Multilayer body, multilayer body with hard coat layer, and method for producing thermoformed article

Abstract

To provide: a multilayer body capable of providing a multilayer body having a hard coat layer excellent in scratch resistance and adhesion to a substrate layer; a multilayer body with a hard coat layer; and a method for producing a thermoformed article.SOLUTION: The multilayer body includes: a substrate layer containing a thermoplastic resin; and a curable resin layer provided on a surface of the substrate layer and containing a hydrogen-bonding functional group. The substrate layer contains a compound containing at least one -NH2 in an amount of 0.05-10 mass% in the substrate layer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a multilayer body, a multilayer body with a hard coat layer, and a method for producing a thermoformed body. [Background technology]

[0002] Polycarbonate resin is widely used in a variety of fields, not only because of its excellent transparency, but also because it is easier to process and has better impact resistance than glass, and because it does not emit toxic gases compared to other plastic materials. It is also used as a thermoforming material for vacuum forming, pressure forming, and other processes.

[0003] On the other hand, polycarbonate resin generally has low surface hardness, and therefore the surface of molded products made of polycarbonate resin tends to be easily scratched. Therefore, when polycarbonate resin is made into a film, it is being considered to form a layer containing an acrylic resin or a hard coat layer (protective layer) on the surface to prevent scratches on the product surface. For example, Patent Document 1 discloses a curable hard coat composition comprising a (meth)acryloyl polymer and inorganic oxide nanoparticles, the (meth)acryloyl polymer having a (meth)acrylic equivalent of 200 to 500 g / eq and a weight-average molecular weight of 5,000 to 200,000, and the inorganic oxide nanoparticles having an average particle size of 6 to less than 95 nm. Furthermore, it also describes that the hard coat composition is applied to the surface of a substrate layer in which a polycarbonate resin and a PMMA resin are laminated. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 031967 Summary of the Invention [Problem to be solved by the invention]

[0005] Here, the multilayer body obtained using the above hard coat composition has a hard coat layer that has excellent scratch resistance and hardness. However, with technological innovation, new materials are required, and in particular, multilayer bodies having a hard coat layer that is excellent in abrasion resistance and adhesion to a substrate layer are required. The present invention aims to solve the above problems, and aims to provide a multilayer body capable of providing a multilayer body having a hard coat layer that has excellent scratch resistance and excellent adhesion to a substrate layer, as well as a method for producing a multilayer body with a hard coat layer and a thermoformed body. [Means for solving the problem]

[0006] In light of the above-mentioned problems, the present inventors have conducted research and found that the above-mentioned problems can be solved by configuring the curable resin layer to contain hydrogen-bonding functional groups and by incorporating a compound containing one or more -NH2 groups into the base layer. Specifically, the above problems were solved by the following means. <1> a substrate layer containing a thermoplastic resin; and a curable resin layer provided on the surface of the substrate layer and containing a hydrogen-bonding functional group; A multilayer body, wherein the base layer contains 0.05 to 10 mass % of a compound containing one or more -NH2 groups. <2> The hydrogen-bonding functional group contains at least one structure selected from —OH and —NH. <1> The multilayer body according to claim 1. <3> The molecular weight of the compound containing one or more -NH2 is 90 to 500. <1> or <2> The multilayer body according to claim 1. <4> The substrate layer includes an acrylic resin layer. <1> ~ <3> 10. The multilayer body according to any one of the preceding items. <5> The curable resin layer contains a structural unit represented by formula (Ac): <1> ~ <4> 10. The multilayer body according to any one of the preceding items. Formula (Ac) [ka] (In the above formula (Ac), R mis a single bond or an alkylene group having 1 to 4 carbon atoms, and R n is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R p is a single bond or a divalent linking group, and R q is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. p and R q At least one of the groups contains a hydrogen-bonding group. * indicates a bonding site with another group.) <6> At least one of the structural units represented by formula (Ac) is a structural unit represented by formula (Ac1). <5> The multilayer body according to claim 1. Formula (Ac1) [ka] (In the above formula (Ac1), R m1 is a methylene group, and R n1 is a hydrogen atom or a methyl group, and R q1 is a hydrocarbon group having 1 to 12 carbon atoms, containing at least one of a vinyl group and a (meth)acryloyl group, and at least one structure selected from -OH and -NH. * is a bonding site to another site.) <7> The curable resin layer further contains a structural unit represented by formula (Ac2): <1> ~ <6> 10. The multilayer body according to any one of the preceding items. Formula (Ac2) [ka] (In the above formula (Ac2), R m is a single bond or an alkylene group having 1 to 4 carbon atoms, and R n is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R p is a single bond or a divalent linking group, and R q2 is a hydrogen atom or a substituent other than a hydrogen-bonding group, a vinyl group, and a (meth)acryloyl group. <8> The curable resin layer contains a structural unit represented by formula (Ac1) and a structural unit represented by formula (Ac2), <1> ~ <7> 10. The multilayer body according to any one of the preceding items. Formula (Ac1) [ka] (In the above formula (Ac1), R m1 is a methylene group, and R n1 is a hydrogen atom or a methyl group, and R q1 is a hydrocarbon group having 1 to 12 carbon atoms, containing at least one of a vinyl group and a (meth)acryloyl group, and at least one structure selected from -OH and -NH. * is a bonding site to another site.) Formula (Ac2) [ka] (In the above formula (Ac2), R m is a single bond or an alkylene group having 1 to 4 carbon atoms, and R n is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R p is a single bond or a divalent linking group, and R q2 is a hydrogen atom or a substituent other than a hydrogen-bonding group, a vinyl group, and a (meth)acryloyl group. <9> The curable resin layer contains a (meth)acryloyl polymer having a (meth)acrylic equivalent of 200 to 600 g / mol. <1> ~ <8> 10. The multilayer body according to any one of the preceding items. <10> the substrate layer includes an acrylic resin layer and a polycarbonate resin layer; <1> ~ <9> 10. The multilayer body according to any one of the preceding items. <11> the curable resin layer is located on the surface of the acrylic resin layer opposite to the polycarbonate resin layer; <10> The multilayer body according to claim 1. <12> For thermoforming, <1> ~ <11> 10. The multilayer body according to any one of the preceding items. <13> <1> ~ <12> 10. A multilayer body with a hard coat layer, wherein the curable resin layer of the multilayer body according to any one of 1 to 8 is cured. <14> the hard coat layer has an evaluation result of 0 or 1 in a cross-cut test in accordance with JIS-K5600-5-6; <13> 2. A multilayer body with a hard coat layer according to claim 1. <15> <1> ~ <12> 10. A method for producing a thermoformed article, comprising thermoforming the multilayer article according to any one of 1 to 9, and then curing the curable resin layer. [Effects of the Invention]

[0007] The present invention makes it possible to provide a multilayer body that can provide a multilayer body having a hard coat layer that has excellent scratch resistance and excellent adhesion to a substrate layer, as well as a method for producing a multilayer body with a hard coat layer and a thermoformed body. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram showing the layer structure of the multilayer body of this embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the upper and lower limits. Furthermore, any combination of the upper and lower limit values ​​of the numerical values ​​in this specification is an example of this embodiment. In this specification, various physical properties and characteristic values ​​are those at 23°C unless otherwise specified. In the description of groups (atomic groups) in this specification, when a notation does not specify whether they are substituted or unsubstituted, it includes both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents. For example, the term "alkyl group" includes not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups). In this specification, when a notation does not specify whether they are substituted or unsubstituted, it is preferable that they be unsubstituted. Examples of the substituent herein include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclicoxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, acyl groups, amino groups, vinyl groups, and (meth)acryloyl groups, and more preferably hydroxy groups, alkyl groups, amino groups, vinyl groups, or (meth)acryloyl groups. The formula weight of these substituents is preferably 15 or more and 200 or less. For example, the formula weight of a methyl group (-CH3) is 15. These substituents may further have a substituent, but it is preferable that they have no substituent.

[0010] In this specification, "(meth)allyl" refers to both or either of allyl and methallyl, "(meth)acrylate" refers to both or either of acrylate and methacrylate, "(meth)acrylic" refers to both or either of acrylic and methacrylic, and "(meth)acryloyl" refers to both or either of acryloyl and methacryloyl.

[0011] The multilayer body in this specification is intended to include those in the form of a film or a sheet. The terms "film" and "sheet" refer to a generally flat shaped body having a small thickness relative to its length and width, respectively. Furthermore, the "film" and "sheet" in this specification may be either a single layer or a multilayer body. If the measurement methods, etc. described in the standards shown in this specification vary from year to year, they will be based on the standards in effect as of January 1, 2023, unless otherwise specified. If the measurement methods, etc. described in the standards shown in this specification are obsolete as of January 1, 2023, they will be based on the standards in effect at the time of obsoleteness. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved. The scale of Figure 1 may not be consistent with reality.

