Laminate, method for manufacturing same, and composition

Abstract

Provided are: a laminate having a coating film that is excellent in terms of substrate adhesion, hardness, flexibility, scratch resistance, and long-term stability under low-temperature and high-temperature environments; a method for manufacturing same; and a composition. A laminate according to the present disclosure comprises a first layer and a second layer on a substrate. The first layer is a cured product of a first composition containing a first resin E having an aromatic ring with a specific hydroxyl value and an isocyanate F. The second layer is a cured product of a second composition containing a compound A, which has 6-10 (meth)acryloyl groups, and satisfying at least one of the following conditions: (1) further containing inorganic fine particles B; (2) the compound A having 6-10 (meth)acryloyl groups includes at least a compound A1 having 6-8 (meth)acryloyl groups and a compound A2 having at least 9-10 (meth)acryloyl groups; and (3) further containing at least one of a compound C having 1-5 (meth)acryloyl groups or a compound D having 11 or more (meth)acryloyl groups.

Description

Laminate, method for manufacturing the same, and composition 【0001】 This disclosure relates to laminates, methods for manufacturing the same, and compositions. 【0002】 Various protective films have been developed to protect various substrates such as glass and metal substrates. Patent Document 1 discloses a glass product in which a two-layer coating film is formed on a glass substrate. 【0003】 Japanese Patent Publication No. 2012-229143 【0004】 While the coating film described in Patent Document 1 exhibits good adhesion to glass substrates, it may have inferior hardness, flexibility, and scratch resistance, resulting in insufficient performance depending on the application. Furthermore, glass articles equipped with a protective film are required to have long-term stability, meaning their performance does not deteriorate even when used for extended periods in low and high temperature environments. 【0005】 This disclosure aims to provide a laminate having a coating film that is excellent in adhesion to a substrate, hardness, flexibility, scratch resistance, and long-term stability in low and high temperature environments, as well as a method for manufacturing the same, and a composition that can be used for the coating film. 【0006】The laminate, its manufacturing method, and composition relating to this disclosure are as shown in [1] to

[17] below. [1] A laminate comprising: a first layer which is a cured product of a first composition comprising a first resin (E) having an aromatic ring with a hydroxyl value of 2 to 300 mg KOH / g and an isocyanate (F), on a substrate; and a second layer which is a cured product of a second composition comprising a compound (A) having 6 to 10 (meth)acryloyl groups and satisfying at least one of the following (1) to (3): (1) further comprising inorganic fine particles (B); (2) the compound (A) having 6 to 10 (meth)acryloyl groups comprises a compound (A1) having at least 6 to 8 (meth)acryloyl groups and a compound (A2) having 9 to 10 (meth)acryloyl groups; (3) further comprising at least one of a compound (C) having 1 to 5 (meth)acryloyl groups and a compound (D) having 11 or more (meth)acryloyl groups. [2] The laminate according to [1], wherein the second composition contains two or more compounds (A) having 6 to 10 (meth)acryloyl groups. [3] The laminate according to [1] or [2], wherein the number average molecular weight of the compounds (A) having 6 to 10 (meth)acryloyl groups contained in the second composition is 500 to 5500. [4] The laminate according to any one of [1] to [3], wherein the second composition contains a compound (A) having 6 to 10 (meth)acryloyl groups, at least one of a compound (C) having 1 to 5 (meth)acryloyl groups and a compound (D) having 11 or more (meth)acryloyl groups, and the mass ratio of compound (A), compound (C), and compound (D) is 98:2 to 70:30. [5] The laminate according to any one of [1] to [4], wherein the second composition contains inorganic fine particles (B), and the inorganic fine particles (B) contain silica (B1) or alumina (B2). [6] The laminate according to any one of [1] to [5], wherein the second composition contains inorganic fine particles (B), and the mass ratio of the compound (A) having 6 to 10 (meth)acryloyl groups to the inorganic fine particles (B) in the second composition is 20:1 to 1:3.[7] The laminate according to any one of [1] to [6], wherein the glass transition temperature of the first resin (E) is -30 to 170°C. [8] The laminate according to any one of [1] to [7], wherein the number average molecular weight of the first resin (E) is 1,000 to 30,000. [9] The laminate according to any one of [1] to [8], wherein the isocyanate (F) comprises a blocked isocyanate with a dissociation temperature of 80°C or higher and less than 180°C.

[10] The laminate according to any one of [1] to [9], wherein the mass ratio of the first resin (E) to the isocyanate (F) in the first composition is 100:1 to 100:15.

[11] A method for producing a laminate, comprising forming on a substrate a first layer which is a cured product of a first composition comprising a first resin (E) having an aromatic ring with a hydroxyl value of 2 to 300 mg KOH / g and an isocyanate (F), and a second layer which is a cured product of a second composition comprising a compound (A) having 6 to 10 (meth)acryloyl groups and satisfying at least one of the following (1) to (3): (1) further comprising inorganic fine particles (B), (2) the compound (A) having 6 to 10 (meth)acryloyl groups comprises a compound (A1) having at least 6 to 8 (meth)acryloyl groups and a compound (A2) having 9 to 10 (meth)acryloyl groups, (3) Further comprising at least one of compound (C) having 1 to 5 (meth)acryloyl groups and compound (D) having 11 or more (meth)acryloyl groups.

[12] A composition comprising compound (A) having 6 to 10 (meth)acryloyl groups and satisfying at least one of the following (1) to (3): (1) Further comprising inorganic fine particles (B), (2) Compound (A) having 6 to 10 (meth)acryloyl groups comprises at least compound (A1) having 6 to 8 (meth)acryloyl groups and compound (A2) having 9 to 10 (meth)acryloyl groups, (3) Further comprising at least one of compound (C) having 1 to 5 (meth)acryloyl groups and compound (D) having 11 or more (meth)acryloyl groups.

[13] The composition according to

[12] , comprising two or more compounds (A) having 6 to 10 (meth)acryloyl groups.

[14] The composition according to

[12] or

[13] , wherein the number average molecular weight of compound (A) having 6 to 10 (meth)acryloyl groups contained in the composition is 500 to 5500.

[15] The composition according to any one of

[12] to

[14] , wherein the composition contains compound (A) having 6 to 10 (meth)acryloyl groups, at least one of compound (C) having 1 to 5 (meth)acryloyl groups and compound (D) having 11 or more (meth)acryloyl groups, and the mass ratio of compound (A) to compound (C) and compound (D) is 98:2 to 70:30.

[16] The composition according to any one of

[12] to

[15] , wherein the composition contains inorganic fine particles (B), and the inorganic fine particles (B) contain silica (B1) or alumina (B2).

