include hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane, ethylene glycol diethyl ether, and propylene glycol monomethyl ether; and aliphatic hydrocarbons such as pentane, hexane, and heptane. These solvents may be used alone or in any combination of two or more kinds in any ratio. The solvent content is preferably 0% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 80% by mass or less, and even more preferably 30% by mass or more and 70% by mass or less, based on the total mass of the coating composition.

[0099] <<Method of manufacturing coating composition>> The coating composition can be obtained by mixing the above-mentioned components (A), (B), (C), and (D), and, if necessary, optional components. The mixing method is not particularly limited, and known mixers such as a planetary centrifugal mixer, a three-roll mill, a kneader, etc. can be used.

[0100] <Method of manufacturing laminate> The laminate 10 can be obtained, for example, by applying the above-mentioned coating composition to the surface of the resin substrate 11 to form a coating film, drying the coating film as necessary, and then irradiating the coating film with active energy rays to harden the coating film. The method for applying the coating composition is not particularly limited, but examples thereof include known methods such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, and spray coating.

[0101] When the coating composition contains a solvent, it is preferable to heat-dry the coating film before curing, as this allows the solvent in the coating film to be effectively removed. The drying temperature for the heat drying is preferably 40° C. or higher and 100° C. or lower, and more preferably 50° C. or higher and 70° C. or lower. If the drying temperature is equal to or higher than the lower limit, the drying time can be shortened. If the drying temperature is equal to or lower than the upper limit, excessive dissolution of the resin substrate 11 can be suppressed. The drying time is preferably from 30 seconds to 5 minutes, more preferably from 1 minute to 3 minutes.

[0102] Examples of active energy rays include ultraviolet rays, electron beams, X-rays, infrared rays, visible light, etc. Among these, ultraviolet rays are preferred. The irradiation dose of the active energy rays can be appropriately selected depending on the active energy rays to be irradiated. When using ultraviolet light, the cumulative light intensity is 50 mJ / cm 2 More than 1000mJ / cm 2 It is preferable to irradiate at a dose of 200 mJ / cm or less, more preferably 200 mJ / cm 2 More than 400mJ / cm 2 The illuminance is 25mW / cm 2 More than 400mW / cm 2 Less than 50mW / cm is preferable. 2 More than 200mW / cm 2 Less than 100 mW / cm is more preferable. 2 More than 150mW / cm 2 The following are more preferred: As the light source, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or an electron beam using a scanning or curtain-type electron beam acceleration path, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a low-pressure mercury lamp, etc. can be used.

[0103] The temperature at which the coating composition is cured (the temperature at which active energy rays are irradiated) may be appropriately set in consideration of the heat resistance, thermal deformation property, etc. of the resin substrate 11. The temperature at which the coating composition is cured is, for example, preferably 40°C or higher and 100°C or lower, and more preferably 50°C or higher and 80°C or lower.

[0104] <Action and effect> In the laminate of the present invention described above, the number of particles contained in the region (α) of the hard coat layer is at least five times the number of particles contained in the region (β), so that the adhesion between the resin substrate and the hard coat layer is excellent and the hardness of the hard coat layer is high. In particular, if the particles contained in the region (α) and the region (β) are particles derived from the resin substrate, the adhesion between the resin substrate and the hard coat layer is even more excellent. The laminate of the present invention has excellent adhesion between the resin substrate and the hard coat layer, and therefore there is no need to provide a primer layer between the resin substrate and the hard coat layer. The laminate of the present invention is suitable as a protective film used, for example, to protect the surface of an article.