[0012] The multilayer body of this embodiment comprises a substrate layer containing a thermoplastic resin, and a curable resin layer provided on the surface of the substrate layer and containing a hydrogen-bonding functional group, wherein the substrate layer contains 0.05 to 10 mass % of a compound containing one or more -NH2 groups. This configuration makes it possible to provide a multilayer body having a hard coat layer that is excellent in abrasion resistance and adhesion to the substrate layer. The curable resin layer forms a hard coat layer by curing the curable resin. However, when the curable resin is cured, a gap caused by the conversion from the van der Waals distance to the covalent bond distance may cause curing shrinkage. Such curing shrinkage may cause a decrease in adhesion between the hard coat layer and the substrate layer. However, if the proportion of curable groups in the curable resin layer is reduced to make the curable resin layer less susceptible to curing shrinkage, the scratch resistance that is inherently required of the hard coat layer tends to deteriorate. In the present invention, by configuring the curable resin layer to have a hydrogen-bonding functional group and blending a compound containing one or more -NH2 groups in the substrate layer, it has been possible to successfully suppress a decrease in adhesion between the substrate layer and the hard coat layer while maintaining scratch resistance. That is, when the substrate layer contains a compound containing one or more -NH2 groups, an interaction represented by hydrogen bonding occurs between the hydrogen-bonding functional group contained in the curable resin layer and the compound containing one or more -NH2 groups contained in the substrate layer during curing of the curable resin layer, thereby improving the adhesion between the substrate layer and the cured curable resin layer (hard coat layer). Furthermore, in the multilayer body of this embodiment, the curable resin layer can be cured after thermoforming.

[0013] <Base material layer> The multilayer body of this embodiment includes a substrate layer, which contains a thermoplastic resin and 0.05 to 10 mass % of a compound containing one or more —NH2 groups. The thermoplastic resin contained in the base layer can be appropriately set depending on the application, but it preferably contains at least one of acrylic resin, polycarbonate resin, polyamide resin, polyolefin resin, and polyester resin, and it is more preferable that it contains acrylic resin and / or polycarbonate resin.

[0014] The base layer used in the present embodiment preferably includes one or more thermoplastic resin layers, more preferably includes at least an acrylic resin layer, even more preferably includes at least an acrylic resin layer and a polycarbonate resin layer, and even more preferably consists of only an acrylic resin layer and a polycarbonate resin layer. The base layer may have other layers, and examples of such other layers include an adhesive layer and a bonding layer. Furthermore, the compound containing one or more -NH2 groups is preferably contained in the acrylic resin layer or the polycarbonate resin layer, and more preferably in the acrylic resin layer.

[0015] The total thickness of the base layer is preferably 100 μm or more, more preferably 120 μm or more, even more preferably 150 μm or more, even more preferably 170 μm or more, and even more preferably 180 μm or more, and is preferably 4000 μm or less, more preferably 2000 μm or less, even more preferably 1000 μm or less, even more preferably 500 μm or less, and even more preferably 300 μm or less.

[0016] <<Compounds containing one or more -NH2>> The base layer in this embodiment contains a compound containing one or more -NH2 groups, which interacts with the hydrogen-bonding functional groups contained in the curable resin layer, thereby improving the adhesion between the two layers. A compound containing one or more -NH2 preferably has one or more -NH2 groups in one molecule, and may have two or more, and preferably has five or less, and may have three or less. The compound containing one or more -NH2 groups used in this embodiment is preferably a compound that is unevenly distributed in the surface layer of the substrate layer (preferably an acrylic resin layer). By using a compound that is unevenly distributed in the surface layer, the adhesion of the resulting multilayer body can be further improved. As the unevenly distributed compound, a compound having a dipole moment is preferred.

[0017] The amino group equivalent of the compound containing one or more -NH2 is preferably 500 g / mol or less, more preferably 300 g / mol or less, and even more preferably 100 g / mol or less. The amino group equivalent is preferably 0 g / mol, and may be 0.1 g / mol or more. By keeping the equivalent below the upper limit, interaction with the hydrogen-bonding functional groups contained in the curable resin layer tends to be further improved. When the base layer of this embodiment contains two or more types of compounds each containing one or more -NH2 groups, the amino group equivalent of the mixture preferably falls within the above range.

[0018] The molecular weight of the compound containing one or more -NH2 groups is preferably 90 or more, more preferably 100 or more, even more preferably 150 or more, still more preferably 170 or more, and even more preferably 200 or more, and is preferably 500 or less, more preferably 450 or less, even more preferably 400 or less, still more preferably 350 or less, and even more preferably 300 or less. By setting the molecular weight at or above the lower limit, bleeding out onto the surface of the base layer tends to be suppressed. Furthermore, by setting the molecular weight at or below the upper limit, the amino group equivalent becomes smaller, and interaction with the hydrogen-bonding functional group contained in the curable resin layer tends to be further improved. When the base layer of this embodiment contains two or more types of compounds containing one or more -NH2, the molecular weight of the compounds containing one or more -NH2 is the sum (weighted average value) of the values ​​obtained by multiplying the molecular weight of each compound containing one or more -NH2 by the mass fraction of the compound containing one or more -NH2.

[0019] Examples of compounds containing one or more -NH2 groups include aliphatic amines, aromatic amines, etc. Specific examples include stearylamine, benzoguanamine, VD-3 manufactured by Shikoku Chemicals Corporation, and the following compounds. [ka]

[0020] The content of the compound containing one or more -NH groups in the substrate layer is 0.05% by mass or more, preferably 0.08% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more, based on the total amount of the substrate layer (in the case of a substrate layer consisting of two or more layers), and is 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.8% by mass or less. By setting the content at or above the lower limit, the adhesion between the substrate and the cured resin layer tends to be further improved. Meanwhile, by setting the content at or below the upper limit, the transparency and heat resistance of the substrate layer tend to be further improved.

[0021] The content of the compound containing one or more -NH2 groups in the substrate layer is 0.05% by mass or more, preferably 0.08% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more, relative to the thermoplastic resin layer (e.g., an acrylic resin layer or a polycarbonate resin layer) in contact with the curable resin layer of the substrate layer, and is 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.8% by mass or less. By setting the content at or above the lower limit, the adhesion between the substrate and the cured resin layer tends to be further improved. Furthermore, by setting the content at or below the upper limit, the transparency and heat resistance of the substrate layer tend to be further improved.

[0022] Furthermore, when the substrate layer (total amount in the case of a substrate layer consisting of two or more layers) is taken as 100 mass %, the proportion (ppm) of nitrogen atoms having unshared electron pairs is preferably 10 ppm or more, more preferably 25 ppm or more, even more preferably 100 ppm or more, and even more preferably 500 ppm or more. Also, it is preferably 50,000 ppm or less, more preferably 20,000 ppm or less, even more preferably 5,000 ppm or less, and even more preferably 1,500 ppm or less. By setting the content at or above the lower limit, the interaction with the hydrogen-bonding functional group contained in the curable resin layer tends to be further improved. Furthermore, by setting the content at or below the upper limit, the transparency and heat resistance of the substrate layer tend to be further improved.

[0023] The content of the compound containing one or more -NH2 groups in the substrate layer is preferably 10 ppm or more, more preferably 25 ppm or more, even more preferably 100 ppm or more, and even more preferably 500 ppm or more, when the thermoplastic resin layer in contact with the curable resin layer of the substrate layer, such as an acrylic resin layer or a polycarbonate resin layer, is taken as 100 mass %. Also, the content is preferably 50,000 ppm or less, more preferably 20,000 ppm or less, even more preferably 5,000 ppm or less, and even more preferably 1,500 ppm or less. By setting the content at or above the lower limit, the interaction with the hydrogen-bonding functional group contained in the curable resin layer tends to be further improved. Furthermore, by setting the content at or below the upper limit, the transparency and heat resistance of the substrate layer tend to be further improved. The base layer may contain only one type of compound containing one or more -NH2 groups, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0024] <<Acrylic resin layer>> The substrate layer in this embodiment preferably includes an acrylic resin layer. The acrylic resin used in the substrate layer is a thermoplastic resin. The (meth)acrylic equivalent in the acrylic resin layer in this embodiment is preferably less than 200 g / mol, more preferably less than 100 g / mol, even more preferably less than 50 g / mol, and even more preferably less than 10 g / mol, and is 0 g / mol or greater. The acrylic resin layer contains at least an acrylic resin, and the acrylic resin layer preferably contains 90% by mass or more, preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 98% by mass or more of the acrylic resin. The acrylic resin layer may further contain at least one thermoplastic resin selected from styrene resins, fluorine-based resins such as polyvinylidene fluoride, and aromatic polyether resins such as polyphenylene ether.

[0025] The acrylic resin is preferably a polymer of one or more (meth)acrylate monomers and / or a copolymer of one or more (meth)acrylate monomers with other monomers.

[0026] Examples of the (meth)acrylate monomer include compounds represented by formula (a1) described below, as well as aryl (meth)acrylates such as benzyl (meth)acrylate and naphthyl (meth)acrylate.

[0027] The (meth)acrylate monomer is not particularly limited as long as it contains a (meth)acryloyl group, but a compound represented by formula (a1) is preferred. [ka] (In formula (a1), Ra 1 is a hydrogen atom or a methyl group, and Ra 2 is an aliphatic group. In the above formula (a1), Ra 1 is a hydrogen atom or a methyl group, and a methyl group is preferred.2 is an aliphatic group, preferably a linear or branched aliphatic group, more preferably a linear aliphatic group. Examples of the aliphatic group include alkyl groups (including cycloalkyl groups), alkynyl groups (including cycloalkynyl groups), and alkenyl groups (including cycloalkenyl groups). An alkyl group is preferred, a linear or branched alkyl group is more preferred, and a linear alkyl group is even more preferred. Ra 2 The aliphatic group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, still more preferably 1 or 2 carbon atoms, and even more preferably 1 carbon atom. The (meth)acrylate monomer represented by formula (a1) is preferably an alkyl (meth)acrylate (preferably an alkyl methacrylate), and more preferably a methyl (meth)acrylate (preferably a methyl methacrylate). Use of methyl methacrylate tends to improve the impact strength of the resulting acrylic resin layer.