[17] The composition according to any one of

[12] to

[16] , wherein the composition contains inorganic fine particles (B), and the mass ratio of the compound (A) having 6 to 10 (meth)acryloyl groups to the inorganic fine particles (B) in the composition is 20:1 to 1:3. 【0007】 This disclosure provides a laminate having a coating film that is excellent in adhesion to a substrate, hardness, flexibility, scratch resistance, and long-term stability in low and high temperature environments, as well as a method for manufacturing the same, and a composition that can be used for the coating film. 【0008】 In this specification, numerical ranges indicated using "~" include the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described stepwise in this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another stepwise numerical range. Also, in numerical ranges described in this specification, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. In this specification, (meth)acryloyl group means either or both of an acryloyl group and a methacryloyl group, and may include these groups. 【0009】The following describes in detail embodiments of the laminate, its manufacturing method, and composition relating to this disclosure. However, this disclosure is not limited to these embodiments. Furthermore, it can be modified and implemented at will without departing from the gist of this disclosure. 【0010】 <Laminate> The laminate according to this disclosure (hereinafter also referred to as "this laminate") comprises a specific first layer and a specific second layer on a substrate. The laminate may have other layers on the underside of the substrate (opposite the side on which the first layer is located), or it may have other layers between the substrate and the first layer, or between the first layer and the second layer, or it may have other layers on the second layer. In other words, the laminate may have the first layer and the second layer on the substrate in this order. However, in the laminate, from the viewpoint of hardness and scratch resistance, it is preferable that the second layer is the outermost layer (surface layer). Also, in the laminate, from the viewpoint of substrate adhesion, it is preferable that the first layer is provided on the surface of the substrate. Furthermore, from the viewpoint of hardness, substrate adhesion, flexibility, scratch resistance and long-term stability, it is preferable that the laminate includes a structural portion composed of a substrate, a first layer, and a second layer (outermost layer). 【0011】 This laminate can be used in a variety of applications, including, for example: display panels (e.g., liquid crystal displays), touchscreen panels (e.g., mobile phones, smartphones, tablet devices, notebook PCs), semiconductor elements, printed circuit boards and other electronic devices; laminates used in building applications such as buildings and houses, vehicles such as ships, aircraft, and automobiles, industrial applications, optical applications, solar panels, food packaging, etc. (e.g., glass products, films, and sheets); and glass products used in beakers, flasks, tableware, etc. 【0012】(Substrate) The substrate of this laminate is not particularly limited and can be appropriately selected according to the application to which this laminate is applied. That is, the material, shape, etc. of the substrate can be appropriately selected according to the application and is not particularly limited. Examples of substrate materials include inorganic materials (e.g., glass, quartz, sapphire), metallic materials (e.g., conductive metals such as aluminum, stainless steel, titanium, gold, silver, copper, and their alloys), ITO (tin-doped indium oxide), IZO (indium oxide / zinc oxide), ATO (antimond-doped tin oxide), ZnO (zinc oxide), Ag (silver thin film), silver nanowires, carbon nanotubes (CNTs), fullerenes, graphene, dispersed resin layers containing these, organic materials (e.g., plastic materials), paper, wood, fibrous materials, etc. The shape of the substrate may be any shape, such as plate-like, sheet-like, or curved. 【0013】 The above-mentioned glass is not particularly limited, but examples include silicate glass, soda-lime glass, and potash glass. The glass may also be tempered glass, laminated glass, heat-resistant glass, etc. 【0014】Examples of organic materials include cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, and polybutylene terephthalate; polyethylene (PE), polypropylene (PP), polymethylpentene, polytetrafluoroethylene, cycloolefin polymer (COP), and cycloolefin polymer. Examples include polyolefins such as polypolymers (COC); vinyl compounds such as polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate (PMMA) and polyacrylic acid esters; polystyrene (PS), polycarbonate (PC), polyimide (PI), polyamide (PA), polyurethane, polysulfone, polyethersulfone, polyetherketone, polyetherimide, polyoxyethylene, norbornene resin, AS resin (SAN), vinylidene chloride resin (PVDC), epoxy resin, urea resin, melamine resin, phenolic resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), and aramid. 【0015】 Among these, the substrate is preferably made of conductive metals such as glass, aluminum, stainless steel, titanium, gold, silver, and copper, as well as their alloys, ITO, ZnO, ATO, polyethylene terephthalate (PET), polycarbonate (PC), cycloolefin polymer (COP), or polypropylene (PP), from the viewpoint of substrate adhesion. 【0016】 The thickness of the substrate is not particularly limited, but for example, it is preferably 5 to 10,000 μm, more preferably 10 to 7,000 μm, and even more preferably 50 to 5,000 μm. That is, the preferred lower limit of the substrate thickness is 5 μm, 10 μm, and 50 μm. The preferred upper limit is 10,000 μm, 7,000 μm, and 5,000 μm. 【0017】 The above-mentioned substrate may be a wiring board on which wiring made of conductive metals such as gold, silver, and copper, as well as alloys thereof, and conductive materials such as ITO, ZnO, and CNTs is provided on the substrate. The thickness of the wiring is not particularly limited, but can be, for example, 5 nm to 100 μm. Furthermore, in the case of ITO wiring, the thickness of the wiring can be, for example, 5 to 500 nm. In the case of copper wiring, the thickness of the wiring can be, for example, 5 to 100 μm. In addition, characters, patterns, images, etc. may be printed on the surface of the above-mentioned substrate. 【0018】 (First Layer) The first layer (anchor coat, undercoat layer) is a cured (solidified) product of a first composition containing a first resin (E) having an aromatic ring with a hydroxyl value of 2 to 300 mg KOH / g, and an isocyanate (F). The first layer is preferably a thermosetting resin layer. The thickness of the first layer can be set as appropriate and is not particularly limited, but is preferably 0.5 to 10 μm, and more preferably 1 to 5 μm. Adhesion, hardness, and flexibility are improved when the thickness is 0.5 to 10 μm. That is, the preferred lower limit of the thickness of the first layer is 0.5 μm and 1 μm. The preferred upper limit is 10 μm and 5 μm. 【0019】 [First Composition] The first composition can be used, for example, as a protective film to protect a substrate including wiring as needed. The protective film has good flexibility, transparency, salt water resistance, adhesion to the substrate, and water vapor barrier properties. The first composition comprises a first resin (E), an isocyanate (F), and other components as needed. 【0020】 [First resin (E)] The first resin (E) has a hydroxyl value of 2 to 300 mg KOH / g, preferably 3 to 200 mg KOH / g. If the hydroxyl value is 2 mg KOH / g or higher, adhesion to the substrate is improved. Also, if the hydroxyl value is 300 mg KOH / g or lower, salt water resistance is improved. That is, the preferred lower limit of the hydroxyl value is 3 mg KOH / g, and the preferred upper limit is 200 mg KOH / g. 【0021】The first resin (E) has an aromatic ring. The presence of the aromatic ring improves adhesion to the substrate and improves salt water resistance. The location of the aromatic ring may be in the main chain of the first resin (E), in the side chain of the first resin (E), or in both the main chain and side chain of the first resin (E), but is not particularly limited. The aromatic ring is not particularly limited and examples include a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, and a pyridine ring. 【0022】 The first resin (E) is, for example, epoxy resin, polyurethane, polyurethane urea, phenoxy resin, phenolic resin, polycarbonate, benzoguanamine resin, polyester, aromatic polyether ketone, alkyd resin, silicone resin, styrene resin, styrene-(meth)acrylic resin, styrene-butadiene resin, etc., but is not limited thereto. The first resin (E) may be used alone or in combination of two or more types. 【0023】 Epoxy resins are compounds having epoxy groups, and known compounds can be used. 【0024】Phenoxy resins are polyhydroxy polyethers having a bisphenol skeleton obtained by reacting aromatic diols (such as bisphenol A and bisphenol F) with epichlorohydrin. Examples of commercially available phenoxy resins include JER1256 (number average molecular weight (hereinafter referred to as Mn) 10,000, hydroxyl value 190 mg KOH / g, glass transition temperature (hereinafter referred to as Tg) 95°C, manufactured by Mitsubishi Chemical Corporation), JER4250 (Mn 9,000, hydroxyl value 180 mg KOH / g, Tg 70°C, manufactured by Mitsubishi Chemical Corporation), JER4275 (Mn 8,000, hydroxyl value 170 mg KOH / g, Tg 68°C, manufactured by Mitsubishi Chemical Corporation), and PKHA (Mn 9,000, hydroxyl value 200 mg KOH / g). (g, Tg 81℃, manufactured by Gabriel Phenoxies), PKHB (Mn 9,500, hydroxyl value 203 mg KOH / g, Tg 84℃, manufactured by Gabriel Phenoxies), PKHC (Mn 11,000, hydroxyl value 201 mg KOH / g, Tg 89℃, manufactured by Gabriel Phenoxies), PKHJ (Mn 16,000, hydroxyl value 200 mg KOH / g, Tg 98℃, manufactured by Gabriel Phenoxies), PKHH (Mn 13,000, hydroxyl value 201 mg KOH) (198 mg KOH / g, Tg 98°C, manufactured by Gabriel Phenoxies), PKFE (Mn 16,000, Tg 98°C, manufactured by Gabriel Phenoxies), PKCP-80 (Tg 30°C, manufactured by Gabriel Phenoxies), YP-50 (Mn 14,000, Tg 84°C, manufactured by Nippon Steel Chemical & Material), YP-55U (hydroxyl value 198 mg KOH / g, Tg 83°C, manufactured by Nippon Steel Chemical & Material), YP-50S (hydroxyl value 284 mg KOH / g, Tg 84°C, manufactured by Nippon Steel Chemical) Examples include YP-70 (hydroxyl value 270 mg KOH / g, Tg 72°C, manufactured by Nippon Steel Chemical & Material Co., Ltd.), FX-293 (weight-average molecular weight (hereinafter, Mw) 45,000, hydroxyl value 163 mg KOH / g, Tg 158°C, manufactured by Nippon Steel Chemical & Material Co., Ltd.), FX-280S (Mw 42,000, hydroxyl value 330 mg KOH / g, Tg 158°C, manufactured by Nippon Steel Chemical & Material Co., Ltd.), and FX-310 (Mw 45,000, Tg 110°C, manufactured by Nippon Steel Chemical & Material Co., Ltd.). 【0025】Polyesters can be synthesized by known synthetic methods such as the reaction of polybasic acids with polyols, or the transesterification reaction of polybasic acid esters with polyols. Furthermore, to synthesize polyesters containing aromatic rings, it is preferable to use, for example, aromatic dicarboxylic acids as the polybasic acid. In addition, polybasic acids can be used not alone, but simultaneously, for example, linear aliphatic dicarboxylic acids, cyclic aliphatic carboxylic acids, and trifunctional or higher carboxylic acids. Note that polybasic acids include compounds containing acid anhydride groups. 【0026】 Aromatic dicarboxylic acids include, but are not limited to, terephthalic acid and isophthalic acid. Linear aliphatic dicarboxylic acids include, but are not limited to, adipic acid, sebacic acid, and azelaic acid. Cyclic aliphatic dicarboxylic acids include, but are not limited to, 1,4-cyclohexanedicarboxylic acid, dicarboxyhydrobisphenol A, dimer acid, 4-methylhexahydrophthalic anhydride, and 3-methylhexahydrophthalic anhydride. Carboxylic acids with three or more functions include, but are not limited to, trimellitic anhydride and pyromellitic anhydride. Other carboxylic acids include, but are not limited to, unsaturated dicarboxylic acids such as fumaric acid, and dicarboxylic acids containing sulfonic acid metal salts such as sodium 5-sulfisophthalate. Polybasic acids can be used alone or in combination of two or more types. 【0027】 The polyol is preferably a diol or a compound having three or more hydroxyl groups. Examples of diols include, but are not limited to, ethylene glycol, propylene glycol, 1,4-butanediol, and neopentyl glycol. Examples of compounds having three or more hydroxyl groups include, but are not limited to, tolmethylolpropane, glycerin, and pentaerythritol. The polyol can be used alone or in combination of two or more types. 【0028】Examples of commercially available polyesters include Elitel UE3250 (Mn 18,000, hydroxyl value 5 mg KOH / g, Tg 40°C, manufactured by Unitika), Elitel UE3223G (Mn 20,000, hydroxyl value 5 mg KOH / g, Tg -1°C, manufactured by Unitika), Elitel UE3201 (Mn 20,000, hydroxyl value 3 mg KOH / g, Tg 65°C, manufactured by Unitika), and Elitel UE3600 (Mn 20,000, hydroxyl value 3 mg KOH / g). (Base value 4 mg KOH / g, Tg 7°C, manufactured by Unitika), Elitel XA-0611 (Mn 17,000, hydroxyl value 4 mg KOH / g, Tg 65°C, manufactured by Unitika), Elitel UE3200G (Mn 15,000, hydroxyl value 6 mg KOH / g, Tg 65°C, manufactured by Unitika), Elitel UE3980 (Mn 8,000, hydroxyl value 17 mg KOH / g, Tg 63°C, manufactured by Unitika), Elitel XP-0544 (Mn 3, Byron 500 (Hydroxyl value 32 mg KOH / g, Tg 51°C, manufactured by Unitika), Byron 300 (Mn 23,000, Hydroxyl value 5 mg KOH / g, Tg 7°C, manufactured by Toyobo MC), Byron 630 (Mn 23,000, Hydroxyl value 5 mg KOH / g, Tg 7°C, manufactured by Toyobo MC), Byron 220 (Mn 3,000, Hydroxyl value 50 mg KOH / g, Tg 53°C, manufactured by Toyobo MC), Byron 802 (Mn 3,000, Examples include Byron GK810 (HK 6,000, HK 19 mg / g, Tg 60°C, manufactured by Toyobo MC Co., Ltd.), Byron GK780 (HK 11,000, HK 11 mg / g, Tg 36°C, manufactured by Toyobo MC Co., Ltd.), Byron GK250 (HK 10,000, HK 11 mg / g, Tg 60°C, manufactured by Toyobo MC Co., Ltd.). In addition, polyurethane, polyurethane urea, phenolic resin, polycarbonate, benzoguanamine resin, aromatic polyether ketone, alkyd resin, silicone resin, styrene resin, styrene-(meth)acrylic resin, styrene-butadiene resin, etc., can also be appropriately selected and used from conventionally known materials that have an aromatic ring and a HK 2 to 300 mg / g. 【0029】The first resin (E) is more preferably a polyester or phenoxy resin having the specific hydroxyl value and aromatic ring described above, from the viewpoint of flexibility. 【0030】 The hydroxyl value of the first resin (E) is 2 to 300 mg KOH / g, but when polyester is used, the hydroxyl value is preferably 2 to 200 mg KOH / g, and more preferably 2 to 100 mg KOH / g. That is, when polyester is used, the preferred lower limit is 2 mg KOH / g, the preferred upper limit is 200 mg KOH / g, and the preferred upper limit is 100 mg KOH / g. When polyester is used for the first resin (E), the light transmittance, transparency, flexibility, and bendability of the protective film are further improved, and the adhesion between the protective film and layers such as the substrate is also further improved. 【0031】 Furthermore, the hydroxyl value of the first resin (E) is 2 to 300 mg KOH / g, but when phenoxy resin is used, the hydroxyl value is preferably 50 to 300 mg KOH / g, and more preferably 150 to 250 mg KOH / g. That is, when phenoxy resin is used, the preferred lower limit is 50 mg KOH / g and 150 mg KOH / g. The preferred upper limit is 300 mg KOH / g and 250 mg KOH / g. When phenoxy resin is used for the first resin (E), the light transmittance and transparency of the protective film are further improved, as is the adhesion between the protective film and the substrate layer, etc. In addition, salt water resistance, flexibility, and bendability are particularly improved. Moreover, when phenoxy resin is used, the refractive index is relatively high, so the visibility of the liquid crystal display screen is further improved. 【0032】 The glass transition temperature (Tg) of the first resin (E) is preferably -30 to 170°C, and more preferably 30 to 160°C. That is, the preferred lower limit of Tg for resin (E) is -30°C and 30°C. The preferred upper limit is 170°C and 160°C. If Tg is -30°C or higher, the cohesive force is further improved. Also, if Tg is 170°C or lower, the adhesion and flexibility are further improved. Note that Tg is a value measured using a DSC (Differential Scanning Calorimetry) measuring device "DSC-220C" (product name, manufactured by Seiko Instruments Corporation). 