[0105] <Other aspects> The laminate of the present invention is not limited to the above. For example, in the laminate 10 of the illustrated example described above, the hard coat layer 12 is provided on the entire surface of one of the surfaces of the resin substrate 11, but the hard coat layer 12 may be provided on only a part of the surface of the resin substrate 11. The hard coat layer 12 may also be provided on a part of or the entire other surface of the resin substrate 11. That is, the hard coat layer 12 may be provided on both surfaces of the resin substrate 11. Although the resin substrate 11 shown in the figure is a sheet having a single layer structure, it may be a sheet having a multilayer structure or may have a three-dimensional shape. When the resin substrate 11 has a multilayer structure, at least the layer on the side in contact with the hard coat layer 12 contains an acrylic resin.

[0106] [Goods] The article of the present invention has the above-described laminate of the present invention on its surface. An example of an article includes an article body and a laminate of the present invention provided on the surface of the article body. The laminate of the present invention is provided on the surface of the article body so that the resin substrate and the article body are in contact with each other. That is, the hard coat layer of the laminate is the outermost layer of the article. The laminate of the present invention may be provided on a part of the surface of the article body, or may be provided on the entire surface. The article can be obtained, for example, by bonding the article body and the laminate of the present invention under heat and pressure so that the resin substrate of the laminate contacts the article body. The article body and the laminate may be bonded via an adhesive. Alternatively, the laminate of the present invention may be molded into a desired shape in advance, unnecessary portions removed as necessary, and then placed in an injection molding mold. A resin material that will become the main body of the article may be injection molded onto the resin substrate side of the laminate, thereby integrating the laminate and the main body of the article to produce an article. The resin substrate of the laminate may also serve as the article body.

[0107] Examples of the articles include plastic molded products such as high pressure laminates (HPL), mobile phones, home appliances, automobile interior and exterior materials, and office automation equipment. [Example]

[0108] The present invention will be described in more detail below with reference to examples. In the following description, "parts" means "parts by mass" unless otherwise specified. It should be noted that the following examples are illustrative of the present invention and are not intended to limit the scope of the present invention.

[0109] [Measurement and Evaluation] <Measurement of average particle size> A light scattering photometer (Otsuka Electronics Co., Ltd., product name "DLS-700") was used to measure the particle diameter (median diameter) corresponding to 50% of the cumulative volume in the particle size distribution by dynamic light scattering, and this was taken as the average particle diameter of the acrylic rubber particles.

[0110] <Measurement of weight average molecular weight (Mw)> The weight average molecular weight (Mw) of the resin was measured by gel permeation chromatography (GPC) under the following conditions, and calculated in terms of standard polystyrene. Equipment: High-speed GPC equipment manufactured by Tosoh Corporation, product name "HLC-8320GPC type" UV detector: Tosoh Corporation, product name "UV-8320" ·Flow rate: 0.35mL / min ·Inlet temperature: 40℃ Oven temperature: 40℃ ·RI temperature: 40℃ ·UV wavelength: 254nm Sample injection volume: 10 μL Columns: Three columns connected in the order of (1) to (3) below (1) Tosoh Corporation, product name "TSKgel superHZM-M" (4.6mm ID x 15cm L) (2) Tosoh Corporation, product name "TSKgel superHZM-M" (4.6mm ID x 15cm L) (3) Tosoh Corporation, product name "TSKgel HZ2000" (4.6mm ID x 15cm L) Guard column: Tosoh Corporation, product name "TSKguardcolumn SuperHZ-L" (4.6mm ID x 3.5cm L) Solvent: THF (stabilizer: BHT) Sample concentration: Adjusted to 0.2% resin by mass

[0111] <Measurement of glass transition temperature (Tg)> The glass transition temperature of the resin was calculated from the Fox equation using the values ​​listed in the Polymer Handbook (J. Brandrup, Interscience, 1989) or the values ​​in the catalogues of the monomer manufacturers.