[0028] As mentioned above, the acrylic resin may also contain other monomer units in addition to (meth)acrylate monomer units. Examples of other monomers include vinyl compounds, styrene compounds, maleimide compounds, cyclic acid anhydrides, and lactone ring compounds, with styrene compounds and / or maleimide compounds being preferred. Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide. Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene, with styrene being preferred. Examples of the maleimide compound include maleimide and N-substituted maleimides such as N-cyclohexylmaleimide compounds, N-phenylmaleimide compounds, N-methylmaleimide compounds, N-ethylmaleimide compounds, N-isopropylmaleimide compounds, Nt-butylmaleimide compounds, N-dodecylmaleimide compounds, N-benzylmaleimide compounds, and N-naphthylmaleimide compounds, and N-substituted maleimides are preferred.

[0029] Examples of the cyclic acid anhydride compound include maleic anhydride compounds and glutaric anhydride compounds, with maleic anhydride compounds being preferred. Maleic anhydride constituting the maleic anhydride compound and glutaric acid constituting the glutaric anhydride compound may each have a substituent, but it is preferred that they have no substituent. Examples of the lactone ring compound include those described in JP-A Nos. 2006-171464 and 2004-168882, the contents of which are incorporated herein by reference.

[0030] A first example of the acrylic resin used in the present embodiment is one in which preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more are structural units derived from (meth)acrylate monomers (hereinafter sometimes referred to as "(meth)acrylate monomer units"). The acrylic resin may contain only one type of (meth)acrylic monomer unit, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range. A first example of the acrylic resin used in this embodiment is specifically polymethyl methacrylate (PMMA).

[0031] A second example of the acrylic resin used in this embodiment contains 60 to 96 mass% of (meth)acrylate monomer units and 4 to 40 mass% in total of at least one of vinyl compound units, styrene compound units, maleimide compound units, cyclic acid anhydride units, and lactone ring compound units. The at least one of vinyl compound units, styrene compound units, maleimide compound units, cyclic acid anhydride units, and lactone ring compound units is preferably at least one of styrene compound units, N-substituted maleimide units, and lactone ring units, and more preferably at least one of styrene compound units and N-substituted maleimide units. The second example of the acrylic resin may contain at least one of a (meth)acrylate monomer unit and a vinyl compound unit, a styrene compound unit, a maleimide compound unit, a cyclic acid anhydride unit, and a lactone ring compound unit, either alone or in combination. When two or more units are contained, the total amount is preferably within the above range. In the second example of the acrylic resin, the total of the (meth)acrylate monomer units, vinyl compound units, styrene compound units, maleimide compound units, cyclic acid anhydride units, and lactone ring compound units preferably accounts for 90% by mass or more, more preferably 95% by mass or more, even more preferably 97% by mass or more, and even more preferably 99% by mass or more, when the acrylic resin is taken as 100% by mass.

[0032] In addition to the above, the acrylic resin contained in the acrylic resin layer may be an acrylic resin formed from the resin composition described in WO 2021 / 100661, or an acrylic resin formed from the resin composition described in WO 2022 / 131014, the contents of which are incorporated herein by reference.

[0033] The glass transition temperature (Tg) of the acrylic resin is preferably 100°C or higher, more preferably 105°C or higher, even more preferably 110°C or higher, even more preferably 115°C or higher, and even more preferably 120°C or higher. By setting the Tg at or above the lower limit, the effect of suppressing crack generation during thermoforming tends to be further improved. Furthermore, the glass transition temperature (Tg) of the acrylic resin may be, for example, 130°C or lower, or even 125°C or lower. The glass transition temperature is measured according to the description in paragraph 0056 of JP 2022-080270 A. When the acrylic resin layer contains two or more kinds of acrylic resins, the glass transition temperature (Tg) of the acrylic resins refers to the glass transition temperature of the mixture.

[0034] The weight-average molecular weight of the acrylic resin is preferably 50,000 or more, more preferably 60,000 or more, even more preferably 70,000 or more, even more preferably 80,000 or more, and even more preferably 90,000 or more. By setting the weight-average molecular weight at or above the lower limit, the impact strength of the resulting acrylic resin layer can be further improved. The weight-average molecular weight of the acrylic resin is preferably 300,000 or less, more preferably 250,000 or less, even more preferably 200,000 or less, even more preferably 170,000 or less, and even more preferably 150,000 or less. By setting the weight-average molecular weight at or below the upper limit, the melt viscosity of the resin composition can be effectively reduced, making it easier to mold a multilayer body. The weight average molecular weight is a polystyrene-equivalent value measured by GPC (gel permeation chromatography). When the acrylic resin is a mixture of two or more types, the weight average molecular weight is the sum (weighted average value) of the values ​​obtained by multiplying the weight average molecular weight of each acrylic resin by its mass fraction.

[0035] In addition to the above components, the acrylic resin layer may contain antioxidants, release agents, ultraviolet absorbers, heat stabilizers, flame retardants, flame retardant assistants, colorants, antistatic agents, fluorescent brighteners, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, antiblocking agents, impact improvers, sliding improvers, hue improvers, acid trapping agents, etc. These components may be used alone or in combination of two or more. When contained, the total content of the above components is preferably 0.1 to 5% by mass of the acrylic resin layer. In particular, in this embodiment, the acrylic resin layer may contain an antioxidant and / or a release agent. The details of the antioxidant and / or the release agent are the same as those of the antioxidant and / or the release agent described in the section on the polycarbonate resin layer below, and the preferred ranges are also the same.

[0036] The acrylic resin layer may be a single layer or multiple layers. It is also possible to have two or more acrylic resin layers, and to blend a compound containing one or more -NH2 groups only in the layer closest to the curable resin layer.

[0037] The thickness of the acrylic resin layer is not particularly limited, but the lower limit is, for example, 1 μm or more, preferably 10 μm or more, more preferably 20 μm or more, even more preferably 50 μm or more, more preferably 60 μm or more, even more preferably 80 μm or more, and may be 100 μm or more. By making the thickness equal to or greater than the lower limit, molding becomes easier and hardness tends to be improved. Furthermore, there is no particular upper limit to the thickness of the acrylic resin layer, but it is preferably 5,000 μm or less, more preferably 2,000 μm or less, even more preferably 1,000 μm or less, even more preferably 500 μm or less, even more preferably 300 μm or less, and even more preferably 150 μm or less.

[0038] <<Polycarbonate resin layer>> The substrate layer in this embodiment preferably includes a polycarbonate resin layer. The polycarbonate resin layer is a layer whose main component is polycarbonate resin, and is preferably a layer containing polycarbonate resin in a proportion of 50% by mass or more, more preferably a layer containing polycarbonate resin in a proportion of 70% by mass or more, even more preferably a layer containing polycarbonate resin in a proportion of 90% by mass or more, still more preferably a layer containing polycarbonate resin in a proportion of 95% by mass or more, or a layer containing polycarbonate resin in a proportion of 100% by mass or less.

[0039] The polycarbonate resin contained in the polycarbonate resin layer preferably contains a bisphenol-type polycarbonate resin. A bisphenol-type polycarbonate resin is one in which 80 mol % or more, preferably 90 mol % or more, and more preferably 95 mol % or more of the structural units constituting the polycarbonate resin are carbonate structural units derived from bisphenol and / or its derivatives. The bisphenol preferably contains at least one of bisphenol A, bisphenol AP, and bisphenol P, and more preferably contains bisphenol A. The bisphenol polycarbonate resin is preferably a bisphenol A polycarbonate resin in which 90% by mass or more is derived from bisphenol A.

[0040] The molecular weight of the polycarbonate resin is not particularly limited, but is preferably 20,000 or more, more preferably 30,000 or more, in terms of weight-average molecular weight. The weight-average molecular weight is preferably 100,000 or less, more preferably 70,000 or less. By setting the weight-average molecular weight at or above the lower limit, the strength of the resulting thermally processable multilayer body can be increased. By setting the weight-average molecular weight at or below the upper limit, moldability tends to be improved. In this embodiment, two or more polycarbonate resins having different weight average molecular weights may be mixed and used, and in this case, the viscosity average molecular weight of the mixture is used.

[0041] The glass transition temperature (Tg) of the polycarbonate resin used in this embodiment is preferably 160° C. or lower, more preferably 155° C. or lower, even more preferably 154° C. or lower, even more preferably 153° C. or lower, even more preferably 152° C. or lower, and even more preferably 151° C. or lower. The glass transition temperature (Tg) of the polycarbonate resin used in this embodiment is, for example, 140° C. or higher, and may further be 143° C. or higher, 145° C. or higher, 147° C. or higher, or 148° C. or higher. The glass transition temperature is measured according to the description in paragraph 0056 of JP 2022-080270 A. When the thermoplastic resin layer in this embodiment contains two or more types of polycarbonate resins, the glass transition temperature of the polycarbonate resins is the sum of the values ​​obtained by multiplying the glass transition temperature of each polycarbonate resin by its mass fraction.