【0033】The number-average molecular weight (Mn) of the first resin (E) is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, and even more preferably 5,000 to 20,000. That is, the preferred lower limit of Mn for resin (E) is 1,000, 2,000, and 5,000. The preferred upper limit is 30,000 and 20,000. If the number-average molecular weight is 1,000 or more, the flexibility of the protective film is increased, resulting in improved flexibility and adhesion to the substrate. If the number-average molecular weight is 30,000 or less, the film strength of the protective film is increased, improving salt water resistance. Note that the number-average molecular weight is a polystyrene equivalent value measured by GPC (gel permeation chromatography). 【0034】 The weight-average molecular weight (Mw) of the first resin (E) is preferably 5,000 to 80,000, and more preferably 10,000 to 70,000. That is, the preferred lower limit of Mw for resin (E) is 5,000 and 10,000. The preferred upper limit is 80,000 and 70,000. The weight-average molecular weight can be measured in the same way as the number-average molecular weight. It is preferable that the first resin (E) satisfies at least one of the above range of number-average molecular weight and the above range of weight-average molecular weight. 【0035】 The total content of the first resin (E) in the first composition (solids) is preferably 80% by mass or more, and more preferably 85% by mass or more, from the viewpoint of adhesion. Furthermore, the total content of the first resin (E) in the first composition (solids) is preferably 99% by mass or less, and more preferably 98% by mass or less, from the viewpoint of hardness and scratch resistance. 【0036】[Isocyanate (F)] Isocyanate (F) can be any isocyanate that has an isocyanate group that can react with the hydroxyl group of the first resin (E), and is not particularly limited. Isocyanate (F) may be, for example, a blocked isocyanate in which the blocking agent dissociates (detaches) upon heating to generate an isocyanate group, or it may contain a blocked isocyanate. That is, isocyanate (F) may consist only of the base isocyanate described later, or it may consist of a blocked isocyanate, or it may consist of a base isocyanate and a blocked isocyanate. The proportion of these isocyanates in isocyanate (F) can be set appropriately within the range in which the effects of this disclosure can be obtained, and is not particularly limited. Isocyanate (F) can function as a curing agent. 【0037】 Examples of isocyanates (F) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates, their derivatives, and blocked isocyanates composed of these (base) isocyanates and blocking agents. 【0038】Aromatic polyisocyanates include, for example, tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), and tetramethylxylylene diisocyanate (1,3- or 1,4- Examples include tranmethylxylylene diisocyanate or a mixture thereof (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4-, or 1,8-naphthalene diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, and the like. 【0039】Aliphatic polyisocyanates include, for example, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, and the like. 【0040】 Alicyclic polyisocyanates include, for example, monocyclic alicyclic diisocyanates and bridged cyclic alicyclic diisocyanates. 【0041】 Monocyclic alicyclic diisocyanates include, for example, 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylene bis(cyclohexyl isocyanate) (4,4'- or 2,4'- or 2,2'-methylene bis(cyclohexyl isocyanate) or a mixture thereof) (hydrogenated MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated toluene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXD), and the like. 【0042】Bridged cyclic alicyclic diisocyanates include, for example, norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, di(isocyanatomethyl) tricyclodecane, and the like. 【0043】 Derivatives of these polyisocyanates include, for example, multimers of the above isocyanate compounds (dimers, trimers, pentamers, heptamers, uretdione, uretonimine, isocyanurate-modified products, polycarbodiimide, etc.), urethane-modified products (e.g., urethane-modified products obtained by modifying or reacting a part of the isocyanate groups in the above isocyanate compounds or multimers with a monoalcohol or polyol), biuret-modified products (e.g., biuret-modified products formed by the reaction of the above isocyanate compounds with water), allophanate-modified products (e.g., allophanate-modified products formed by the reaction of the above isocyanate compounds with a monoalcohol or polyol component), urea-modified products (e.g., urea-modified products formed by the reaction of the above isocyanate compounds with a diamine), oxadiazinetrione (e.g., oxadiazinetrione formed by the reaction of the above isocyanate compounds with carbon dioxide gas, etc.), adducts, and the like. 【0044】 Among these, as isocyanate (F), it is preferable to use a trimethylolpropane adduct of tolylene diisocyanate, an isocyanurate form of tolylene diisocyanate, an oligomer of 4,4'-diphenylmethane diisocyanate, a biuret form of hexamethylene diisocyanate (HDI), an isocyanurate form of hexamethylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, an oligomer of hexamethylene diisocyanate, a uretdione of hexamethylene diisocyanate, an isocyanurate form of a copolymer composed of tolylene diisocyanate and hexamethylene diisocyanate, an isocyanurate form of isophorone diisocyanate, an oligomer of isophorone diisocyanate, and the like. 【0045】Examples of commercially available isocyanates (F) include Coronate L, Coronate HL, Coronate 2030, Coronate 2031, Millionate MR, Millionate MTL (all trade names, manufactured by Nippon Polyurethane Co., Ltd.), Takenate D-102, Takenate D-110N, Takenate D-200, Takenate D-202, Takenate 300S, Takenate 500 (all trade names, manufactured by Takeda Pharmaceutical Company Limited), Sumidur N3300, Sumidur T-80, Sumidur 44S, Sumidur PF, Sumidur L, Sumidur N, Desmodule L, Desmodule IL, Desmodule N, Desmodule HL, Desmodule T65, Desmodule 15, Desmodule R, Desmodule RF, Desmodule SL, Desmodule Z4273 (all trade names, manufactured by Sumika Covestro Urethane Co., Ltd.). 【0046】 Blocked isocyanates include, for example, isocyanates in which compounds such as aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates have been blocked. The dissociation temperature of a blocked isocyanate is the temperature at which the blocking agent is released, preferably 80°C or higher and less than 180°C, and more preferably 90°C or higher and 150°C or lower. If the dissociation temperature is 80°C or higher, the storage stability and adhesion of the resin composition are further improved. If the dissociation temperature is less than 180°C, curing is accelerated and hardness is further improved. 【0047】Preferred blocking agents include, for example, methyl ethyl ketone oxime (MEKO, dissociation temperature 150°C), dimethylpyrazole (DMP, dissociation temperature 110°C), diethyl malonate (DEM, dissociation temperature 110°C), ε-caprolactam (E-CAP, dissociation temperature 170°C), butanone oxime (dissociation temperature 160°C), phenol (dissociation temperature 170°C), and activated methylene compounds (dissociation temperature 90°C). Considering the heat resistance of the substrate, methyl ethyl ketone oxime (MEKO, dissociation temperature 150°C), dimethylpyrazole (DMP, dissociation temperature 110°C), diethyl malonate (DEM, dissociation temperature 110°C), and activated methylene compounds (dissociation temperature 90°C) with dissociation temperatures of 150°C or lower are more preferred. Note that the dissociation temperature may vary slightly depending on the type of isocyanate. 【0048】 Examples of commercially available blocked isocyanates include, for example, Sumijool BL3175, Desmodule BL1100 / 1, Desmodule PL350 (all product names, manufactured by Sumika Covestro Urethane Co., Ltd.), Duranate MF-K60B, SBN-70D, MF-B60B, MF-B90B, 17B-60P, TPA-B80B, TPA-B80E, and E402-B8. Examples include, but are not limited to, 0B (all product names, manufactured by Asahi Kasei Chemicals), BI-7950, BI-7951, BI-7960, BI-7961, BI-7963, BI-7982, BI-7991, BI-7992 (all product names, manufactured by Baxenden), Karens MOI-BM, Karens MOI-BP (all product names, manufactured by Showa Denko), etc. 【0049】 Isocyanate (F) can be used alone or in combination of two or more types. In this laminate, using two or more types of isocyanate (F) in combination further improves adhesion and other properties. 【0050】The isocyanate (F) is preferably used in amounts of 1 to 15 parts by mass, and more preferably 2 to 13 parts by mass, per 100 parts by mass of the first resin (E). That is, the mass ratio of the first resin (E) to the isocyanate (F) in the first composition is preferably 100:1 to 100:15, and more preferably 100:2 to 100:13. Using the isocyanate (F) within this range further improves adhesion to the substrate and hardness. 【0051】 [Other ingredients] The first composition may further contain additives such as an antifoaming agent and a leveling agent. 【0052】 Examples of defoaming agents include, but are not limited to, acrylic resins, vinyl ether resins, olefin resins, butadiene resins, modified siloxane resins, dimethylpolysiloxanes, silicones, modified silicones such as fluorine-modified silicones, and petroleum-based resins. Defoaming agents can be used alone or in combination of two or more types. 【0053】 The defoaming agent is preferably added in an amount of 0.1 to 5 parts by mass, more preferably 0.1 to 1 part by mass, per 100 parts by mass of the first resin (E). If the defoaming agent content is 0.1 parts by mass or more, the first composition will be less likely to foam when mixed, and fewer bubbles will remain on the protective film, thus improving visibility. Furthermore, if the defoaming agent content is 5 parts by mass or less, the transparency of the protective film and its adhesion to the substrate will be further improved. 【0054】 Leveling agents improve the smoothness, transparency, and adhesion of the protective film to the substrate upon addition. Examples of leveling agents include, but are not limited to, acrylic resins, modified silicones, polyether-modified polysiloxane copolymers, dimethylpolysiloxane compounds, silicone-modified copolymers, and organically modified polysiloxanes. Leveling agents can be used alone or in combination of two or more types. 【0055】The first composition may further contain a solvent. Adding a solvent makes it easier to adjust the viscosity to one suitable for printing (coating). The solvent can be appropriately selected depending on the solubility of the first resin (E) used, the printing method, etc. Preferred solvents include ester solvents, ketone solvents, glycol ether solvents, aliphatic solvents, alicyclic solvents, aromatic solvents, alcohol solvents, and water. Examples of ester solvents include, but are not limited to, ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, dimethyl carbonate, ε-caprolactone, and γ-butyrolactone. Examples of ketone solvents include, but are not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diisobutyl ketone, diacetone alcohol, isophorone, and cyclohexanone. Glycol ether solvents include, but are not limited to, monoethers such as ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol monobutyl ether, and their acetate esters; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether, and their acetate esters; and the like. Aliphatic solvents include, but are not limited to, n-hexane, and alicyclic solvents include, but are not limited to, cyclohexane and methylcyclohexane. Aromatic solvents include, but are not limited to, toluene, xylene, and tetralin. Solvents can be used individually or in combination of two or more types. 【0056】 The amount of solvent is, for example, 5 to 75% by mass of the total 100% by mass of the non-volatile content of the first composition and the solvent. 【0057】The first composition may further contain a coloring agent. When the first composition containing a coloring agent is used, for example, as a protective film in a touch panel, the hue can be corrected by incorporating a coloring agent corresponding to the hue of the liquid crystal display. Alternatively, if the protective film becomes discolored, the quality of the protective film can be improved by incorporating a coloring agent that cancels out the discoloration. In particular, the protective film may have a yellow hue, and in this case, incorporating a coloring agent containing at least one selected from the group consisting of red, blue, and purple will make the yellow less noticeable and further improve the quality of the protective film. 【0058】 Pigments and dyes are preferred as colorants. Pigments include inorganic pigments and organic pigments. Dyes include oil-soluble dyes, acid dyes, direct dyes, basic dyes, mordant dyes, and acid mordant dyes. Among these, pigments are preferred in terms of durability, such as heat resistance. 【0059】 (Second layer) The second layer (hard coat, topcoat layer) is a cured (solidified) product of a second composition that includes a compound (A) having 6 to 10 (meth)acryloyl groups and satisfies at least one of the following (1) to (3). Preferably, the second layer is an active energy ray (e.g., UV) curable resin layer. (1) It further includes inorganic fine particles (B), (2) The compound (A) having 6 to 10 (meth)acryloyl groups includes a compound (A1) having at least 6 to 8 (meth)acryloyl groups and a compound (A2) having 9 to 10 (meth)acryloyl groups, (3) It further includes at least one of a compound (C) having 1 to 5 (meth)acryloyl groups and a compound (D) having 11 or more (meth)acryloyl groups. 【0060】[Second Composition] Hereafter, a second composition that satisfies the condition in (1) above will also be referred to as second composition (1), a second composition that satisfies the condition in (2) above will also be referred to as second composition (2), and a second composition that satisfies the condition in (3) above will also be referred to as second composition (3). The second composition may satisfy only one of the conditions in (1) to (3) above, two of them, or all three. In other words, the compositions of second composition (1) to second composition (3) may overlap or be different. Furthermore, the scratch resistance of the laminate produced is further improved when the second composition satisfies the condition in (1) above. Also, the hardness of the laminate produced is further improved when the second composition satisfies the condition in (2) above. Furthermore, the flexibility of the laminate produced is further improved when the third composition satisfies the condition in (3) above. The second composition comprises the above-mentioned compound (A) (for example, compound (A1) and compound (A2)) and may optionally include the inorganic fine particles (B), compound (C), compound (D), and other components described above. Each of these components that the second composition may contain is described in detail below. 【0061】 [Compound (A)] The second composition contains compound (A). By including compound (A), an appropriate hardness can be obtained. Compound (A) is a compound having 6 to 10 (meth)acryloyl groups (a compound with 6 to 10 functionalities). Specifically, compound (A) can be obtained by reacting a polyisocyanate with a mono(meth)acrylate or poly(meth)acrylate having a hydroxyl group, by reacting an isocyanate group-containing urethane prepolymer obtained by reacting a polyol and polyisocyanate under conditions of excess isocyanate groups with a mono(meth)acrylate or poly(meth)acrylate having a hydroxyl group, or by reacting a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and polyisocyanate under conditions of excess hydroxyl groups with a (meth)acrylate having an isocyanate group. 【0062】An example of a method for producing compound (A) is shown below, but the method for producing compound (A) is not limited to this method. For example, urethane (meth)acrylate can be obtained by stirring polyisocyanate and hydroxyl group-containing (meth)acrylate in an oxygen atmosphere at 60 to 100°C for 4 to 8 hours in the presence of a suitable urethane catalyst. 【0063】 Specific examples of the above-mentioned urethane catalysts include copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo[2.2.2]octane, and 2,6,7-trimethyl-1,4-diazabicyclo[2.2.2]octane. Among these, dibutyltin dilaurate is particularly preferred as the urethane catalyst. 