[0112] <Measurement of hydroxyl value> The hydroxyl value of the reactive group-containing resin was determined by the following method. First, the sample was dissolved in acetic anhydride and pyridine, acetylated, and then titrated with 0.5 mol / L ethanolic potassium hydroxide solution using phenolphthalein as an indicator. A blank test was also conducted in the same manner except that no sample was used, and the hydroxyl value was calculated using the following formula (4). Hydroxyl value = (BA) × f × 56.1 × 0.5 / S + acid value (4) f: Potency of 0.5 mol / L ethanolic potassium hydroxide S: Sample amount (g) A: Amount of ethanolic potassium hydroxide used in titration (mL) B: Amount of ethanolic potassium hydroxide used in the blank test (mL) The calculated hydroxyl value is a value assuming that the introduction rate of the hydroxyl monomer is 100% and the acid value is zero.

[0113] <Measurement of gel content> 50 mL of acetone was added to 0.5 g of the coating composition and stirred at 65°C for 4 hours. The mixture was then centrifuged at 4°C and 14,000 rpm for 30 minutes. After removing the supernatant, 50 mL of acetone was added again and centrifuged again under the same conditions. After removing the supernatant, the precipitated gel was vacuum dried for 8 hours and its mass was measured. The gel content was calculated using the following formula (2). Gel content (%) = (mass of gel part (g) / 0.5) × 100 (2)

[0114] <Measurement of particle count> The laminate was cut in the thickness direction (stacking direction), and the cut surface was observed at a magnification of 2000 times using a scanning electron microscope (manufactured by JEOL Ltd., product name "JSM1400Flash type"), and the observed image was binarized using image processing software (ImageJ). The cut surface was divided into two equal parts in the direction perpendicular to the thickness direction of the hard coat layer, that is, a region (α) on the resin substrate side and a region (β) on the outermost surface side. From the binarized image, the number of particles (particle diameter 0.05 μm or more) observed in region (α) was counted, and the number of particles in region (α) 12α was counted. 2 Similarly, the number of particles (particle diameter 0.05 μm or more) observed in the region (β) was counted, and the number of particles was calculated by dividing the number of particles by 1 μm in the region (β). 2 The particle number ratio (R) was calculated using the following formula (3). Ratio of particle number (R) = 1 μm of area (α) 2 Number of particles per 1 μm of area (β) 2 Number of particles per particle (3)

[0115] <Evaluation of Adhesion> A grid of 100 squares was cut at 1 mm intervals on the surface of the hard coat layer side of the laminate using a cutter knife. Cellophane tape (manufactured by Nichiban Co., Ltd.) was attached to the cut surface of the hard coat layer and then rapidly peeled off. The number of peeled squares was counted and the adhesion was evaluated according to the following evaluation criteria. ◎: The mass does not come off at all. O: 1 to 4 squares are peeled off. △: 5 to 15 squares are peeled off. ×: 16 or more squares are peeled off.

[0116] <Hardness measurement> A scratch hardness test was carried out on the surface of the hard coat layer side of the laminate in accordance with CEN (European Committee for Standardization) standard EN438-2, and the load at which scratches were visible was determined, and the hardness was evaluated according to the following evaluation criteria. ○: The load is 3.0N or more. △: The load is 1.0N or more and less than 3.0N. ×: The load is less than 1.0 N.