[0042] For details of the polycarbonate resin, reference can be made to paragraphs 0011 to 0020 of JP-A-2012-144604 and paragraphs 0014 to 0035 of JP-A-2019-002023, the contents of which are incorporated herein by reference, as long as they do not deviate from the spirit of this embodiment.

[0043] The polycarbonate resin layer may also contain components other than polycarbonate resin. Examples of components other than polycarbonate resin include thermoplastic resins other than polycarbonate resin, thermosetting resins, antioxidants, release agents, UV absorbers, heat stabilizers, flame retardants, flame retardant assistants, colorants, antistatic agents, fluorescent brighteners, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, antiblocking agents, impact improvers, sliding improvers, color improvers, and acid trapping agents. When the polycarbonate resin layer contains components other than polycarbonate resin, the total content of the components other than polycarbonate resin is preferably 0.001 to 3% by mass of the polycarbonate resin layer.

[0044] The polycarbonate resin layer preferably contains an antioxidant and / or a release agent. Examples of antioxidants include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants. Among these, in this embodiment, phosphorus-based antioxidants and phenol-based antioxidants (more preferably hindered phenol-based antioxidants) are preferred. Phosphorus-based antioxidants are particularly preferred because they provide excellent color to the molded product.

[0045] For information on antioxidants, see paragraph 0063 of JP 2018-090677 A, paragraph 0076 of JP 2018-188496 A, and paragraphs 0047 to 0062 of WO 2021 / 241471 A, the contents of which are incorporated herein by reference.

[0046] In addition to the above, the antioxidants can be found in paragraphs 0057 to 0061 of JP 2017-031313 A, the contents of which are incorporated herein by reference.

[0047] The content of the antioxidant is preferably 0.001 parts by mass or more, and more preferably 0.008 parts by mass or more, per 100 parts by mass of the polycarbonate resin layer. The upper limit of the content of the antioxidant is preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, even more preferably 0.2 parts by mass or less, even more preferably 0.15 parts by mass or less, still more preferably 0.10 parts by mass or less, and particularly preferably 0.08 parts by mass or less, per 100 parts by mass of the resin composition.

[0048] By setting the content of the antioxidant to the above lower limit or more, a molded product with better hue and heat discoloration resistance can be obtained. On the other hand, by setting the content of the antioxidant to the above upper limit or less, a molded product with good wet heat stability can be obtained without deteriorating heat discoloration resistance. The antioxidant may be used alone or in combination of two or more. When two or more antioxidants are used, the total amount is preferably within the above range.

[0049] Next, the release agent contained in the polycarbonate resin layer will be described. The type of release agent is not particularly limited, but examples thereof include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polyethers having a number average molecular weight of 100 to 5,000, and polysiloxane-based silicone oils.

[0050] For details about the release agent, please refer to paragraphs 0035 to 0039 of WO 2015 / 190162, the contents of which are incorporated herein by reference.

[0051] The content of the release agent is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, and even more preferably 0.008 part by mass or more, relative to 100 parts by mass of the polycarbonate resin layer, and the upper limit is preferably 0.5 part by mass or less, more preferably 0.3 part by mass or less, and even more preferably 0.2 part by mass or less. The release agent may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0052] The thickness of the polycarbonate resin layer is preferably 100 μm or more, more preferably 150 μm or more. By making the thickness equal to or greater than the lower limit, the rigidity of molded articles such as polarizing sheets tends to be ensured. Furthermore, the thickness of the polycarbonate resin layer is preferably 3000 μm or less, more preferably 2000 μm or less, even more preferably 1000 μm or less, even more preferably 800 μm or less, and even more preferably 600 μm or less. By making the thickness equal to or less than the upper limit, the thermal processability tends to be improved.

[0053] <<Substrate manufacturing method>> The substrate used in this embodiment can be formed into a sheet by, for example, using an extruder that extrudes a resin composition containing an acrylic resin and a compound containing one or more -NH2 groups, melting the thermoplastic resin, introducing it into an extrusion die, and molding it into a sheet. The substrate used in this embodiment can also be formed by, for example, using a main extruder that extrudes a resin composition (which will form a layer in contact with the curable resin layer) containing an acrylic resin and a compound containing one or more -NH2 groups, and a sub-extruder that extrudes a resin composition containing a polycarbonate resin, melting the resin under the conditions of each resin used, introducing it into an extrusion die, laminating it inside the die and forming it into a sheet, or laminating it after forming it into a sheet.

[0054] <Curable resin layer> The multilayer body of this embodiment has a curable resin layer containing a hydrogen-bonding functional group provided on the surface of the base layer. The curable resin layer that may be included in the multilayer body of this embodiment is preferably a layer that has a surface hardness higher than that of the base layer when cured. A multilayer body or molded article with a hard coat layer, which includes a hard coat layer formed by curing such a curable resin layer, has high scratch resistance on its surface.

[0055] The hydrogen-bonding functional group preferably contains at least one structure selected from —OH and —NH, and more preferably contains —OH. The hydrogen-bonding functional group is preferably contained in a thermosetting resin, and is preferably contained in a (meth)acryloyl polymer having a (meth)acrylic equivalent of 200 to 1200 g / mol, which will be described later, and / or a curable resin containing a structural unit represented by formula (Ac), which will be described later (sometimes referred to as "curable resin A" in this specification). Examples of thermosetting resins include at least one resin selected from acrylic resins (e.g., (meth)acryloyl polymers described below), urethane resins, epoxy resins, phenolic resins, unsaturated polyester resins, melamine resins, and vinyl ester resins, which resins contain hydrogen-bonding functional groups.

[0056] The curable resin layer is preferably obtained by applying a hard coat material that can be cured by heat or active energy rays, followed by curing.

[0057] In a first embodiment, the curable resin layer contains a (meth)acryloyl polymer having a (meth)acrylic equivalent of 200 to 1200 g / mol (preferably 200 to 600 g / mol). By setting the (meth)acrylic equivalent to or above the lower limit, the adhesion of the multilayer body with the hard coat layer tends to be further improved. Furthermore, by setting the (meth)acrylic equivalent to or below the upper limit, the hardness and scratch resistance of the cured product tend to be further improved.

[0058] The (meth)acryloyl equivalent of the (meth)acryloyl polymer having a (meth)acrylic equivalent of 200 to 1200 g / mol is preferably 205 g / mol or more, and more preferably 208 g / mol or more. From the viewpoint of further improving the adhesion of the multilayer body with a hard coat layer, it is even more preferably 250 g / mol or more, even more preferably 300 g / mol or more, and even more preferably 330 g / mol or more. From the viewpoint of further improving the scratch resistance, it is preferably 600 g / mol or less, more preferably 500 g / mol or less, and even more preferably 400 g / mol or less. From the viewpoint of further improving the hardness and scratch resistance of the cured product, it is even more preferably 330 g / mol or less, even more preferably 300 g / mol or less, even more preferably 250 g / mol or less, and even more preferably 235 g / mol or less. The curable resin layer of this embodiment may contain only one (meth)acryloyl polymer having a (meth)acrylic equivalent of 200 to 1200 g / mol, or may contain two or more (meth)acryloyl polymers. When two or more (meth)acrylic equivalents are contained, it is preferable that the (meth)acrylic equivalent of the mixture is within the above range.

[0059] The (meth)acryloyl polymer is a polymer obtained by polymerizing one or more (meth)acrylates, and may be a copolymer with a monomer other than (meth)acrylate in a proportion of less than 30% by mass. Alternatively, the polymer may be a polymer obtained by polymerizing one or more (meth)acrylates to which a (meth)acryloyl group has been added. For example, a (meth)acryloyl polymer may be obtained by adding hydroxy(meth)acrylate to a homopolymer of glycidyl (meth)acrylate or a copolymer with other monomers.

[0060] The (meth)acryloyl polymer is preferably an acryloyl polymer.

[0061] The (meth)acrylate constituting the (meth)acryloyl polymer is preferably a (meth)acrylate having two or more (preferably 2 to 5, more preferably 2) (meth)acryloyl groups. The (meth)acrylate constituting the (meth)acryloyl polymer may also include a monofunctional (meth)acrylate. Examples of these (meth)acrylates include the (meth)acrylates described in paragraphs 0051 to 0059 of WO 2018 / 131682 and the (meth)acrylates described in paragraphs 0015 to 0018 of WO 2016 / 047655, the contents of which are incorporated herein by reference.

[0062] Examples of the monomer other than (meth)acrylate constituting the (meth)acryloyl polymer include vinyl compounds, styrene compounds, maleimide compounds, cyclic acid anhydrides, and lactone ring compounds. Examples of the vinyl compounds, styrene compounds, maleimide compounds, cyclic acid anhydrides, and lactone ring compounds are the same as those exemplified as the other monomer other than the (meth)acrylate monomer unit that may be contained in the base layer. The proportion of monomers other than the (meth)acrylate is preferably less than 20% by mass, more preferably less than 10% by mass, even more preferably less than 5% by mass, even more preferably less than 3% by mass, and even more preferably less than 1% by mass.