【0064】 Examples of polyisocyanates used in the production of urethane (meth)acrylate include aliphatic diisocyanates and aromatic diisocyanates. Examples of aliphatic diisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Examples of aromatic diisocyanates include toluene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate. The bond position of the isocyanate group to the aromatic group may be ortho, meta, or para. Furthermore, the diisocyanate may form an isocyanurate ring as a trimer. Among these, aliphatic diisocyanates are preferred as polyisocyanates from the viewpoint of suppressing yellowing when considering optical applications. 【0065】 When manufacturing urethane (meth)acrylate, the hydroxyl group-containing (meth)acrylate used is preferably a (meth)acrylic acid ester having three or more (meth)acryloryl groups, from the viewpoint of hardness and scratch resistance of the hard coat film surface. Specifically, pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate are preferred as hydroxyl group-containing (meth)acrylates. 【0066】 Compound (A) can be used alone or in combination of two or more types, but from the viewpoint of hardness and adhesion, it is preferable to use two or more types of compound (A) in combination. 【0067】 Compound (A) may, for example, include compound (A1) having at least 6 to 8 (meth)acryloyl groups and compound (A2) having 9 to 10 (meth)acryloyl groups. By using compound (A1) and compound (A2) in combination, an appropriate hardness can be easily obtained. 【0068】 The number-average molecular weight (Mn) of compound (A) is preferably 500 to 5500, and more preferably 600 to 5000. That is, the preferred lower limit for the Mn of compound (A) is 500 and 600. The preferred upper limit is 5,500 and 5,000. If the number-average molecular weight of compound (A) is 500 or more, adhesion and long-term stability (cold-heat cycle) in low-temperature and high-temperature environments are further improved. Also, if the number-average molecular weight of compound (A) is 5500 or less, hardness and scratch resistance are further improved. When two or more compounds (A) are used in combination, it is preferable that the Mn of all compounds (A) are within the above range. 【0069】 The number-average molecular weight of compound (A) can be adjusted by various materials used in the production of compound (A), namely, combinations of polyols, polyisocyanates, and hydroxyl group-containing mono(meth)acrylates or poly(meth)acrylates. 【0070】 The total content of compound (A) in the second composition (solids) is preferably 30% by mass or more, and more preferably 35% by mass or more, from the viewpoint of adhesion and hardness. Furthermore, the total content of compound (A) in the second composition (solids) is preferably 97% by mass or less, and more preferably 95% by mass or less, from the viewpoint of flexibility. 【0071】[Inorganic Fine Particles (B)] The second composition may contain inorganic fine particles (B). Including inorganic fine particles (B) in the second composition further improves scratch resistance. The type of inorganic fine particles (B) is not particularly limited, but examples include metal oxides such as silica, alumina, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide (ATO), cerium oxide, and barium titanate, as well as fine metal powders such as magnesium fluoride, sodium fluoride, gold, silver, nickel, and copper. Among these, from the viewpoint of scratch resistance, it is preferable that the inorganic fine particles (B) contain silica (B1) or alumina (B2). The inorganic fine particles (B) may or may not be surface treated by silane coupling treatment or grafting. 【0072】 The mass ratio of compound (A) to inorganic fine particles (B) in the second composition is preferably 20:1 to 1:3, and more preferably 10:1 to 1:2, from the viewpoint of hardness and scratch resistance. 【0073】 The average particle size of the inorganic fine particles (B) is preferably 1 to 150 nm, and more preferably 2 to 100 nm. That is, the preferred lower limit for the average particle size of the inorganic fine particles (B) is 1 nm and 2 nm. The preferred upper limit is 150 nm and 100 nm. The average particle size of the inorganic fine particles (B) is the cumulative 50% diameter (D50 diameter) of the particle size distribution calculated on a volume basis, and can be measured using a particle size distribution analyzer that uses dynamic light scattering as its measurement principle. 【0074】 [Compound (C)] The second composition may contain compound (C). Compound (C) is a compound having 1 to 5 (meth)acryloyl groups. Including compound (C) in the second composition further improves flexibility. Examples of compound (C) include urethane (meth)acrylate resin, epoxy (meth)acrylate resin, polyester (meth)acrylate resin, acrylic (meth)acrylate resin, etc., which have 1 to 5 (meth)acryloyl groups. Compound (C) can be used alone or in combination of two or more types. 【0075】Examples of the urethane (meth)acrylate resin include a resin having a urethane bond obtained by urethane reaction between an aliphatic polyisocyanate or aromatic polyisocyanate and a (meth)acrylate having a hydroxyl group, and 1 to 5 (meth)acryloyl groups. 【0076】 As the aliphatic polyisocyanate and the aromatic polyisocyanate, those described above can be used in the same manner in compound (A). 【0077】Examples of the hydroxyl group-containing (meth)acrylates include dihydric alcohols such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, and hydroxypivalic acid neopentyl glycol mono(meth)acrylate. Mono(meth)acrylates; mono or di(meth)acrylates of trivalent alcohols such as trimethylolpropanedi(meth)acrylate, ethoxylated trimethylolpropane(meth)acrylate, propoxylated trimethylolpropanedi(meth)acrylate, glycerin di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, or mono and di(meth)acrylates having hydroxyl groups obtained by modifying some of the alcoholic hydroxyl groups with ε-caprolactone. Examples include: compounds having a monofunctional hydroxyl group and three or more functional (meth)acryloyl groups, such as pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate; (meth)acrylate compounds having oxyalkylene chains, such as dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polyethylene glycol mono(meth)acrylate; (meth)acrylate compounds having block-structured oxyalkylene chains, such as polyethylene glycol-polypropylene glycol mono(meth)acrylate and polyoxybutylene-polyoxypropylene mono(meth)acrylate; and (meth)acrylate compounds having random-structured oxyalkylene chains, such as poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate and poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate. 【0078】Examples of the epoxy (meth)acrylate resin include those obtained by reacting (meth)acrylic acid with the epoxy groups of epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. 【0079】 Examples of the polyester (meth)acrylate resin include those obtained by reacting the hydroxyl groups of a polyester polyol with (meth)acrylic acid. 【0080】 Examples of the aforementioned acrylic (meth)acrylate resin include those obtained by polymerizing glycidyl methacrylate and, if necessary, alkyl (meth)acrylate or other (meth)acrylate monomers to obtain an acrylic resin having epoxy groups, and then reacting the epoxy groups with (meth)acrylic acid. 【0081】Furthermore, as the above compound (C), for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate with a number average molecular weight in the range of 150 to 1000, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate with a number average molecular weight in the range of 150 to 1000, neo- Pentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol Aliphatic alkyl (meth)acrylates such as thritol penta(meth)acrylate, dicyclopentenyl (meth)acrylate, methyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, etc., and glycerol (meth)acrylate. , 2-hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, γ-(meth)acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate,Examples include nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydipropylene glycol (meth)acrylate, phenoxypolypropylene glycol (meth)acrylate, polybutadiene (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polyethylene glycol-polybutylene glycol (meth)acrylate, polystyreneethyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, methoxylated cyclodecatriene (meth)acrylate, and phenyl (meth)acrylate. 【0082】 [Compound (D)] The second composition may contain compound (D). Compound (D) is a compound having 11 or more (meth)acryloyl groups. Examples of compound (D) include urethane (meth)acrylate resin, epoxy (meth)acrylate resin, polyester (meth)acrylate resin, acrylic (meth)acrylate resin, etc., which have 11 or more (meth)acryloyl groups. Compound (D) can be used alone or in combination of two or more types. 【0083】In the second composition, the number average molecular weight (Mn) of compound (C) and compound (D) is preferably 250 to 10,000, and more preferably 1,000 to 9,500. That is, the preferred lower limit for the Mn of compound (C) and compound (D) is 250 and 1,000. The preferred upper limit is 10,000 and 9,500. If the number average molecular weight of compound (C) and compound (D) is 250 or higher, adhesion and flexibility are further improved. Also, if the number average molecular weight of compound (C) and compound (D) is 10,000 or lower, hardness and scratch resistance are further improved. Compound (C) and compound (D) can be used individually or in combination of two or more. When two or more are used in combination, it is preferable that the Mn of all compounds (C) and compound (D) used are within the above range. 【0084】 The acryloyl equivalents of compound (C) and compound (D) in the second composition are preferably 50 to 700, and more preferably 300 to 650. That is, the preferred lower limit for the acryloyl equivalents of compound (C) and compound (D) is 50 and 300. The preferred upper limit is 700 and 650. If the acryloyl equivalents of compound (C) and compound (D) are both 50 or higher, adhesion, flexibility, and long-term stability in low and high temperature environments are further improved. Also, if the acryloyl equivalents of compound (C) and compound (D) are both 700 or lower, hardness and scratch resistance are further improved. Compound (C) and compound (D) can be used individually or in combination of two or more. When two or more are used in combination, it is preferable that the acryloyl equivalents of all compounds (C) and (D) used are within the above range. Acryloyl equivalent is an index expressed as (molecular weight / number of acryloyl groups in one molecule). 【0085】 The second composition preferably contains at least one of the compounds (C) and (D) described above, and may contain both. Including these compounds in the second composition further improves flexibility, i.e., bendability. 【0086】In the second composition, the mass ratio of compound (A), compound (C), and compound (D) is preferably 98:2 to 70:30, and more preferably 95:5 to 80:20, from the viewpoint of flexibility and scratch resistance. 【0087】 [Other Components] The second composition may contain a photopolymerization initiator. Adding a photopolymerization initiator can further improve curability. The second composition may also contain a photosensitizer from the viewpoint of curability. Furthermore, the second composition may contain additives such as leveling agents and solvents. The leveling agents and solvents can be used in the first composition in the same way as described above. The amounts of these additives can be set as appropriate and are not particularly limited. 【0088】 Examples of the photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. 【0089】 Examples of the photosensitizers include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, and sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothironium-p-toluenesulfonate. 【0090】 The thickness of the second layer can be set as appropriate and is not particularly limited, but is preferably 3 to 15 μm, and more preferably 5 to 10 μm. If the thickness is 3 μm or more, the hardness and scratch resistance are further improved, and if the thickness is 15 μm or less, the adhesion and long-term stability in low and high temperature environments are further improved. 【0091】[Other Layers] In addition to the substrate, the first layer, and the second layer, the laminate may also have the following other layers. For example, from the viewpoint of heat shielding function, color tone, adhesion, film strength, etc., a heat reflective film made of metal, oxide, nitride, carbide, nitrogen oxide, etc. may be formed between the substrate (e.g., a glass substrate) and the first layer. 【0092】 <Method for Manufacturing a Laminate> In the method for manufacturing a laminate according to this disclosure (hereinafter also referred to as this manufacturing method), a first layer, which is a cured product of the first composition described above, and a second layer, which is a cured product of the second composition described above, are formed on a substrate. More specifically, this manufacturing method can be carried out, for example, by the following procedure (steps). Multiple steps may be carried out in parallel, or each step may be carried out sequentially. 【0093】 First, a first composition is prepared. The first composition can be produced by blending the above-mentioned raw materials (first resin (E), isocyanate (F), and various additives, etc.) and mixing them with a stirrer or the like. For example, known stirring devices such as planetary mixers and despers can be used as the stirrer. 【0094】Next, the first composition can be applied to the substrate and heated as necessary to form a first layer, which is a cured product of the first composition. The first layer can function, for example, as a protective film for a wiring circuit. As for the application (printing) method of the first composition, any known application method can be used. Preferred application methods include gravure coaters, roll coaters, comma coaters, knife coaters, air knife coaters, curtain coaters, kiss coaters, shower coaters, flow coaters, spin coaters, dipping, spraying, applicators, bar coaters, screen printing, flexographic printing, offset printing, gravure printing, and gravure offset printing, with screen printing being more preferred. A drying (curing) process may also be performed after printing. Drying can be performed using known drying equipment such as hot air ovens, infrared ovens, microwave ovens, and combined ovens that combine these. Drying conditions using a hot air oven can be, for example, 80 to 180°C for 10 to 120 minutes, preferably 90 to 150°C for 15 to 60 minutes. 【0095】 Next, a second composition is prepared. The second composition can be produced by blending the above-mentioned raw materials (compound (A), inorganic fine particles (B), compound (C), compound (D), etc.) and mixing them with a stirrer or the like. The stirrer can be the same one used for the first composition as described above. 【0096】 Next, the second composition can be applied to the first layer, and a second layer, which is a cured product of the second composition, can be formed by irradiating it with active energy rays as needed. The method for applying the second composition can be the same as the method used for the first composition. As active energy rays, for example, ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays can be used. These active energy rays can be irradiated using conventionally known equipment, and the irradiation intensity and irradiation time can be set as appropriate and are not particularly limited. For example, a high-pressure mercury lamp can be used as the light source, with an irradiation intensity of 50 to 300 mW / cm². ２ By irradiating with ultraviolet light for 1 to 10 seconds, a second layer can be formed. Thus, a laminate can be obtained in which the first layer and the second layer are formed in this order on the substrate. 【0097】 <Composition> The composition relating to this disclosure is identical to the second composition described above, and its preferred form and other characteristics are also the same, so a description is omitted. This composition can produce a coating film with excellent hardness, flexibility, scratch resistance, and long-term stability in low and high temperature environments. 