[0117] [Manufacturing of resin substrates] <Production of acrylic rubber particles (X-1-1)> In a nitrogen atmosphere, 206 parts of deionized water was placed in a reaction vessel equipped with a reflux condenser, and the temperature was raised to 80°C. Component (i) shown below was added, and while stirring, 1 / 10 of raw material (ii) shown below (part of the raw materials for elastic copolymer (x-1)) was added and held for 15 minutes. Next, the remaining raw material (ii) was continuously added so that the increase rate of the monomer mixture relative to water was 8% by mass / hour. Polymerization was then carried out by holding for 1 hour to obtain a polymer latex. Next, 0.2 parts of sodium formaldehyde sulfoxylate was added to the polymer latex. After holding for 15 minutes, raw material (iii) shown below (part of the raw materials for elastic copolymer (x-1)) was continuously added while stirring at 80°C under a nitrogen atmosphere so that the increase rate of the monomer mixture relative to water was 4% by mass / hour. Polymerization was then carried out by holding for 2 hours to obtain a latex of elastic copolymer (x-1). To this latex of elastic copolymer (x-1), 0.2 parts of sodium formaldehyde sulfoxylate was added. After 15 minutes of stirring at 80°C under a nitrogen atmosphere, raw material (iv) (raw material for rigid polymer (x-2)) shown below was continuously added so that the rate of increase of the monomer mixture relative to water was 10% by mass / hour. The mixture was then held for 1 hour to allow polymerization, yielding a latex of acrylic rubber particles (X-1-1) with a core-shell structure. The average particle diameter of the acrylic rubber particles (X-1-1) was 0.28 μm. The latex of the acrylic rubber particles (X-1-1) was filtered through a filter with a mesh size of 50 μm, and then subjected to coagulation, aggregation, and solidification reactions using calcium acetate, followed by filtration, washing with water, and drying to obtain acrylic rubber particles (X-1-1).

[0118] Component (i) Sodium formaldehyde sulfoxylate: 0.4 parts Ferrous sulfate: 0.00004 parts Disodium ethylenediaminetetraacetate: 0.00012 parts

[0119] Raw material (ii) Methyl methacrylate: 11.25 parts n-Butyl acrylate: 12.5 parts Styrene: 1.25 parts Allyl methacrylate: 0.094 parts 1,3-butylene glycol dimethacrylate: 0.75 parts t-Butyl hydroperoxide: 0.044 parts Mono-n-dodecyloxytetraoxyethylene sodium phosphate (manufactured by Toho Chemical Industry Co., Ltd., trade name "Phosphanol RS-610NA"): 0.75 parts

[0120] Raw material (iii) n-Butyl acrylate: 30.9 parts Styrene: 6.6 parts Allyl methacrylate: 0.66 parts 1,3-butylene glycol dimethacrylate: 0.09 parts Cumene hydroperoxide: 0.11 parts Mono-n-dodecyloxytetraoxyethylene sodium phosphate (manufactured by Toho Chemical Industry Co., Ltd., trade name "Phosphanol RS-610NA"): 0.6 parts

[0121] Raw materials (iv) Methyl methacrylate: 35.6 parts Methyl acrylate: 1.9 parts n-Octyl mercaptan: 0.11 parts t-Butyl hydroperoxide: 0.06 parts

[0122] <Production of Reactive Group-Containing Resin (X-2-1)> A reaction vessel equipped with a stirrer, reflux condenser, and nitrogen gas inlet was charged with 80 parts methyl methacrylate, 5 parts n-butyl acrylate, 15 parts 2-hydroxypropyl methacrylate, 0.25 parts n-octyl mercaptan, 0.4 parts lauryl peroxide, 0.02 parts methyl methacrylate / methacrylate salt / methacrylate ethyl sulfonate copolymer, 0.3 parts sodium sulfate, and 145 parts deionized water. The atmosphere in the vessel was thoroughly purged with nitrogen gas, and the mixture was then heated to 75°C with stirring and allowed to polymerize in a nitrogen gas stream. After 2 hours, the temperature was raised to 95°C and maintained for an additional 60 minutes to complete the polymerization. The resulting polymer beads were dehydrated and dried to obtain a reactive group-containing resin (X-2-1). The resulting reactive group-containing resin (X-2-1) had a weight average molecular weight (Mw) of 96,800, a glass transition temperature (Tg) of 78°C, and a hydroxyl value of 58 mgKOH / g.