[0063] A second embodiment of the curable resin layer includes a constitutional unit represented by formula (Ac). Formula (Ac) [ka] (In the above formula (Ac), R m is a single bond or an alkylene group having 1 to 4 carbon atoms, and R n is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R p is a single bond or a divalent linking group, and R q is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. p and R q At least one of the groups contains a hydrogen-bonding group. * indicates a bonding site with another group.)

[0064] In the above formula (Ac), R m represents a single bond or an alkylene group having 1 to 4 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group.

[0065] In the above formula (Ac), R n is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0066] In the above formula (Ac), R p represents a single bond or a divalent linking group, and preferably a single bond.

[0067] In the above formula (Ac), R qis a hydrocarbon group having 1 to 12 carbon atoms and having at least one of a vinyl group and a (meth)acryloyl group, and is preferably a hydrocarbon group having 1 to 12 carbon atoms and having at least one (meth)acryloyl group. The number of carbon atoms in the hydrocarbon group is preferably 2 or more, and is preferably 10 or less, and more preferably 6 or less. The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a straight-chain or branched aliphatic hydrocarbon group, and even more preferably a straight-chain aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and examples of the substituent include the substituents described above, and is preferably a hydroxy group. R q The total number of vinyl groups and (meth)acryloyl groups is at least one, but is preferably one. In the above formula (Ac), R p and R q At least one of R contains a hydrogen-bonding group. q Preferably, R contains a hydrogen-bonding group (preferably a hydroxyl group). q It is preferred that the aryl group is present as a substituent on the hydrocarbon group.

[0068] In the above formula (Ac), R q is preferably a group consisting of a combination of —(CHR)— (wherein R is a hydrogen atom or a hydroxyl group) and a —CH2-(meth)acryloyl group.

[0069] At least one of the constitutional units represented by formula (Ac) is preferably a constitutional unit represented by formula (Ac1). Formula (Ac1) [ka] (In the above formula (Ac1), R m1 is a methylene group, and R n1 is a hydrogen atom or a methyl group, and R q1is a hydrocarbon group having 1 to 12 carbon atoms, containing at least one of a vinyl group and a (meth)acryloyl group, and at least one structure selected from -OH and -NH. * is a bonding site to another site.)

[0070] In the above formula (Ac1), R n1 is a hydrogen atom or a methyl group, and is preferably a hydrogen atom. In the above formula (Ac1), R q1 is a hydrocarbon group having 1 to 12 carbon atoms, containing at least one of a vinyl group and a (meth)acryloyl group, and at least one structure selected from -OH and -NH, and is preferably a hydrocarbon group having 1 to 12 carbon atoms and containing a (meth)acryloyl group and -OH. The number of carbon atoms in the hydrocarbon group is preferably 2 or more, and is preferably 10 or less, and more preferably 6 or less. The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, and even more preferably a linear aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and examples of the substituent include the substituents described above, and is preferably a hydroxy group. R q1 The total number of vinyl groups and (meth)acryloyl groups is at least one, but is preferably one.

[0071] In the above formula (Ac1), R q1 is preferably a group consisting of a combination of —(CHR)— (wherein R is a hydrogen atom or a hydroxyl group) and a —CH2-(meth)acryloyl group.

[0072] In this embodiment, the content of the structural unit represented by formula (Ac1) is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and preferably 85 parts by mass or less, more preferably 80 parts by mass or less, relative to 100 parts by mass of the curable resin A contained in the curable resin layer. By making the content equal to or greater than the lower limit, the hardness and scratch resistance of the cured product tend to be further improved. Meanwhile, by making the content equal to or less than the upper limit, the adhesion of the multilayer body with a hard coat layer tends to be improved. The curable resin A may contain only one type of structural unit represented by formula (Ac), or may contain two or more types. When two or more types are contained, the total amount preferably falls within the above range.

[0073] The third embodiment of the curable resin layer preferably further contains a structural unit represented by formula (Ac2) in addition to the structural unit represented by formula (Ac). Formula (Ac2) [ka] (In the above formula (Ac2), R m is a single bond or an alkylene group having 1 to 4 carbon atoms, and R n is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R p is a single bond or a divalent linking group, and R q2 is a hydrogen atom or a substituent other than a hydrogen-bonding group, a vinyl group, and a (meth)acryloyl group.

[0074] In the above formula (Ac2), R m , R n and R p are each independently R in formula (Ac). m , R n and R p The same applies to the preferred range. In the above formula (Ac2), R q2is a hydrogen atom or a substituent other than a hydrogen-bonding group, a vinyl group, and a (meth)acryloyl group. Examples of the substituent include the above-mentioned substituents, and it is preferably an alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group is also preferably a linear or branched alkyl group, and more preferably a linear alkyl group. Specifically, the alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group. Also, R q2 An example of the substituent of R is an epoxy group. q2 Hydrogen-bonding functional groups are also exemplified as the substituents of the above. The hydrogen-bonding functional groups are groups containing at least one structure selected from -OH and -NH, and examples thereof include a hydroxy group and an amino group.

[0075] In this embodiment, the content of the structural unit represented by formula (Ac2) is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and preferably 70 parts by mass or less, more preferably 60 parts by mass or less, relative to 100 parts by mass of curable resin A contained in the curable resin layer. By setting the content at or above the lower limit, the adhesion of the multilayer body with the hard coat layer tends to be improved. Furthermore, by setting the content at or below the upper limit, the hardness and scratch resistance of the cured product tend to be further improved. The curable resin A may contain only one type of structural unit represented by formula (Ac2), or may contain two or more types. When two or more types are contained, the total amount preferably falls within the above range.

[0076] In this embodiment, the curable resin containing a structural unit represented by formula (Ac) is preferably a curable resin A1 containing a structural unit represented by formula (Ac1-1) and a structural unit represented by formula (Ac2-1). In the curable resin A1, the mass ratio of the structural unit represented by formula (Ac1-1) to the curable resin containing the structural unit represented by formula (Ac2-1) is preferably 100:15 to 70, and more preferably 100:20 to 60. Furthermore, of the curable resin A contained in the curable resin layer, the total amount of the structural unit represented by formula (Ac1-1) and the structural unit represented by formula (Ac2-1) preferably accounts for 90 mass% or more, more preferably 95 mass% or more, even more preferably 97 mass% or more, and even more preferably 99 mass% or more, and is 100 mass% or less. Curing resin A1 [ka]

[0077] In this embodiment, it is preferable that the curable resin layer satisfies both the first embodiment and the second embodiment. That is, the curable resin layer in this embodiment preferably contains a (meth)acryloyl polymer having a (meth)acrylic equivalent of 200 to 1200 g / mol (preferably 200 to 600 g / mol) and contains a structural unit represented by formula (Ac), and more preferably contains a (meth)acryloyl polymer having a (meth)acrylic equivalent of 200 to 1200 g / mol (preferably 200 to 600 g / mol) and containing a structural unit represented by formula (Ac).

[0078] The weight-average molecular weight of the curable resin A is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 15,000 or more, and particularly preferably 25,000 or more, and is preferably 200,000 or less, more preferably 150,000 or less, even more preferably 100,000 or less, and particularly preferably 50,000 or less. When the curable resin layer used in this embodiment contains two or more types of curable resin A, the weight average molecular weight is the sum (weighted average value) of the values ​​obtained by multiplying the weight average molecular weight of each curable resin A by the mass fraction of each component. The weight average molecular weight is a polystyrene-equivalent value measured by GPC (gel permeation chromatography).

[0079] The content of the curable resin A (preferably curable resin A1) in the curable resin layer used in this embodiment is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 75% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the solid content of the curable resin layer (i.e., when the mass of the hard coat layer is 100% by mass), and is preferably 100% by mass or less, and more preferably 99% by mass or less.

[0080] <<Other hard coating agents>> The curable resin layer may contain, in addition to the curable resin A, other hard coating agents. Other hard coating agents include polyorganosiloxane-based hard coating agents, with organosilica being preferred.

[0081] [Multifunctional acrylate compounds] The curable resin layer may further contain a polyfunctional acrylate compound. The polyfunctional acrylate compound can improve the hardness of the cured product by reacting with, for example, a (meth)acryloyl group, an epoxy group, a hydroxyl group, or the like, possessed by the (meth)acryloyl polymer. Here, "polyfunctional" means having two or more functionalities, preferably three or more functionalities, more preferably three to eight functionalities, and even more preferably three to six functionalities.

[0082] The polyfunctional acrylate compound is not particularly limited, but examples thereof include pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.

[0083] The content of the polyfunctional acrylate compound is preferably 70% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less, based on the total content of the (meth)acryloyl polymer and the polyfunctional acrylate compound.

[0084] [Inorganic particles] The curable resin layer may further contain inorganic particles, which can improve the hardness and scratch resistance of the cured product.

[0085] The inorganic particles are not particularly limited, but examples thereof include silica, alumina, titania, zirconia, diamond, and the like.