【0098】 The present disclosure will be described below based on examples, but the present disclosure is not limited to these examples. In the examples, "parts" and "%" refer to "parts by mass" and "mass%", respectively. 【0099】 <Method for Calculating the Number Average Molecular Weight of Polyisocyanates> For polyisocyanates with molecular weight distribution shown in GPC, the number average molecular weight can be determined from the NCO% as follows. Place 1 g of polyisocyanate and 20 mL of 0.5 mol / liter dibutylamine toluene solution in an Erlenmeyer flask, dilute with 100 mL of acetone, and react at 25°C for 30 minutes. Then, titrate with 0.5 mol / liter hydrochloric acid aqueous solution. Perform the titration in the same manner, except that polyisocyanate is not placed in the Erlenmeyer flask, and determine the blank. Then, the NCO% and number average molecular weight can be calculated using the following formula. NCO% = {(Y1 - X1) × 0.5 × 42.02} / (1 × 1000) × 100 X1: Amount of hydrochloric acid solution required for titration of the polyisocyanate-containing solution (mL) Y1: Amount of hydrochloric acid solution required for titration of the blank solution that does not contain polyisocyanate (mL) Number average molecular weight of polyisocyanate = (42.02 × (number of NCOs) / (NCO%) × (non-volatile content) *NCO: isocyanate group *42.02: molecular weight of NCO *Number of NCOs: number of NCOs contained in one molecule of polyisocyanate) *NCO%: mass % of NCOs contained in one molecule of polyisocyanate *Non-volatile content: non-volatile mass % of polyisocyanate However, in this specification, the NCO% of the polyisocyanate in each example is the catalog value (the median value if a range is given). 【0100】 <Method for Calculating the Average Molecular Weight of Polyols> The average molecular weight of polyols was calculated using either the catalog value (the median value if a range is provided) or the molecular weight calculated from the chemical formula. 【0101】 <Content of Polyacrylate Containing Hydroxyl Groups> The content of polyacrylate containing hydroxyl groups was calculated as follows: 100% if the catalog value is 97% or higher; 100% if the catalog value is less than 97% (the median if a range is provided); and 100% if the hydroxyl value is provided. % Content of Polyacrylate Containing Hydroxyl Groups = (Hydroxyl Value) × 1000 / (Molecular Weight of Potassium Hydroxide) × (Molecular Weight of Polyacrylate Containing Hydroxyl Groups) × 100 【0102】 <Average molecular weight of polyacrylates containing hydroxyl groups> The average molecular weight of polyacrylates containing hydroxyl groups was calculated using catalog values ​​(the median value if a range is provided) or molecular weights calculated from the chemical formula. 【0103】 <Number-average molecular weight of urethane acrylate> The number-average molecular weight (Mn) of urethane acrylate was measured using a gel permeation chromatography system "HLC-8220GPC" (product name) manufactured by Tosoh Corporation. The separation columns were four columns of "TSK-GEL SUPER H5000", "TSK-GEL SUPER H4000", "TSK-GEL SUPER H3000", and "TSK-GEL SUPER H2000" (all product names) manufactured by Tosoh Corporation, connected in series. The mobile phase was tetrahydrofuran at 40°C, and the number-average molecular weight in polystyrene equivalent was measured at a flow rate of 0.6 ml / min, rounded to the nearest ten. 【0104】<Synthesis of Compound (A)> [Synthesis Example A1] 596.5 parts by mass of PE-3A (trade name, manufactured by THERMO F.S., pentaerythritol triacrylate, content 100% by mass, average molecular weight 298.3) and 0.1 parts by mass of Neostan U-810 (trade name, manufactured by Nitto Kasei Co., Ltd., tin catalyst) were added to a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel. After raising the liquid temperature to 50°C, 168.2 parts by mass of Duranate 50M-HDI (trade name, manufactured by Asahi Kasei Corporation, content 100% by mass, NCO content 50.0% by mass, average molecular weight 168.2, hexamethylene diisocyanate) were added dropwise from the dropping funnel over 30 minutes. After the temperature rise subsided, the temperature was increased to 80°C and the reaction was allowed to proceed for 3 hours. Fourier transform infrared spectroscopy (FT-IR) showed an absorption peak (2250 cm⁻¹) originating from the isocyanate group. －１ After confirming that the ) had disappeared, the temperature was lowered to room temperature (25°C). Then, a compound having six acryloyl groups, urethane acrylate A1-1 (compound A1-1) (non-volatile content 100% by mass, number average molecular weight 800) was obtained. 【0105】 [Synthesis Example A2] In Synthesis Example A1, 168.2 parts by mass of Duranate 50M-HDI was replaced with 223.2 parts by mass of Vestanat IPDI (trade name, manufactured by Evonik, content 100% by mass, NCO content 37.7% by mass, average molecular weight 223.2, isophorone diisocyanate). Otherwise, the process was the same as in Synthesis Example A1 to obtain urethane acrylate A1-2 (compound A1-2) (non-volatile content 100% by mass, number average molecular weight 900), a compound having six acryloyl groups. 【0106】 [Synthesis Example A3] In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 446.4 parts by mass of Vestanat IPDI, 225.0 parts by mass of PTMG250 (trade name, manufactured by Mitsubishi Chemical Corporation, polytetramethylene glycol, average molecular weight 225.0), and 0.1 parts by mass of Neostan U-810 were added. The mixture was then heated to 80°C and reacted for 3 hours, and an absorption peak (2250 cm) originating from the isocyanate group was observed in FT-IR. －１It was confirmed that the amount had decreased to 50% of the amount before the reaction. Then, 596.5 parts by mass of PE-3A (product name, manufactured by THERMO F.S., pentaerythritol triacrylate, content 100% by mass, average molecular weight 298.3) was added, and the reaction was carried out at 80°C for 3 hours. Subsequently, an absorption peak (2250 cm) originating from the isocyanate group was observed in FT-IR. －１ After confirming that the ) had disappeared, the temperature was lowered to room temperature to obtain urethane acrylate A1-3 (compound A1-3) (non-volatile content 100% by mass, number average molecular weight 1300), which is a compound having six acryloyl groups in the non-volatile content. 【0107】 [Synthesis Examples A4 to A9] Except for changing the amounts (parts by mass) of VESTANAT IPDI and PTMG250 to the formulations shown in Table 1, urethane acrylates A1-4 to A1-9 (compounds A1-4 to A1-9), which are compounds having six acryloyl groups, were obtained in the same manner as in Synthesis Example A3. 【0108】 [Synthesis Example A10] VESTANAT IPDI and PTMG250 used in Synthesis Example A3 were replaced with Tolonate IDT70B (trade name, manufactured by VENECOREX, isophorone diisocyanate trimer (IPDI nurate), content 70% by mass, NCO content 12.3% by mass, average molecular weight 717.4), 1,6-hexanediol (manufactured by UBE), and 4HBA (trade name, manufactured by Mitsubishi Chemical Corporation, 4-hydroxybutyl acrylate, content 100% by mass, average molecular weight 144.2), and the blending amounts (parts by mass) of each material were changed as shown in Table 1. Except for these changes, the process was the same as in Synthesis Example A3 to obtain urethane acrylate A1-10 (compound A1-10) (non-volatile content 79.9% by mass, number average molecular weight 2500), a compound having eight acryloyl groups. 【0109】[Synthesis Example A11] In Synthesis Example A3, PTMG250 was replaced with Tolonate IDT70B and Uniol D-400G (trade name, manufactured by NOF Corporation, polypropylene glycol, content 100% by mass, average molecular weight 400.0), and the blending amounts (parts by mass) of each material were changed as shown in Table 1. Except for these changes, the process was the same as in Synthesis Example A3 to obtain urethane acrylate A2-1 (compound A2-1) (non-volatile content 91.9% by mass, number average molecular weight 3500), a compound having nine acryloyl groups. 【0110】 [Synthesis Example A12] PTMG250 and PE-3A used in Synthesis Example A3 were replaced with 1,6-hexanediol and Purchase DPPA (trade name, manufactured by MOLEKULA, dipentaerythritol pentaacrylate, content 100% by mass, average molecular weight 144.2), respectively, and the blending amounts (parts by mass) of each material were changed as shown in Table 1. Except for these changes, the process was the same as in Synthesis Example A3 to obtain urethane acrylate A2-2 (compound A2-2) (non-volatile content 100.0% by mass, number average molecular weight 2000), a compound having 10 acryloyl groups. 【0111】 [Synthesis Example A13] In Synthesis Example A2, PE-3A was replaced with Purchase DPPA, and the proportions (parts by mass) of each material were changed as shown in Table 1. Except for these changes, the process was the same as in Synthesis Example A2 to obtain urethane acrylate A2-3 (compound A2-3) (non-volatile content 100.0% by mass, number average molecular weight 1300), a compound having 10 acryloyl groups. 【0112】 【0113】<Synthesis of Compound (C)> [Synthesis Example C1] Duranate 50M-HDI and PE-3A used in Synthesis Example A1 were replaced with Duranate TPA100 (trade name, manufactured by Asahi Kasei Corporation, content 100% by mass, NCO content 23.1% by mass, average molecular weight 545.7, hexamethylene diisocyanate trimer (HDI nurate)) and 4HBA (trade name, manufactured by Mitsubishi Chemical Corporation, 4-hydroxybutyl acrylate, content 100% by mass, average molecular weight 144.2), and the blending amounts (parts by mass) of each material were changed as shown in Table 2. Except for these changes, the process was the same as in Synthesis Example A1 to obtain urethane acrylate C-1 (compound C-1) (non-volatile content 100.0% by mass, number average molecular weight 1000), a compound having three acryloyl groups. 【0114】 [Synthesis Example C2] In Synthesis Example A2, PE-3A was replaced with Praxel FA4DT (trade name, manufactured by Daicel Corporation, caprolactone-modified acrylate, content 100% by mass, average molecular weight 572.6), and the blending amounts (parts by mass) of each material were changed as shown in Table 2. Except for these changes, the process was the same as in Synthesis Example A2 to obtain urethane acrylate C-2 (compound C-2) (non-volatile content 100.0% by mass, number average molecular weight 1400), a compound having two acryloyl groups. 【0115】 <Synthesis of Compound (D)> [Synthesis Example D1] Except for adding Purchase DPPA and changing the amount (parts by mass) of each material as shown in Table 2, the same procedure as in Synthesis Example C1 was used to obtain urethane acrylate D-1 (compound D-1) (non-volatile content 100.0% by mass, number average molecular weight 1800), a compound having 11 acryloyl groups. 【0116】[Synthesis Example D2] A four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel contained 3074.6 parts by mass of Tolonate IDT70B (trade name, manufactured by VENECOREX, isophorone diisocyanate trimer, content 70% by mass, NCO content 12.3% by mass), 2642.8 parts by mass of Duranate W (trade name, manufactured by Asahi Kasei Corporation, content 100% by mass, NCO content 31.8% by mass, average molecular weight 264.3, hydrogenated methylenediphenyl diisocyanate), 2700.0 parts by mass of PTMG250 (trade name, manufactured by Mitsubishi Chemical Corporation, polytetramethylene glycol, average molecular weight 225.0), and 0.1 parts by mass of Neostan U-810. Then, the temperature was raised to 80°C and the reaction was carried out for 3 hours, and an absorption peak originating from the isocyanate group (2250 cm⁻¹) was observed in FT-IR. －１ It was confirmed that the amount had decreased to 20% of the amount before the reaction. Then, 1491.4 parts by mass of PE-3A (trade name, manufactured by THERMO F.S., pentaerythritol triacrylate, content 100% by mass, average molecular weight 298.3) was added, and the reaction was continued at 80°C for 3 hours. Subsequently, an absorption peak (2250 cm) originating from the isocyanate group was observed in FT-IR. －１ After confirming that the ) had disappeared, the temperature was lowered to room temperature to obtain urethane acrylate D-2 (compound D-2) (non-volatile content 90.7% by mass, number average molecular weight 9000), which is a compound having 15 acryloyl groups in the non-volatile content. 【0117】[Synthesis Example D3] In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 1573.4 parts by mass of Purchase DPPA (trade name, manufactured by MOLEKULA, dipentaerythritol pentaacrylate, content 100% by mass, average molecular weight 524.5) and 0.1 parts by mass of Neostan U-810 (trade name, manufactured by Nitto Kasei Co., Ltd., tin catalyst) were added, and the liquid temperature was raised to 50°C. Then, 545.7 parts by mass of Duranate TPA100 (trade name, manufactured by Asahi Kasei Corporation, content 100% by mass, NCO content 23.1% by mass, average molecular weight 545.7, hexamethylene diisocyanate trimer (HDI nurate)) were added dropwise from the dropping funnel over 30 minutes. After the temperature rise subsided, the temperature was increased to 80°C and the reaction was allowed to proceed for 3 hours. Fourier transform infrared spectroscopy (FT-IR) showed an absorption peak (2250 cm⁻¹) originating from the isocyanate group. －１ After confirming that the ) had disappeared, the temperature was lowered to room temperature (25°C). Then, urethane acrylate D-3 (compound D-3) (non-volatile content 100% by mass, number average molecular weight 2200), a compound having 15 acryloyl groups, was obtained. 【0118】 【0119】 Furthermore, the materials used in the synthesis of each compound shown in Tables 1 and 2 are those shown in Table 3 below. 【0120】 【0121】[Example 1] A resin varnish with a non-volatile content of 40% was prepared by dissolving 100 parts by mass of Byron 200 (trade name, manufactured by Toyobo MC Co., Ltd., hydroxyl value 6 mg KOH / g, number average molecular weight Mn 17000, Tg 67°C, non-volatile content 100%, aromatic polyester), which corresponds to the first resin (E), in 150 parts by mass of isophorone. Next, 8.3 parts by mass of Duranate MF-B60B (trade name, manufactured by Asahi Kasei Corporation, HDI-based blocked isocyanate, dissociation temperature 120°C, non-volatile content 60%), which corresponds to isocyanate (F), in the resin varnish to prepare an anchor liquid (first composition). Next, the first composition was applied to Eagle XG alkali-free glass (Corning, 0.7 mm) and a 50 μm thick polyethylene terephthalate (PET) film (Toray Industries, Inc., "Lumirror U403") using a bar coater. After that, it was dried in a 130°C oven for 30 minutes to form an anchor layer (first layer) with a film thickness of 2.0 μm. Subsequently, the following materials were mixed and dissolved to prepare a hard coat liquid (second composition, 45% non-volatile content). (Compound (A1) and Compound (C)) ・Miramer M600 (trade name, manufactured by MIWON, a mixture of 95.3% dipentaerythritol hexaacrylate (DPE-6A), a compound having six acryloyl groups, and 4.7% dipentaerythritol pentaerythritol (DPE-5A), a compound having five acryloyl groups) 100 parts by mass, (Inorganic fine particles (B)) ・MEK-AC-2140Z (trade name, manufactured by Nissan Chemical Corporation, silica nanoparticles, MEK (methyl ethyl ketone, non-volatile content 46.0%) dispersion 217.4 parts by mass (non-volatile content 100 parts by mass), (Additives) ・BYK-UV3500 (trade name, manufactured by BYK, leveling agent) 0.05 parts by mass, ・DAIDO UV-CURE 7.0 parts by mass of #174 (product name, manufactured by Daido Chemical Industries, Ltd., photopolymerization initiator), 3.0 parts by mass of Escure One (product name, manufactured by iGM, photopolymerization initiator), and 139.3 parts by mass of methyl ethyl ketone. The above second composition was coated onto the anchor layer (first layer) using a bar coater so that the film thickness after drying was 6.0 μm. Then, it was heated with a high-pressure mercury lamp at 400 mJ / cm². ２Ultraviolet rays were irradiated, and two types of laminates having a first layer and a second layer were prepared (a laminate with a glass substrate and a laminate with a PET film as the substrate), and the evaluations described below were performed. The evaluation results are shown in Table 4. Note that the blending amount (parts by mass) of each component in Table 4 means the blending amount (content) of the non-volatile component. 