[0123] <Production of Thermoplastic Resin (X-4-1)> A reaction vessel was charged with 200 parts of nitrogen-substituted deionized water, 1 part of potassium oleate and 0.3 parts of potassium persulfate as emulsifiers, 40 parts of methyl methacrylate, 10 parts of n-butyl acrylate, and 0.005 parts of n-octyl mercaptan, and the mixture was stirred at 65°C under a nitrogen atmosphere for 3 hours to complete the polymerization. Subsequently, a monomer mixture consisting of 48 parts of methyl methacrylate and 2 parts of n-butyl acrylate was added dropwise over 2 hours, and after the completion of the dropwise addition, the mixture was maintained for 2 hours to complete the polymerization. The obtained latex was added to a 0.25% by mass aqueous sulfuric acid solution to cause coagulation, followed by filtration, washing with water, and drying to obtain a thermoplastic resin (X-4-1). The weight average molecular weight (Mw) of the resulting thermoplastic resin (X-4-1) was 1,000,000.

[0124] <Production of acrylic resin composition (X1)> 24 parts of acrylic rubber particles (X-1-1) as particles (X-1), 76 parts of reactive group-containing resin (X-2-1) as reactive group-containing resin (X-2), 2 parts of thermoplastic resin (X-4-1) as additive (X-4), 2.1 parts of benzotriazole-based ultraviolet absorber (manufactured by ADEKA Corporation, trade name "ADEKA STAB LA-31RG"), 0.45 parts of hindered amine-based light stabilizer (manufactured by BASF Japan Ltd., trade name "Chimassorb 2020"), and 0.1 parts of hindered phenol-based antioxidant (manufactured by BASF Japan Ltd., trade name "Irganox 1076") were added and mixed using a Henschel mixer. The resulting mixture was melt-kneaded using a 35 mmφ screw-type twin-screw extruder (L / D=26) under conditions of a cylinder temperature of 200 to 240°C and a die temperature of 240°C to obtain a pellet-shaped acrylic resin composition (X1). The gel content of the acetone-insoluble matter of the acrylic resin composition (X1) was 20%. The acetone-soluble matter contained a reactive group-containing resin (X-2-1) as an acrylic resin having a weight-average molecular weight of 300,000 or less and a thermoplastic resin (X-4-1) as an acrylic resin having a weight-average molecular weight of more than 300,000, and the glass transition temperature of the acrylic resin having a weight-average molecular weight of 300,000 or less was 78°C.

[0125] <Manufacturing of resin substrate> The acrylic resin composition (X1) was dried at 80°C for a whole day and night. The acrylic resin composition (X1) was plasticized using a 40 mmφ extruder equipped with a 400-mesh screen mesh and the cylinder temperature was set to 230°C, and then formed into a sheet-like resin substrate having a thickness of 50 μm using a single-layer feed block die set to 240°C.

[0126] [Examples 1 to 5, Comparative Examples 1 to 4] Each component was mixed based on the formulation shown in Tables 1 and 2 to prepare a coating composition. The resulting coating composition was applied to one surface of a resin substrate using a No. 14 bar coater to form a coating film on the resin substrate. The coating film was then dried at 60°C or 70°C for 3 minutes, and then exposed to an integrated light dose of 200 mJ / cm2 in an air atmosphere at 25°C. 2 So, the illuminance is 100mW / cm 2 The coating was cured by irradiating it with ultraviolet light at 1000 kJ / cm to obtain a laminate in which a hard coat layer having a thickness of 10 μm was formed on the resin substrate. The number of particles contained in the hard coat layer of the obtained laminate was measured, and the adhesion and hardness were evaluated. The results are shown in Tables 1 and 2 and Figures 2 to 5. The region indicated by reference numeral 13 in Figures 2 and 4 is an air layer.