[0086] The inorganic particles may be surface-treated. By surface-treating the inorganic particles, they can be stably dispersed in the curable resin layer. In this case, the surface treatment agent used is not particularly limited, but a silane compound, an alcohol, an amine, a carboxylic acid, a sulfonic acid, a phosphonic acid, or the like may be used. These surface treatment agents may be used alone or in combination of two or more. By the surface treatment, a polymerizable group (preferably a vinyl group or a (meth)acrylic group) can be introduced onto the surface of the inorganic particles. The inorganic particles described above may be used alone or in combination of two or more kinds. The average particle size of the inorganic particles is preferably 5 nm or more, more preferably 8 nm or more, and from the viewpoint of improving the scratch resistance, etc. of the resulting cured product, it is even more preferably 20 nm or more, particularly preferably 30 nm or more, and is preferably 95 nm or less, more preferably 70 nm or less, and from the viewpoint of improving the scratch resistance, etc. of the resulting cured product, it is even more preferably 60 nm or less. In this specification, "particle diameter" refers to the maximum distance between two points on the outer surface of a particle. Furthermore, "average particle diameter" refers to the average value of the maximum distance between two points on the outer surface of each particle, which is determined by randomly selecting 30 particles observed under a transmission electron microscope (TEM).

[0087] The content of inorganic particles is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to the total mass of the curable resin layer, and is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

[0088] [Leveling agent] The curable resin layer may further contain a leveling agent, which has functions such as leveling properties (making the coating film flat and smooth) and improving the fingerprint wiping properties, stain resistance, and abrasion resistance of the cured product.

[0089] The leveling agent is not particularly limited, but examples thereof include fluorine-based leveling agents and silicone-based leveling agents.

[0090] As the fluorine-based leveling agent, the compound having perfluoropolyether bond can be mentioned.As the fluorine-based leveling agent, commercially available products can be used, for example, Megafac RS-56, RS-75, RS-76-E, RS-76-NS, RS-78, RS-90 (manufactured by DIC Corporation), KY-1203, X-71-1203E, KY-1207, KY-1211 (manufactured by Shin-Etsu Chemical Co., Ltd.), Optool UD120 (manufactured by Daikin Industries, Ltd.), Ftergent 710FL, 220P, 208G, 601AD, 602A, 650A, 228P, 240GFTX-218 (manufactured by Neos Corporation) etc.

[0091] Examples of silicone leveling agents include acrylic group-containing polyether-modified polydimethylsiloxane, etc. Commercially available silicone leveling agents can be used, such as BYK-UV3500 and BYK-UV3505 (manufactured by BYK Japan Co., Ltd.).

[0092] Of these, the leveling agent preferably contains a fluorine-based leveling agent from the viewpoint of improving the ease of wiping off fingerprints from the cured product, etc. The above-mentioned leveling agents may be used alone or in combination of two or more kinds.

[0093] The content of the leveling agent is preferably 0.001 to 10 mass %, more preferably 0.001 to 5 mass %, even more preferably 0.01 to 4 mass %, and particularly preferably 0.1 to 3 mass %, relative to the total mass of the curable resin layer.

[0094] [Photopolymerization initiator] The curable resin layer may further contain a photopolymerization initiator, which has the function of accelerating the curing reaction when curing the curable resin layer.

[0095] The photopolymerization initiator is not particularly limited, but an α-hydroxyalkylphenone-based photoinitiator is preferred. The photopolymerization initiator is not particularly limited, but examples thereof include 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Irgacure 1173), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure TPO), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819), 2,2'-dimethoxy-2-phenylacetophenone (Irgacure 651), oligo(2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone (E Examples of suitable photopolymerization initiators include oligo(2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone (EsacureONE) and 1-hydroxycyclohexyl-phenyl ketone (Omnirad184). Among these, from the viewpoint of increasing heat resistance, the photopolymerization initiator preferably contains at least one of oligo(2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone (EsacureONE) and 1-hydroxycyclohexyl-phenyl ketone (Omnirad184), and more preferably contains 1-hydroxycyclohexyl-phenyl ketone (Omnirad184). The above-mentioned photopolymerization initiators may be used alone or in combination of two or more.

[0096] The content of the photopolymerization initiator is preferably 1% by mass or more, more preferably 2% by mass or more, and is preferably 10% by mass or less, more preferably 6% by mass or less, even more preferably 5% by mass or less, and particularly preferably 4% by mass or less, relative to the total mass of the curable resin layer.

[0097] [Light stabilizer] The curable resin layer may further contain a light stabilizer, which has the function of improving the weather resistance of the cured product.

[0098] The light stabilizer is not particularly limited, but examples thereof include hindered amine light stabilizers.

[0099] Hindered amine light stabilizers include bis(1-undecaneoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate (ADK STAB LA-81), tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate (ADK STAB LA-52), tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate (ADK STAB LA-57), and 1,2,2,6,6-pentamethy-4-piperidylbutane-1,2,3,4-tetracarboxylate (ADK STAB LA-58). methyl-4-piperidyl methacrylate (ADEKASTAB LA-82), bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl) sebacate (Tinuvin 123), bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin 770DF), bis(1,2,2,6,6-pentamethyl-4-piperidyl)-((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl)butyl malonate (Tinuvin 144), and the like.

[0100] Among these, the light stabilizer preferably includes a hindered amine light stabilizer. The above light stabilizers may be used alone or in combination of two or more kinds.

[0101] The content of the light stabilizer is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and is preferably 15% by mass or more, more preferably 7% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, relative to the total mass of the curable resin layer.

[0102] [Polymerization inhibitor] The curable resin layer may further contain a polymerization inhibitor, which has the function of suppressing a polymerization reaction of the curable resin layer due to light, heat, etc., and improving the storage stability of the multilayer body.

[0103] The polymerization inhibitor is not particularly limited, but examples thereof include phenothiazine, mequinol (4-methoxyphenol), hydroquinone, 2-hydroxynaphthoquinone, N-isopropyl-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, and 2-mercaptobenzimidazole.

[0104] Among these, the polymerization inhibitor preferably contains at least one of phenothiazine, mequinol, and hydroquinone, and more preferably contains phenothiazine. The above-mentioned polymerization inhibitors may be used alone or in combination of two or more.

[0105] The content of the polymerization inhibitor is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, relative to the total mass of the curable resin layer.

[0106] [Additives] The curable resin layer may further contain additives other than those mentioned above. The additives are not particularly limited, but examples thereof include heat stabilizers, antioxidants, flame retardants, flame retardant assistants, ultraviolet absorbers, release agents, colorants, antistatic agents, fluorescent brighteners, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, etc. These additives may be used alone or in combination of two or more.

[0107] [Configuration of curable resin layer] The curable resin layer is in an uncured state, and for example, the (meth)acryloyl polymer has a polymerizable functional group (such as a (meth)acryloyl group). The curable resin layer is easy to conform and is less likely to crack after molding, so it has excellent moldability, particularly three-dimensional moldability. However, for example, within the scope that does not impair the effects of the present invention, the (meth)acryloyl polymer in the curable resin layer may have a crosslinked structure due to a curing reaction of some of the (meth)acryloyl groups during the molding process.

[0108] The thickness of the curable resin layer is preferably 1 μm or more, more preferably 3 μm or more, and is preferably 30 μm or less, more preferably 10 μm or less.

[0109] <Multilayer body with hard coat layer> The multilayer body with a hard coat layer of this embodiment is a multilayer body of this embodiment in which the curable resin layer is cured. When the curable resin layer is cured, it functions as a hard coat layer. The curable resin layer is preferably cured by heat or by active energy rays, more preferably by active energy rays, an example of which is ultraviolet rays.

[0110] The thickness of the hard coat layer is preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 2 μm or more, even more preferably 4 μm or more, and even more preferably 5 μm or more. By making the thickness equal to or greater than the lower limit, the pencil hardness of the entire multilayer body due to the hard coat layer tends to be further improved. The upper limit of the thickness of the hard coat layer is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 12 μm or less, even more preferably 10 μm or less, and even more preferably 8 μm or less. By making the thickness equal to or less than the upper limit, the processability during thermoforming tends to be further improved.

[0111] In addition to the above, the hard coat layer may be described in paragraphs 0045 to 0055 of JP 2013-020130 A, paragraphs 0073 to 0076 of JP 2018-103518 A, and paragraphs 0062 to 0082 of JP 2017-213771 A, the contents of which are incorporated herein by reference.

[0112] <Layer structure and properties of multilayer bodies> Next, the layer structure of the multilayer body of this embodiment will be described. FIG. 1 shows an example of the multilayer body of this embodiment, with 1 indicating the multilayer body, 2 indicating a curable resin layer, 3 indicating an acrylic resin layer, 4 indicating a polycarbonate resin layer, and 5 indicating a substrate layer composed of the acrylic resin layer 3 and the polycarbonate resin layer 4. In FIG. 1, the substrate layer 5 is composed of an acrylic resin layer and a polycarbonate resin layer, but the substrate layer 5 may be composed of only one acrylic resin layer or only one polycarbonate resin layer. The substrate layer may also have two or more acrylic resin layers and / or polycarbonate resin layers. Furthermore, other layers such as thermoplastic resin layers and adhesive layers other than the acrylic resin layer and the polycarbonate resin layer may be included. In this embodiment, as shown in FIG. 1, it is preferable that the curable resin layer 2 is located on the surface of the acrylic resin layer 3 opposite to the polycarbonate resin layer 4. Furthermore, the curable resin layer 2 is provided on the surface of the base layer 5. When the base layer 5 is composed of two or more layers, the layer of the base layer 5 that is closest to the curable resin layer 2 (acrylic resin layer 3 in FIG. 1) contains a compound containing one or more -NH2. However, all of the base layers may contain a compound containing one or more -NH2.