【0122】 <Evaluation Items> (Adhesion) Using the laminate prepared on glass, a tape adhesion test was carried out. The tape adhesion test was carried out in accordance with JIS K5600. A cutter knife was inserted so as to form a total of 100 grids of 10 grids × 10 grids at intervals of 1 mm in width to a depth such that the laminate reached the substrate but was not cut, and cellophane tape (25 mm width, manufactured by Nichiban Co., Ltd.) was attached to the coating film surface. Then, after rapidly peeling off the cellophane tape by hand, the state of the remaining grids was observed. The results were evaluated based on the following evaluation criteria. - Evaluation Criteria A: No peeling (0 peeled grids) (Very good) B: The edge of the grid is slightly chipped, or peeling of 1 grid or more and 5 grids or less is observed (Good) C: Peeling of 6 grids or more is observed (Not practical) 【0123】 (Pencil Hardness) Using the laminate prepared on glass, in accordance with JIS K5600-5-4, pencils of various hardnesses were applied to the surface of the hard coat layer (second layer) of the laminate at an angle of 45°, and a load was applied to conduct a scratching test. The results were evaluated based on the following evaluation criteria. - Evaluation Criteria AA: 7H or higher (Very good) A: 5 - 6H (Good) B: 3 - 4H (No problem in practical use) C: 2H or lower (Not practical) 【0124】 (Scratch Resistance) Using the laminate prepared on glass, the scratch resistance was evaluated by a "Gakushin-type friction fastness tester" manufactured by Tester Sangyo Co., Ltd. A friction element with a load of 1000 g attached (surface area 4 cm ２Steel wool #0000 was attached to the tool and passed back and forth 10 times over the surface (2 cm x 15 cm) of the hard coat layer (second layer). After that, the number of scratches on the surface of the hard coat layer was counted and evaluated according to the following criteria. Fewer scratches are better, and if there are 9 or fewer scratches, it can be used without any practical problems. Evaluation criteria AA: No scratches (very good) A: 1 to 3 scratches (good) B: 4 to 9 scratches (no practical problems) C: 10 or more scratches (not practical) 【0125】 (Flexibility) Using a laminate fabricated on a PET film, the laminate was set up in a bending resistance tester (Yuasa System Equipment Co., Ltd. unloaded U-shaped stretch tester for planar materials) with the hard coat layer (second layer) facing downwards, and subjected to 10,000 folds at a diameter of 3 mm and a speed of 60 times / minute. The measurement results were then evaluated based on the following evaluation criteria: AAA: No cracks (very good) AA: 1 to 2 cracks (good) A: 3 to 5 cracks (good) B: 6 to 8 cracks (no practical problems) C: 9 or more cracks (not practical) 【0126】 (Long-term stability under low and high temperature environments) Long-term stability (cold and hot cycling) tests were conducted using a laminate fabricated on glass with an ESPEC "Small Thermal Shock Device TSE-11-A (product name)". Specifically, the coating surface was visually observed after 200 cycles at low temperature: -40°C, high temperature: 100°C, and exposure time: 40 minutes each, and evaluated based on the following evaluation criteria: A: No cracks (very good) B: One crack (no practical problem) C: Two or more cracks (not practical) 【0127】 [Examples 2-11] As shown in Table 4, two types of laminates having a first layer and a second layer were prepared and evaluated in the same manner as in Example 1, except that the hard coat liquid (second composition) was changed. Specifically, in Examples 2-11, Miramer M600, which was used in the second composition in Example 1, was replaced with compounds A1-1 to A1-10 synthesized in the above-described synthesis example. In Example 11, the amount of methyl ethyl ketone in Example 1 was changed from 139.3 parts by mass to 114.2 parts by mass. The evaluation results are shown in Table 4. 【0128】 【0129】 [Example 12] Two types of laminates having a first layer and a second layer were prepared in the same manner as in Example 1, except that a hard coat liquid (second composition, 45% non-volatile content) was used, which was prepared by mixing and dissolving the following materials, and were evaluated. The evaluation results are shown in Table 5. Note that the amount (parts by mass) of each component in Table 5 refers to the amount (content) of non-volatile content. (Compound (A2)) 108.8 parts by mass of the above compound A2-1 (non-volatile content 91.9%) (100 parts by mass of non-volatile content), (Inorganic fine particles (B)) 217.4 parts by mass of MEK-AC-2140Z (product name, manufactured by Nissan Chemical Corporation, silica nanoparticles, MEK (methyl ethyl ketone, non-volatile content 46.0%) dispersion (100 parts by mass of non-volatile content), (Additives) 0.05 parts by mass of BYK-UV3500 (product name, manufactured by BYK Corporation, leveling agent), 7.0 parts by mass of DAIDO UV-CURE #174 (product name, manufactured by Daido Chemical Industries, Ltd., photopolymerization initiator), 3.0 parts by mass of Escure One (product name, manufactured by iGM Corporation, photopolymerization initiator), 130.5 parts by mass of methyl ethyl ketone. 【0130】 [Examples 13-14] As shown in Table 5, two types of laminates having a first layer and a second layer were prepared and evaluated in the same manner as in Example 12, except that the hard coat liquid (second composition) was changed. Specifically, in Examples 13-14, compound A2-1 used in the second composition in Example 12 was replaced with compounds A2-2 to A2-3 synthesized in the above-described synthesis example, and the amount of methyl ethyl ketone was changed from 130.5 parts by mass to 139.3 parts by mass. The evaluation results are shown in Table 5. 【0131】[Example 15] As shown in Table 5, in Example 1, the amount of Miramer M600 corresponding to compounds (A1) and (C) used in the second composition was changed to 50 parts by mass, and further, 50 parts by mass of compound A1-4 was used. In addition, inorganic fine particles (B) were not added to the second composition, and the amount of methyl ethyl ketone was changed from 139.3 parts by mass to 134.5 parts by mass. Except for these changes, two types of laminates having a first layer and a second layer were prepared in the same manner as in Example 1 and evaluated. The evaluation results are shown in Table 5. 【0132】 [Example 16] As shown in Table 5, in Example 1, the amount of Miramer M600 used, corresponding to compounds (A1) and (C) used in the second composition, was changed to 47.2 parts by mass. Furthermore, 7.8 parts by mass of Purchase DPPA (trade name, manufactured by MOLEKULA, dipentaerythritol pentaacrylate, content 100% by mass, average molecular weight 524.5) and 45 parts by mass of the above compound A2-2 were used in the second composition. In addition, inorganic fine particles (B) were not added to the second composition, and the amount of methyl ethyl ketone was changed from 139.3 parts by mass to 134.5 parts by mass. Except for these changes, two types of laminates having a first layer and a second layer were prepared in the same manner as in Example 1 and evaluated. The evaluation results are shown in Table 5. 【0133】 [Examples 17-19] In Example 1, 100 parts by mass of Miramer M600 used in the second composition was replaced with 50 parts by mass of compound A1-4 and 50 parts by mass of compound A2-1, A2-2, or A2-3 (amount of non-volatile content), as shown in Table 5. In Examples 17-19, inorganic fine particles (B) were not added to the second composition. In Example 17, 139.3 parts by mass of methyl ethyl ketone was changed to 130.1 parts by mass, and in Examples 18 and 19, 134.5 parts by mass of methyl ethyl ketone was changed. Except for these changes, two types of laminates having the first layer and the second layer were prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5. 【0134】[Example 20] As shown in Table 5, two types of laminates having a first layer and a second layer were prepared and evaluated in the same manner as in Example 12, except that the hard coat liquid (second composition) was changed. Specifically, in Example 12, compound A2-1 used in the second composition was changed to compounds A1-4 and A2-2 synthesized in the above-described synthesis example, and the amount of methyl ethyl ketone was changed from 130.5 parts by mass to 139.3 parts by mass. The evaluation results are shown in Table 5. 【0135】 [Example 21] As shown in Table 5, two types of laminates having a first layer and a second layer were prepared and evaluated in the same manner as in Example 1, except that the hard coat liquid (second composition) was changed. Specifically, in Example 1, 100 parts by mass of Miramer M600 used in the second composition was changed to the following: ・60 parts by mass of compound A2-1 synthesized in the above-described synthesis example, corresponding to compound (A2) ・40 parts by mass of Aronics M450 (trade name, manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol tetraacrylate (PE-4A) with a content of 90% by mass and an average molecular weight of 352.3, and pentaerythritol triacrylate (PE-3A) with a content of 10% by mass and an average molecular weight of 298.3), corresponding to compound (C). In addition, inorganic fine particles (B) were not added to the second composition, and 139.3 parts by mass of methyl ethyl ketone was changed to 129.2 parts by mass. Aside from the above, two types of laminates having a first layer and a second layer were prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5. 【0136】[Example 22] As shown in Table 5, two types of laminates having a first layer and a second layer were prepared and evaluated in the same manner as in Example 1, except that the hard coat liquid (second composition) was changed. Specifically, in Example 1, the 100 parts by mass of Miramer M600 used in the second composition was changed to 30 parts by mass, and the following were added: 50 parts by mass of compound A2-3 synthesized in the above-described synthesis example, which corresponds to compound (A2); 20 parts by mass of Aronics M315 (trade name, manufactured by Toagosei Co., Ltd., a mixture of isocyanurate ethylene oxide modified triacrylate (INE-3A) with a content of 92% by mass and an average molecular weight of 423.4, and isocyanurate ethylene oxide modified diacrylate (INE-2A) with a content of 8% by mass and an average molecular weight of 369.3), which corresponds to compound (C). Furthermore, the second composition did not contain inorganic fine particles (B), and the amount of methyl ethyl ketone was changed from 139.3 parts by mass to 134.5 parts by mass. Except for these changes, two types of laminates having the first and second layers were prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5. 【0137】 [Example 23] As shown in Table 5, two types of laminates having a first layer and a second layer were prepared and evaluated in the same manner as in Example 1, except that the hard coat liquid (second composition) was changed. Specifically, in Example 1, the amount of Miramer M600 used in the second composition was changed from 100 parts by mass to 30 parts by mass, and the following were added: 50 parts by mass of compound A2-3 synthesized in the above-described synthesis example, which corresponds to compound (A2); and 20 parts by mass of Aronics M315, which corresponds to compound (C). Other than these, two types of laminates having a first layer and a second layer were prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5. 【0138】 【0139】[Example 24] Two types of laminates having a first layer and a second layer were prepared in the same manner as in Example 1, except that a hard coat liquid (second composition, 45% non-volatile content) was used, which was prepared by mixing and dissolving the following materials, and were evaluated. The evaluation results are shown in Table 6. Note that the amount (parts by mass) of each component in Table 6 refers to the amount (content) of non-volatile content. (Compound (A1)) 90 parts by mass of the above compound A1-1 (non-volatile content 100.0%), (Compound (C)) 10 parts by mass of the above compound C-1 (non-volatile content 100.0%), (Additives) 0.05 parts by mass of BYK-UV3500 (trade name, manufactured by BYK, leveling agent), 7.0 parts by mass of DAIDO UV-CURE #174 (trade name, manufactured by Daido Chemical Industries, Ltd., photopolymerization initiator), 3.0 parts by mass of Escure One (trade name, manufactured by iGM, photopolymerization initiator), 134.5 parts by mass of methyl ethyl ketone. 【0140】 [Examples 25-33] Except for changing the compounds (A1) and (C) used in Example 24, and their respective amounts (non-volatile content), as shown in Table 6, two types of laminates having a first layer and two layers were prepared in the same manner as in Example 24 and evaluated. The evaluation results are shown in Table 6. 【0141】 【0142】[Example 34] Two types of laminates having a first layer and a second layer were prepared in the same manner as in Example 1, except that a hard coat liquid (second composition, 45% non-volatile content) was used, which was prepared by mixing and dissolving the following materials, and were evaluated. The evaluation results are shown in Table 7. Note that the amount (parts by mass) of each component in Table 7 refers to the amount (content) of non-volatile content. (Compound (A1)) 90 parts by mass of the above compound A1-4 (non-volatile content 100.0%), (Compound (D)) 10 parts by mass of the above compound D-1 (non-volatile content 100.0%), (Additives) 0.005 parts by mass of TEGO Rad 2250 (trade name, manufactured by Evonik, leveling agent), 10 parts by mass of Megafac RS-90 (trade name, manufactured by DIC, additive (reactive surface modifier), non-volatile content 10.0%) (non-volatile content amount 1 part by mass), 5.0 parts by mass of DAIDO UV-CURE #174 (trade name, manufactured by Daido Chemical Industries, Ltd., photopolymerization initiator), 120.6 parts by mass of methyl ethyl ketone. 【0143】 [Examples 35-40] Except for changing the compounds (A1) and (D) used in Example 34, and their respective amounts (non-volatile content), as shown in Table 7, two types of laminates having a first layer and a second layer were prepared in the same manner as in Example 34 and evaluated. The evaluation results are shown in Table 7. Note that the methyl ethyl ketone in Example 34 was changed to 120.4 parts by mass in Example 35, 120.0 parts by mass in Example 36, 119.5 parts by mass in Example 37, 118.5 parts by mass in Example 38, 117.5 parts by mass in Example 39, and 120.6 parts by mass in Example 40. 【0144】 【0145】[Example 41] Two types of laminates having a first layer and a second layer were prepared in the same manner as in Example 1, except that a hard coat liquid (second composition, 45% non-volatile content) was used, which was prepared by mixing and dissolving the following materials, and were evaluated. The evaluation results are shown in Table 8. Note that the amount (parts by mass) of each component in Table 8 refers to the amount (content) of non-volatile content. (Compound (A1)) 100 parts by mass of the above compound A1-4 (non-volatile content 100.0%), (Inorganic fine particles (B)) 10.87 parts by mass of MEK-AC-2140Z (trade name, manufactured by Nissan Chemical Corporation, silica nanoparticles, MEK (methyl ethyl ketone, non-volatile content 46.0%) dispersion (5 parts by mass of non-volatile content), (Additives) 0.05 parts by mass of BYK-UV3500 (trade name, manufactured by BYK Corporation, leveling agent), 7.0 parts by mass of DAIDO UV-CURE #174 (trade name, manufactured by Daido Chemical Industries, Ltd., photopolymerization initiator), 3.0 parts by mass of Escure One (trade name, manufactured by iGM Corporation, photopolymerization initiator), 134.7 parts by mass of methyl ethyl ketone. 【0146】[Examples 42-48] Except for changing the type and amount (non-volatile content) of inorganic fine particles (B) used in Example 41 as shown in Table 8, two types of laminates having a first layer and a second layer were prepared in the same manner as in Example 41 and evaluated. The evaluation results are shown in Table 8. The inorganic fine particles (B) used in Examples 46-48 are as follows. - PGM-AC-2140Y (product name, manufactured by Nissan Chemical Corporation, silica nanoparticles, MEK, PGME (propylene glycol monoethyl ether), non-volatile content 46.8%) dispersion 217.4 parts by mass (non-volatile content 100 parts by mass), - PGM-ST (product name, manufactured by Nissan Chemical Corporation, silica nanoparticles, PGME (propylene glycol 1-monomethyl ether, non-volatile content 30.5%) dispersion 327.87 parts by mass (non-volatile content 100 parts by mass), - KT-110AL (product name, manufactured by Toyo Chem Co., Ltd., alumina particles, MEK (methyl ethyl ketone) / cyclohexanone aliphatic solvent (non-volatile content 35.0%) dispersion 285.71 parts by mass (non-volatile content 100 parts by mass). Furthermore, the amounts of methyl ethyl ketone used in Examples 42 to 48 were 135.0 parts by mass for Example 42, 136.9 parts by mass for Example 43, 144.2 parts by mass for Example 44, 149.0 parts by mass for Example 45, 143.1 parts by mass for Example 46, 28.9 parts by mass for Example 47, and 71.0 parts by mass for Example 48. 