[0127] [Table 1]

[0128] [Table 2]

[0129] The meanings of the abbreviations in Tables 1 and 2 are as follows: Note that blank spaces in Tables 1 and 2 mean that the component is not blended (amount blended: 0 parts). 4-HBA: 4-hydroxybutyl acrylate (dispersion parameter (δD) 16.7 MPa) 1 / 2 , polarization term (δP) 6.6MPa 1 / 2 , hydrogen bond term (δH) 10.8 MPa 1 / 2 ) EC-A: Ethoxydiethylene glycol acrylate (Kyoeisha Chemical Co., Ltd., product name "Light Acrylate EC-A"), dispersion parameter (δD) 16.2 MPa 1 / 2 , polarization term (δP) 5.1MPa 1 / 2 , hydrogen bond term (δH) 6.5MPa 1 / 2 ) 2-MTA: 2-methoxyethyl acrylate (dispersion parameter (δD) 16.3 MPa) 1 / 2 , polarization term (δP) 5.6MPa 1 / 2 , hydrogen bond term (δH) 7.2MPa 1 / 2 ) LA: Lauryl acrylate (dispersion parameter (δD) 16.0 MPa 1 / 2 , polarization term (δP) 2.4MPa 1 / 2 , hydrogen bond term (δH) 3.2MPa 1 / 2 , (A) component comparison product ((A') component) Aronix M402: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., product name "Aronix M402") Aronix M315: A mixture of EO-modified isocyanuric acid diacrylate and EO-modified isocyanuric acid triacrylate (manufactured by Toagosei Co., Ltd., product name "Aronix M315") KAYARAD R-604: Dioxane glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD R-604") LR-2697: Acrylic resin with hydroxyl groups (manufactured by Mitsubishi Chemical Corporation, product name "Dianal LR-2697", glass transition temperature 119°C, weight average molecular weight 9,700) BR-80: Acrylic resin without hydroxyl groups (manufactured by Mitsubishi Chemical Corporation, product name "Dianal BR-80", glass transition temperature 104°C, weight average molecular weight 100,000) Omnirad 1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by IGM Group BV, trade name "Omnirad 1173") Tinuvin PS: Benzotriazole-based UV absorber, 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole (manufactured by BASF, trade name "Tinuvin PS") Tinuvin 292: Hindered amine light stabilizer, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (manufactured by BASF, trade name "Tinuvin 292") PGM: Propylene glycol monomethyl ether

[0130] As is clear from the results in Table 1, the laminates obtained in each example had excellent adhesion between the resin substrate and the hard coat layer. In addition, the hard coat layer had high hardness. On the other hand, as is clear from the results in Table 2, the laminates obtained in Comparative Examples 1 and 2 had poor adhesion between the resin substrate and the hard coat layer. Therefore, the hardness of the hard coat layer of the laminates obtained in Comparative Examples 1 and 2 was not evaluated. The laminates obtained in Comparative Examples 3 and 4 had excellent adhesion between the resin substrate and the hard coat layer, but the hardness of the hard coat layer was low. [Explanation of symbols]

[0131] 10 Laminate 11 Resin substrate 12 Hard coat layer 13 Air Layer

Claims

1. A resin substrate and a hard coat layer provided on the resin substrate, the resin substrate contains an acrylic resin, the hard coat layer is made of a cured product of an active energy ray-curable coating composition containing an unsaturated double bond-containing compound, a laminate in which, when the hard coat layer is cut in the thickness direction and the cut surface is divided into two equal parts in a direction perpendicular to the thickness direction, i.e., a region (α) on the resin substrate side and a region (β) on the outermost surface side, the number of particles contained in the region (α) is 5 times or more the number of particles contained in the region (β), and the particles are derived from the resin substrate.

2. The laminate according to claim 1 , wherein the resin substrate is in the form of a sheet.

3. the resin substrate is composed of an acetone soluble component and an acetone insoluble component, the content of the acetone insoluble matter (gel content) in the total amount of the resin substrate is 15% or more, The acetone soluble component includes an acrylic resin having a weight-average molecular weight of 300,000 or less and an acrylic resin having a weight-average molecular weight of more than 300,000, 2. The laminate according to claim 1, wherein the acrylic resin having a weight average molecular weight of 300,000 or less has a glass transition temperature Tg of 95°C or less.

4. An article having the laminate according to any one of claims 1 to 3 on a surface thereof.

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