[0113] The multilayer body of the present embodiment may have other layers in addition to those described above. Specific examples include an adhesive layer, a pressure-sensitive adhesive layer, an antifouling layer, an antireflection layer, and a polarizing layer. For details of the antireflection layer, please refer to paragraphs 0062 to 0083 of JP 2023-114940 A, paragraphs 0013 to 0041 of JP 2022-174051 A, and paragraphs 0043 to 0046 of JP 2021-081596 A, the contents of which are incorporated herein by reference.

[0114] In the multilayer body of the present embodiment, the multilayer body with a hard coat layer obtained by curing the curable resin layer preferably has an evaluation result of 0 or 1 in the cross-cut test of the hard coat layer in accordance with JIS-K5600-5-6, and more preferably 0. Such excellent evaluation results in the cross-cut test are achieved by the base layer containing a compound having one or more -NH2 groups.

[0115] The total thickness of the multilayer body of this embodiment is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more, even more preferably 100 μm or more, and even more preferably 200 μm or more. A larger total thickness tends to improve the rigidity of the multilayer body. Furthermore, the total thickness of the multilayer body is preferably 10,000 μm or less, more preferably 5,000 μm or less, and may be 3,000 μm or less. By achieving such a total thickness, when the multilayer sheet is pressed between rolls and the resin is cooled during molding of the multilayer body, the resin is cooled all the way to the inside of the multilayer body, thereby improving the moldability of the multilayer body.

[0116] <Thermoformed body and method for manufacturing the thermoformed body> Since the cured product can be used as a thermoforming film (functional film, decorative film), it is preferably formed so as to cover the surface of a molded article. That is, in one embodiment, there is provided a thermoforming film-containing molded article comprising a molded article and the cured product according to the present invention arranged on the surface of the molded article.

[0117] The molded article is not particularly limited, but is preferably a molded article having an uneven surface. Examples of the molded article include goggles, sinks, organs, beds, and vehicle housings.

[0118] In a preferred embodiment, the molded article is a molded article having a textured surface, and the multilayer body is three-dimensionally decorated and molded (TOM molding) onto the molded article, thereby providing a three-dimensionally decorated molded article comprising a molded article having a textured surface and a multilayer body arranged on the textured surface.

[0119] According to one aspect of the present invention, there is provided a method for producing a cured product. The method for producing a cured product includes a curing step of curing the multilayer body described above. The method for producing a cured product includes applying a multilayer body to a surface of a molded article. The method may further include a molding step of molding the above.

[0120] The molding step is a step of molding a multilayer body on the surface of a molded article. The molding is preferably three-dimensional molding. Since the curable resin layer of the multilayer body is in an uncured state, the moldability of the multilayer body, particularly the three-dimensional moldability, is high. As a result, even in the case of three-dimensional molding, the conformability of the multilayer body is high, and even if the multilayer body after molding is wiped and cleaned with a solvent, it remains clean. Lacking is unlikely to occur.

[0121] [Molded products] The molded article is not particularly limited, but for example, the above-mentioned molded articles can be used.

[0122] [Multilayer body] As the multilayer body, the above-mentioned ones are used.

[0123] [Molding] The molding method is not particularly limited, but three-dimensional molding is preferred, and three-dimensional decoration (TOM) molding is more preferred. As described above, the three-dimensional decoration (TOM) molding includes: (1) a vacuum process in which a lower chamber (open at the top) containing a molded article having a textured surface is placed, an upper chamber (open at the bottom) containing a heater, and the multilayer body of the present invention sandwiched between the lower chamber and the upper chamber are airtightly sealed, followed by a vacuum process; (2) a heating process in which the multilayer body is heated using the heater; (3) a contact process in which the molded article having textured surfaces is brought into contact with the heated multilayer body; (4) an upper chamber de-vacuum process in which the upper chamber is placed under atmospheric pressure; and (5) a lower chamber de-vacuum process in which the lower chamber is placed under atmospheric pressure. The upper chamber de-vacuum process may further include an upper chamber pressurization process in which compressed air is introduced into the upper chamber after the upper chamber de-vacuum process. The lower chamber de-vacuum process may further include a trimming process in which a portion of the multilayer body placed on the textured surface is removed after the lower chamber de-vacuum process.

[0124] [Curing process] The curing step is a step of curing the multilayer body. More specifically, it is a step of curing the curable resin layer in the multilayer body by a curing reaction to obtain a cured film of the curable resin layer.

[0125] The curing reaction is not particularly limited, but is preferably carried out by irradiation with active energy rays.

[0126] Examples of the active energy rays include ultraviolet rays, electron beams, and radioactive rays, and ultraviolet rays are preferred.

[0127] The amount of irradiation of active energy rays is not particularly limited, but the cumulative exposure at an ultraviolet wavelength of 365 nm is Light intensity: 100mJ / cm 2 Preferably, it is 300 mJ / cm or more. 2 More preferably, it is 5000 mJ / cm or more. 2 Preferably, it is 3000 mJ / cm or less. 2 More preferably, it is:

[0128] <Application> The multilayer body, the multilayer body with a hard coat layer, and the molded body of this embodiment can be suitably used for optical parts, designed products, anti-reflection molded bodies, etc. An example of the shape of the molded body of this embodiment is a film or a sheet. The multilayer body and molded article of this embodiment are suitable for use in components for display devices, electrical and electronic devices, office automation equipment, portable information terminals, machine parts, home appliances, vehicle parts, various containers, lighting equipment, etc. Among these, they are particularly suitable for use in housings for various displays, electrical and electronic devices, office automation equipment, portable information terminals, and home appliances, lighting equipment, and vehicle parts (particularly vehicle interior parts), surface films for smartphones and touch panels, etc., optical materials, and optical discs. In particular, the molded article of this embodiment is preferably used as a sensor film for touch panels or an anti-reflection molded article for various displays. [Example]

[0129] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or the like, measurements can be made using other instruments with equivalent performance.

[0130] 1.Raw materials <Base material layer> Methacrylic resin: PMMA, Delpowder 80N, manufactured by Asahi Kasei Corporation, polymethyl methacrylate, methyl methacrylate / methyl acrylate = 97.5 / 2.5 weight ratio, weight average molecular weight 100,000, reduced viscosity 0.54 dl / g, glass transition temperature 105°C Polymethacrylate ester: Polyimilex PML203, manufactured by Nippon Shokubai Co., Ltd., N-phenylmaleimide-N-cyclohexylmaleimide-methyl methacrylate-styrene copolymer, weight-average molecular weight 200,000 Stearylamine: Manufacturer: Nissan Amine AB, NOF Corporation, molecular weight 269 Benzoguanamine: Manufacturer: Tokyo Chemical Industry Co., Ltd., molecular weight 187 VD-3: Manufacturer: Shikoku Kasei Kogyo Co., Ltd., molecular weight 245 [ka] Stearyl alcohol: Manufacturer: NOF Corporation NNA-45, molecular weight 270 Glycerin Monostearate: Manufacturer: Riken Vitamin Co., Ltd., molecular weight 358 Polycarbonate resin: Mitsubishi Engineering Plastics Corporation, Iupilon S-2000N

[0131] <Hard coat layer (curable resin layer)> Main component 1: SMP-360A, manufactured by Kyoeisha Chemical Co., Ltd., acrylic polymer (curable resin A1) containing formula (Ac1-1) and formula (Ac2-1), acrylic equivalent: 350 to 370 g / mol, Mw: 20,000 to 30,000, dilution solvent: methyl isobutyl ketone (MIBK), solid content: 50% by mass Main component 2: SMP-220A, manufactured by Kyoeisha Chemical Co., Ltd., acrylic polymer (curable resin A1) containing formula (Ac1-1) and formula (Ac2-1), acrylic equivalent: 210 to 230 g / mol, Mw: 20,000 to 30,000, dilution solvent: propylene glycol monomethyl ether (PGME), solid content: 50% by mass

[0132] Curing resin A1 [ka]

[0133] Subsidiary agent: MEK-AC4130Y, organosilica sol, manufactured by Nissan Chemical Industries, Ltd. Polymerization initiator: Esacure One, manufactured by Lamberti, α-hydroxyalkylphenone photoinitiator Slip agent: BYK-UV3575, BYK, modified polydimethylsiloxane with acrylic groups Solvent: Cyclohexanone

[0134] <Preparation of Hard Coat Layer-Forming Composition 1 (HC1)> 70 parts by mass of main agent 1 (SMP-360A), 30 parts by mass of auxiliary agent (MEK-AC4130Y), 3 parts by mass of polymerization initiator (Esacure One), and 4 parts by mass of slip agent (BYK-UV3575) were dissolved in a solvent (cyclohexanone) to obtain hard coat layer-forming composition 1 (HC1) with a solids concentration of 25% by mass.