【0147】[Example 49] Two types of laminates having a first layer and a second layer were prepared in the same manner as in Example 1, except that a hard coat liquid (second composition, non-volatile content 45%) was used, which was prepared by mixing and dissolving the following materials, and were evaluated. The evaluation results are shown in Table 8. (Compound (A1)) - Compound A1-4 (non-volatile content 100.0%) 90 parts by mass, (Compound (D)) - Compound D-2 (non-volatile content 90.7%) 11 parts by mass (non-volatile content 10 parts by mass), (Inorganic fine particles (B)) - MEK-AC-2140Z (product name, manufactured by Nissan Chemical Corporation, silica nanoparticles, MEK (methyl ethyl ketone, non-volatile content 46.0%) dispersion 217.4 parts by mass (non-volatile content 100 parts by mass), (Additives) - TEGO Rad 2250 (product name, manufactured by Evonik, leveling agent) 0.005 parts by mass, - Megafac RS-90 (product name, manufactured by DIC Corporation, additive (reactive surface modifier), non-volatile content 10.0%) 10 parts by mass (non-volatile content 1 part by mass), - 5.0 parts by mass of DAIDO UV-CURE #174 (product name, manufactured by Daido Chemical Industries, Ltd., photopolymerization initiator), - 124.4 parts by mass of methyl ethyl ketone. 【0148】 【0149】 [Comparative Example 1] Two types of laminates having a first layer and a second layer were prepared in the same manner as in Example 1, except that a hard coat liquid (second composition, 45% non-volatile content) was used, which was prepared by mixing and dissolving the following materials, and were evaluated. The evaluation results are shown in Table 9. Note that the amount (parts by mass) of each component in Table 9 refers to the amount (content) of non-volatile content. (Compound (A1)) 100 parts by mass of the above compound A1-1 (non-volatile content 100.0%), (Additives) 0.05 parts by mass of BYK-UV3500 (trade name, manufactured by BYK, leveling agent), 7.0 parts by mass of DAIDO UV-CURE #174 (trade name, manufactured by Daido Chemical Industries, Ltd., photopolymerization initiator), 3.0 parts by mass of Escure One (trade name, manufactured by iGM, photopolymerization initiator), 134.5 parts by mass of methyl ethyl ketone. 【0150】[Comparative Examples 2-7] Compound (A1) used in Comparative Example 1 was changed to compound (A1) or (A2) shown in Table 9. In Comparative Example 7, the additive was also changed as shown in Table 9. In Comparative Example 5, the amount of methyl ethyl ketone was changed to 124.3 parts by mass, and in Comparative Example 7, the amount of methyl ethyl ketone was changed to 120.6 parts by mass. Except for these changes, two types of laminates having a first layer and two layers were prepared and evaluated in the same manner as in Comparative Example 1. The evaluation results are shown in Table 9. 【0151】 [Comparative Example 8] Two types of laminates having a first layer and a second layer were prepared in the same manner as in Example 1, except that a hard coat liquid (second composition, non-volatile content 45%) was used, which was prepared by mixing and dissolving the following materials, and were evaluated. The evaluation results are shown in Table 9. (Compound (C)) 100 parts by mass of Aronics M450 (trade name, manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol tetraacrylate (PE-4A) with a content of 90% by mass and an average molecular weight of 352.3, and pentaerythritol triacrylate (PE-3A) with a content of 10% by mass and an average molecular weight of 298.3), (additives) 0.05 parts by mass of BYK-UV3500 (trade name, manufactured by BYK, leveling agent), 7.0 parts by mass of DAIDO UV-CURE #174 (trade name, manufactured by Daido Chemical Industries, Ltd., photopolymerization initiator), 3.0 parts by mass of Escure One (trade name, manufactured by iGM, photopolymerization initiator), 134.5 parts by mass of methyl ethyl ketone. 【0152】 [Comparative Example 9] In the second composition of Comparative Example 8, 217.4 parts by mass of MEK-AC-2140Z (trade name, manufactured by Nissan Chemical Corporation), which is an inorganic fine particle (B), and a dispersion of MEK (methyl ethyl ketone, non-volatile content 46.0%) (100 parts by mass of non-volatile content) were added. The amount of methyl ethyl ketone was also changed to 139.3 parts by mass. Except for these changes, two types of laminates having a first layer and a second layer were prepared in the same manner as in Comparative Example 8 and evaluated. The evaluation results are shown in Table 9. 【0153】[Comparative Examples 10-11] Except for changing compound (C) used in Comparative Examples 8 and 9 to compound C-2, two types of laminates having a first layer and a second layer were prepared in the same manner as in Comparative Examples 8 and 9, and evaluated. The evaluation results are shown in Table 9. 【0154】 [Comparative Example 12] Two types of laminates having a first layer and a second layer were prepared in the same manner as in Example 1, except that a hard coat liquid (second composition, non-volatile content 45%) was used, which was prepared by mixing and dissolving the following materials, and were evaluated. The evaluation results are shown in Table 9. (Compound (C)) ・Arronix M450 (trade name, manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol tetraacrylate (PE-4A) with a content of 90% by mass and an average molecular weight of 352.3, and pentaerythritol triacrylate (PE-3A) with a content of 10% by mass and an average molecular weight of 298.3, 20 parts by mass, (Compound (D)) ・The above compound D-2 (non-volatile content 90.7%) 88 parts by mass (non-volatile content 80 parts by mass), (Additives) ・TEGO Rad 2250 (trade name, manufactured by Evonik, leveling agent) 0.005 parts by mass, ・Megafac RS-90 (trade name, manufactured by DIC, additive (reactive surface modifier), non-volatile content 10.0%) 10 parts by mass (non-volatile content amount 1 part by mass), ・DAIDO UV-CURE #174 (product name, manufactured by Daido Chemical Industries, Ltd., photopolymerization initiator) 5.0 parts by mass, Methyl ethyl ketone 112.4 parts by mass. 【0155】 [Comparative Example 13] In the second composition of Comparative Example 12, 217.4 parts by mass of MEK-AC-2140Z (trade name, manufactured by Nissan Chemical Corporation), which is an inorganic fine particle (B), and a dispersion of MEK (methyl ethyl ketone, non-volatile content 46.0%) (100 parts by mass of non-volatile content) were added. The amount of methyl ethyl ketone was also changed to 117.2 parts by mass. Except for these changes, two types of laminates having a first layer and a second layer were prepared in the same manner as in Comparative Example 12 and evaluated. The evaluation results are shown in Table 9. 【0156】 【0157】[Example 50] A resin varnish with a non-volatile content of 40% was prepared by dissolving 100 parts by mass of Elitel UE3410 (trade name, manufactured by Unitika Corporation), which corresponds to the first resin (E), in 150 parts by mass of isophoron. Next, 8.3 parts by mass (5 parts by mass of non-volatile content) of Duranate MF-B60B (trade name, manufactured by Asahi Kasei Corporation, HDI-based blocked isocyanate, dissociation temperature 120°C, non-volatile content 60%), which corresponds to isocyanate (F), was dissolved in the resin varnish to prepare an anchor liquid (first composition). Then, the first composition was coated onto Eagle XG alkali-free glass (manufactured by Corning, 0.7 mm) and a 50 μm thick polyethylene terephthalate (PET) film (Toray Industries, Inc., "Lumirror U403") using a bar coater. Subsequently, the material was dried in a 130°C oven for 30 minutes to form an anchor layer (first layer) with a film thickness of 2.0 μm. Next, the following materials were mixed and dissolved to prepare a hard coat solution (second composition, 45% non-volatile content). (Compound (A1) and Compound (C)) ・Miramer M600 (trade name, manufactured by MIWON, a mixture of 95.3% dipentaerythritol hexaacrylate (DPE-6A), a compound having six acryloyl groups, and 4.7% dipentaerythritol pentaerythritol (DPE-5A), a compound having five acryloyl groups) 47.2 parts by mass, (Compound (A2)) ・The above compound A2-2 (non-volatile content 100.0%) 45 parts by mass, (Compound (C)) ・Purchase DPPA (trade name, manufactured by MOLEKULA, dipentaerythritol pentaacrylate, content 100% by mass, average molecular weight 524.5) 7.8 parts by mass, (additives) - BYK-UV3500 (product name, manufactured by BYK, leveling agent) 0.05 parts by mass, - DAIDO UV-CURE #174 (product name, manufactured by Daido Chemical Industries, Ltd., photopolymerization initiator) 7.0 parts by mass, - Escure One (product name, manufactured by iGM, photopolymerization initiator) 3.0 parts by mass, - methyl ethyl ketone 134.5 parts by mass. The above second composition was coated onto the anchor layer (first layer) using a bar coater to a film thickness of 6.0 μm after drying. Then, it was heated with a high-pressure mercury lamp at 400 mJ / cm². ２Two types of laminates having a first layer and a second layer were fabricated by irradiating them with ultraviolet light (a laminate with a glass substrate and a laminate with a PET film substrate), and the evaluations described below were performed. The evaluation results are shown in Table 10. Note that the amount (parts by mass) of each component in Table 10 refers to the amount (content) of non-volatile components. 【0158】 [Examples 51-58] As shown in Table 10, two types of laminates having a first layer and a second layer were prepared and evaluated in the same manner as in Example 50, except that the type of first resin (E) used in the anchor liquid (first composition) was changed. Specifically, in Examples 51-58, the first resin (E) was changed to the following. The evaluation results are shown in Table 10.・Eritel UE3510 (product name, manufactured by Unitika Corporation, hydroxyl value 4 mg KOH / g, number average molecular weight Mn 34000, non-volatile content 100%, aromatic polyester) ・Eritel UE3400 (product name, manufactured by Unitika Corporation, hydroxyl value 4 mg KOH / g, number average molecular weight Mn 25000, non-volatile content 100%, aromatic polyester) ・Eritel UE3200G (product name, manufactured by Unitika Corporation, hydroxyl value 6 mg KOH / g, number average molecular weight Mn 15000, non-volatile content 100%, aromatic polyester) ・Eritel UE9900 (product name, manufactured by Unitika Corporation, hydroxyl value 8 mg KOH / g, number average molecular weight Mn 15000, non-volatile content 100%, aromatic polyester) ・Eritel UE3320 (product name, manufactured by Unitika Corporation, hydroxyl value 60 mg KOH / g, number average molecular weight Mn 1800, non-volatile content 100%, aromatic polyester) FX-393 (product name, manufactured by Nippon Steel Chemical & Material Co., Ltd., hydroxyl value 164 mg KOH / g, number average molecular weight Mn 10500, non-volatile content 100%, phenoxy resin) FX-293 (product name, manufactured by Nippon Steel Chemical & Material Co., Ltd., hydroxyl value 160 mg KOH / g, number average molecular weight Mn 10500, non-volatile content 100%, phenoxy resin) YP-55U (product name, manufactured by Nippon Steel Chemical & Material Co., Ltd., hydroxyl value 198 mg KOH / g, number average molecular weight Mn 10000, non-volatile content 100%, phenoxy resin) 【0159】 【0160】[Examples 59-68] As shown in Table 11, two types of laminates having a first layer and a second layer were prepared and evaluated in the same manner as in Example 1, except that the type of isocyanate (F) used in the anchor liquid (first composition) and its amount (non-volatile content) were changed. In Examples 64-68, the isocyanate (F) was changed to the following. The evaluation results are shown in Table 11. Note that the amount (parts by mass) for each component in Table 11 refers to the amount (content) of non-volatile content. (Blocked Isocyanates) ・Duranate MF-K60B (Product name, manufactured by Asahi Kasei Corporation, HDI-based blocked isocyanate, dissociation temperature 90°C, non-volatile content 60%) ・Desmodure PL350 (Product name, manufactured by Sumitomo Covestro Urethane Co., Ltd., HDI-based blocked isocyanate, dissociation temperature 120°C, non-volatile content 75%) ・Desmodure BL1100 / 1 (Product name, manufactured by Sumitomo Covestro Urethane Co., Ltd., TDI-based blocked isocyanate, dissociation temperature 170°C, non-volatile content 100%) (Isocyanates) ・Sumidure N3300 (Trade name, manufactured by Sumitomo Covestro Urethane Co., Ltd., HDI, non-volatile content 100%) ・Desmodure IL 1351 BA (product name, manufactured by Sumitomo Covestro Urethane Co., Ltd., TDI, non-volatile content 51%) 【0161】 【0162】[Comparative Examples 14-16] As shown in Table 12, two types of laminates having a first layer and a second layer were prepared and evaluated in the same manner as in Example 50, except that the type of first resin (E) used in the anchor liquid (first composition) was changed. In Comparative Examples 14-16, the first resin (E) was changed to the following. The evaluation results are shown in Table 12. Note that the blending amount (parts by mass) for each component in Table 12 refers to the blending amount (content) of non-volatile components. - BX-5 (Trade name, manufactured by Sekisui Chemical Co., Ltd., hydroxyl value 321 mg KOH / g, number average molecular weight Mn 130,000, non-volatile content 100%, acetal resin) - CAB-551-0.2 (Trade name, manufactured by Eastman Chemical Company, hydroxyl value 53 mg KOH / g, number average molecular weight Mn 30,000, non-volatile content 100%, cellulose acetate butyrate resin) - CA-398-3 (Trade name, manufactured by Eastman Chemical Company, hydroxyl value 116 mg KOH / g, number average molecular weight Mn 50,000, non-volatile content 100%, cellulose acetate resin) 【0163】 [Comparative Example 17] As shown in Table 12, two types of laminates having a first layer and a second layer were prepared in the same manner as in Example 50, except that isocyanate (F) was not added to the anchor liquid (first composition), and were evaluated. The evaluation results are shown in Table 12. 【0164】 [Comparative Example 18] As shown in Table 12, two types of laminates were prepared in the same manner as in Example 50, except that the anchor liquid (first composition) was not used and the first layer was not prepared, and only the second layer was prepared on the substrate, and the results were evaluated. The evaluation results are shown in Table 12. 【0165】 【0166】 [Examples 69-76] As shown in Table 13, two types of laminates were prepared in the same manner as in Example 16, except that the thickness of the first layer and the second layer (film thickness after curing) was changed, and the results were evaluated. The evaluation results are shown in Table 13. 【0167】 【0168】From the above, it can be seen that this laminate, comprising a specific first layer and a specific second layer on a substrate, exhibits excellent adhesion to the substrate, hardness and flexibility, scratch resistance, and long-term stability in low and high temperature environments. 【0169】 This disclosure is not limited to the embodiments described above, and may be modified as appropriate without departing from its spirit. Furthermore, this disclosure may be implemented by combining the embodiments described above or examples thereof as appropriate. 【0170】 The laminates, their manufacturing methods, and compositions relating to this disclosure can be used in a variety of applications, including electronic devices such as display panels, touchscreen panels, semiconductor elements, and printed circuit boards; laminates used in building applications such as buildings and houses, vehicles such as ships, aircraft, and automobiles, industrial applications, optical applications, solar panels, and food packaging; and glass products used in beakers, flasks, tableware, etc. 【0171】 This application claims priority based on Japanese Patent Application No. 2024-217320, filed on 12 December 2024, and incorporates all of its disclosures herein.

Claims

1. A laminate comprising: a first layer on a substrate which is a cured product of a first composition comprising a first resin (E) having an aromatic ring with a hydroxyl value of 2 to 300 mg KOH / g and an isocyanate (F); and a second layer which is a cured product of a second composition comprising a compound (A) having 6 to 10 (meth)acryloyl groups and satisfying at least one of the following (1) to (3): (1) further comprising inorganic fine particles (B); (2) the compound (A) having 6 to 10 (meth)acryloyl groups comprises a compound (A1) having at least 6 to 8 (meth)acryloyl groups and a compound (A2) having 9 to 10 (meth)acryloyl groups. (3) Furthermore, the compound comprises at least one of the following: compound (C) having 1 to 5 (meth)acryloyl groups and compound (D) having 11 or more (meth)acryloyl groups.

2. The laminate according to claim 1, wherein the second composition contains two or more compounds (A) having 6 to 10 (meth)acryloyl groups.

3. The laminate according to claim 1 or 2, wherein the number average molecular weight of compound (A) having 6 to 10 (meth)acryloyl groups contained in the second composition is 500 to 5500.

4. The laminate according to any one of claims 1 to 3, wherein the second composition comprises a compound (A) having 6 to 10 (meth)acryloyl groups, at least one of a compound (C) having 1 to 5 (meth)acryloyl groups and a compound (D) having 11 or more (meth)acryloyl groups, and the mass ratio of compound (A), compound (C), and compound (D) is 98:2 to 70:

30.

5. The laminate according to any one of claims 1 to 4, wherein the second composition contains inorganic fine particles (B), and the inorganic fine particles (B) contain silica (B1) or alumina (B2).

6. The laminate according to any one of claims 1 to 5, wherein the second composition contains inorganic fine particles (B), and the mass ratio of the compound (A) having 6 to 10 (meth)acryloyl groups to the inorganic fine particles (B) in the second composition is 20:1 to 1:

3.

7. The laminate according to any one of claims 1 to 6, wherein the glass transition temperature of the first resin (E) is -30 to 170°C.

8. The laminate according to any one of claims 1 to 7, wherein the number average molecular weight of the first resin (E) is 1,000 to 30,000.

9. The laminate according to any one of claims 1 to 8, wherein the isocyanate (F) comprises a blocked isocyanate having a dissociation temperature of 80°C or higher and less than 180°C.

10. The laminate according to any one of claims 1 to 9, wherein the mass ratio of the first resin (E) to the isocyanate (F) in the first composition is 100:1 to 100:

15.

11. A method for producing a laminate, comprising forming a first layer on a substrate which is a cured product of a first composition comprising a first resin (E) having an aromatic ring with a hydroxyl value of 2 to 300 mg KOH / g and an isocyanate (F), and a second layer which is a cured product of a second composition comprising a compound (A) having 6 to 10 (meth)acryloyl groups and satisfying at least one of the following (1) to (3): (1) further comprising inorganic fine particles (B), (2) the compound (A) having 6 to 10 (meth)acryloyl groups comprises a compound (A1) having at least 6 to 8 (meth)acryloyl groups and a compound (A2) having 9 to 10 (meth)acryloyl groups, (3) Furthermore, the compound comprises at least one of the following: compound (C) having 1 to 5 (meth)acryloyl groups and compound (D) having 11 or more (meth)acryloyl groups.

12. A composition comprising a compound (A) having 6 to 10 (meth)acryloyl groups, and satisfying at least one of the following (1) to (3): (1) further comprising inorganic fine particles (B); (2) the compound (A) having 6 to 10 (meth)acryloyl groups comprises a compound (A1) having at least 6 to 8 (meth)acryloyl groups and a compound (A2) having 9 to 10 (meth)acryloyl groups; (3) further comprising at least one of a compound (C) having 1 to 5 (meth)acryloyl groups and a compound (D) having 11 or more (meth)acryloyl groups.

13. The composition according to claim 12, comprising two or more compounds (A) having 6 to 10 (meth)acryloyl groups.

14. The composition according to claim 12 or 13, wherein the number average molecular weight of compound (A) having 6 to 10 (meth)acryloyl groups contained in the composition is 500 to 5500.

15. The composition according to any one of claims 12 to 14, wherein the composition comprises a compound (A) having 6 to 10 (meth)acryloyl groups, at least one of a compound (C) having 1 to 5 (meth)acryloyl groups and a compound (D) having 11 or more (meth)acryloyl groups, and the mass ratio of compound (A), compound (C), and compound (D) is 98:2 to 70:

30.

16. The composition according to any one of claims 12 to 15, wherein the composition contains inorganic fine particles (B), and the inorganic fine particles (B) contain silica (B1) or alumina (B2).

17. The composition according to any one of claims 12 to 16, wherein the composition contains inorganic fine particles (B), and the mass ratio of the compound (A) having 6 to 10 (meth)acryloyl groups to the inorganic fine particles (B) in the composition is 20:1 to 1:3.

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