[0135] <Preparation of Hard Coat Layer-Forming Composition 2 (HC2)> 70 parts by mass of main agent 2 (SMP-220A), 30 parts by mass of auxiliary agent (MEK-AC4130Y), 3 parts by mass of polymerization initiator (Esacure One), and 4 parts by mass of slip agent (BYK-UV3575) were dissolved in a solvent (cyclohexanone) to obtain hard coat layer forming composition 2 (HC2) with a solids concentration of 25% by mass.

[0136] <Production of base layer 1> A compound having an amino group or a compound having a hydroxy group was blended with the resin for forming the base layer shown in Table 2 or Table 3 in the proportions (units: mass %) shown in Table 2 or Table 3, and the mixture was melt-kneaded at a cylinder temperature of 240°C using a vented twin-screw extruder TEX30α (manufactured by The Japan Steel Works, Ltd.) with a screw diameter of 32 mm and a screw L / D = 31.5, and pellets were obtained by strand cutting.

[0137] The pellets were used to prepare a monolayer film (thickness: 200 μm). Specifically, the pellets were continuously introduced and extruded using a T-die melt extruder consisting of a vented twin-screw extruder TEX30α (manufactured by The Japan Steel Works, Ltd.) with a barrel diameter of 32 mm and a screw L / D of 31.5, at a cylinder temperature of 240°C. The extrusion rate of the acrylic resin was controlled so that the PMMA resin film would be 200 μm thick. The extrusion was performed in the form of a sheet through a T-die connected to the extruder, and then cooled while transferring a mirror surface using three mirror-finishing rolls heated to 90°C, 90°C, and 100°C from the upstream side. This produced a monolayer film consisting of an acrylic resin containing a compound having an amino group or a compound having a hydroxy group.

[0138] <Production of base layer 2> Substrate 2 was molded using a multilayer extrusion device equipped with a single-screw extruder with a 32 mm shaft diameter, a single-screw extruder with a 65 mm shaft diameter, a feed block connected to all extruders, and a 650 mm-wide T-die connected to the feed block. Acrylic resin pellets obtained in the production of substrate 1 were continuously introduced into the single-screw extruder with a 32 mm shaft diameter at a cylinder temperature of 240 °C and extruded. Polycarbonate resin (pellets) were continuously introduced into the single-screw extruder with a 65 mm shaft diameter at a cylinder temperature of 280 °C and extruded. The feed block connected to all extruders was equipped with a two-type, two-layer distribution pin. The laminar flow was laminated and extruded into a sheet through a T-die. The mirror surface was transferred and cooled using three mirror-finished rolls heated to 100 °C, 100 °C, and 125 °C from the upstream side, resulting in substrate layer 2 consisting of a polycarbonate resin layer (200 μm thick) and an acrylic resin layer (55 μm thick).

[0139] 2. Examples 1 to 8 and Comparative Examples 1 to 4 A composition for forming a hard coat layer shown in Table 2 or Table 3 was applied to the surface of the substrate layer obtained above (the acrylic resin layer side in Example 8), and dried at 130°C for 3 minutes to form a curable resin layer with a thickness of 4 μm, thereby obtaining a multilayer body. The curable resin layer of the multilayer body obtained above was irradiated with ultraviolet light to obtain a multilayer body with a hard coat layer having a thickness of 4 μm. The resulting multilayer body with a hard coat layer was evaluated as follows.

[0140] <Cross-cut test> The surface side of the hard coat layer of the obtained multilayer body with a hard coat layer was cut with a cutter at 2 mm intervals, and cross-cut to create a grid of 25 squares (checkerboard pattern). Cellotape (registered trademark) was pressed onto the cut surface of the surface of the hard coat layer, and the tape was then forcefully peeled off. This procedure was repeated four times from all four sides. The surface condition after peeling was visually classified into a grade of 0 to 5. The samples classified into grades 0 to 5 are shown in Table 1 below. Five experts carried out the series of tasks and evaluated them by majority vote.

[0141] [Table 1]

[0142] <Scratch resistance> The surface of the hard coat layer of the obtained multilayer body with a hard coat layer was scratched by moving #0000 steel wool back and forth 15 times under a pressure of 100 gf / cm. The appearance after scratching was evaluated according to the following criteria. A: No scratches are visible B: Very slight scratches C: Some scratches are visible D: Scratches are visible all over the surface

[0143] The results of the cross-cut test and the evaluation of the scratch resistance are shown in Table 2 or Table 3.

[0144] [Table 2]

[0145] [Table 3]

[0146] In Table 2 or Table 3 above, the proportion (ppm by mass) of nitrogen atoms having an unshared electron pair indicates the proportion (ppm by mass) of nitrogen atoms having an unshared electron pair when the thermoplastic resin layer in contact with the curable resin layer in the base layer is taken as 100% by mass. As is clear from the above results, the multilayer bodies of the present invention had excellent adhesion between the substrate layer and the hard coat layer, and also excellent scratch resistance (Examples 1 to 8). In contrast, when the compound containing one or more -NH2 groups was not included (Comparative Examples 1 to 4), the adhesion between the substrate layer and the hard coat layer was poor. [Explanation of symbols]

[0147] 1 Multilayer body 2 Curable resin layer 3 Acrylic resin layer 4 Polycarbonate resin layer 5 Base material layer

Claims

1. a substrate layer containing a thermoplastic resin; and a curable resin layer provided on the surface of the substrate layer and containing a hydrogen-bonding functional group; The base material layer is -NH ２ A multilayer body comprising a base layer containing 0.05 to 10 mass % of a compound containing one or more of the following:

2. 2. The multilayer body according to claim 1, wherein the hydrogen-bonding functional group comprises at least one structure selected from the group consisting of --O--H and --N--H.

3. -NH ２ 3. The multilayer body according to claim 1, wherein the compound containing one or more of the following has a molecular weight of 90 to 500.

4. The multilayer body according to any one of claims 1 to 3, wherein the substrate layer comprises an acrylic resin layer.

5. The multilayer body according to any one of claims 1 to 4, wherein the curable resin layer contains a structural unit represented by formula (Ac): Formula (Ac) 【Chemical 1】 (In the above formula (Ac), R ｍ is a single bond or an alkylene group having 1 to 4 carbon atoms, and R ｎ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ｐ is a single bond or a divalent linking group, and R ｑ is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. ｐ and R ｑ At least one of the groups contains a hydrogen-bonding group. * indicates a bonding site with another group.)

6. 6. The multilayer body according to claim 5, wherein at least one of the structural units represented by formula (Ac) is a structural unit represented by formula (Ac1). Formula (Ac1) 【Chemistry 2】 (In the above formula (Ac1), R ｍ１ is a methylene group, and R ｎ１ is a hydrogen atom or a methyl group, and R ｑ１ is a hydrocarbon group having 1 to 12 carbon atoms, containing at least one of a vinyl group and a (meth)acryloyl group, and at least one structure selected from -O-H and -N-H. * indicates a bonding site to other sites.

7. The multilayer body according to any one of claims 1 to 6, wherein the curable resin layer further comprises a structural unit represented by formula (Ac2): Formula (Ac2) 【Chemistry 3】 (In the above formula (Ac2), R ｍ is a single bond or an alkylene group having 1 to 4 carbon atoms, and R ｎ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ｐ is a single bond or a divalent linking group, and R ｑ２ is a hydrogen atom or a substituent other than a hydrogen-bonding group, a vinyl group, and a (meth)acryloyl group.

8. The multilayer body according to any one of claims 1 to 7, wherein the curable resin layer comprises a structural unit represented by formula (Ac1) and a structural unit represented by formula (Ac2). Formula (Ac1) 【Chemistry 4】 (In the above formula (Ac1), R ｍ１ is a methylene group, and R ｎ１ is a hydrogen atom or a methyl group, and R ｑ１ is a hydrocarbon group having 1 to 12 carbon atoms, containing at least one of a vinyl group and a (meth)acryloyl group, and at least one structure selected from -O-H and -N-H. * indicates a bonding site to other sites.) Formula (Ac2) 【Chemistry 5】 (In the above formula (Ac2), R ｍ is a single bond or an alkylene group having 1 to 4 carbon atoms, and R ｎ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ｐ is a single bond or a divalent linking group, and R ｑ２ is a hydrogen atom or a substituent other than a hydrogen-bonding group, a vinyl group, and a (meth)acryloyl group.

9. The multilayer body according to any one of claims 1 to 8, wherein the curable resin layer comprises a (meth)acryloyl polymer having a (meth)acrylic equivalent of 200 to 600 g / mol.

10. the substrate layer includes an acrylic resin layer and a polycarbonate resin layer; The multilayer body according to any one of claims 1 to 9.

11. The multilayer body according to claim 10, wherein the curable resin layer is located on the surface of the acrylic resin layer opposite to the polycarbonate resin layer.

12. The multilayer body according to any one of claims 1 to 11, which is suitable for thermoforming.

13. A multilayer body with a hard coat layer, wherein the curable resin layer of the multilayer body according to any one of claims 1 to 12 is cured.

14. 14. The multi-layer body with a hard coat layer according to claim 13, wherein the hard coat layer has an evaluation result of 0 or 1 in a cross-cut test in accordance with JIS-K5600-5-6.

15. A method for producing a thermoformed article, comprising thermoforming the multilayer article according to any one of claims 1 to 12, and then curing the curable resin layer.

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